TRANSACTIONS

OF THE

WISCONSIN ACADEMY

■ ' ' ' ’ . ■ ' i ■ . ;

SCIENCES, ARTS AND LETTERS

VOL. XIX, PART II

V i '■ ■■ - ' . : . ■ : \

MADISON, WISCONSIN

The annual half -volume of the Transactions is issued by the

Wisconsin Academy of Sciences, Arts, and Letters, under the

editorial supervision of the Secretary.

Arthur Beatty,

Secretary.

TRANSACTIONS

OF THE

WISCONSIN ACADEMY

OF

SCIENCES, ARTS AND LETTERS

VOL. XIX, PART II

1919

CONTENTS

Page

North American Ascochytae. J. J. Davis — - 653

Notes on Parasitic Fungi in Wisconsin, IV. (With two

Figures). J. J. Davis - - - - - — 671

Notes on Parasitic Fungi, V. J. J. Davis - 690

Notes on Parasitic Fungi, VI. J. J. Davis _ 705

Contribution to the Chemistry of American Conifers. (With

one Table). A. W. Schorger _ _ _ _ 728

Pigments of Flowering Plants. Nellie A. Wakeman _ 767

History of the United States Pharmacopoeia, I. The Galen¬

ical Oleoresins. Andrew G. Du Mez _ 907

Studies of Zygospore Formation in Phycomycetes Nitens

Kunze. (With Plates XVI-XVIII). Mary Lucille

Keene _ 1195

Proceedings of the Academy, 1917 and 1918 _ l _ 1221

List of Officers and Members, corrected to September 1,

1918 _ _ _ _ _ _ _ _ _ _ 1233

Extracts from the Charter of the Academy, _ 1257

Constitution _ 1260

Index of Volume XIX___ _ _ _ _ iii iY

Davis — North American Ascochytae

655

NORTH AMERICAN ASCOCHYTAE

A Descriptive List of Species; Compiled by J. J. Davis.

A list of North American species of Phyllosticta was published

by Ellis & Everhart in 1900 and a similar list of species of

Septoria, Phleospora, Rhabdospora and Phlyctaena prepared by

Dr. George Martin and Mr. J. B. Ellis was issued in the Journal

of Mycology, vol. Ill [1887]. The present list enumerates

species of another of the genera of the same group.

To the genus Ascockyta are referred species the sporules of

which, as ordinarily observed, are uniseptate and so remain;

those in which the sporules remain continuous nearly or quite to

the time of full maturity becoming then uniseptate; species in

which a majority of the sporules are continuous but a minority

uniseptate. In the first two classes 2-3 septate sporules occur

rarely. Species in which the sporules are uniseptate until ma¬

turity becoming then triseptate are referred to Stagonospora.

Ascochyta is separated from Phyllosticta on the one side and

Stagonospora on the other by somewhat shadowy lines. Some

species that have been placed in this genus I am referring to

Stagonospora and to Marssonina.

1 Ascochyta achlydis Dearn. (Mycologia 8: 101-2.)

Spots scattered, numerous small ones, 2mm., mostly sterile,

and a few large ones 1 cm. or more in diameter with a central,

sharply delimited, thin, arid, deciduous area surrounded by a

diffuse dark red or purple brown border 1-5 mm. in width;

pycnidia nearly concolorous with the arid area, epiphyllous

although visible from the under side, 150-200^; sporules hya¬

line, 2-3 guttulate, obscurely uniseptate, rounded at the ends,

14-20 x 5-6%^. On leaves of Achlys triphylla.

656 Wisconsin Academy of Sciences, Arts, and Letters.

2 Ascochyta achlyicola Ell. & Evht.

Proc. Acad. Nat. Sci. Phila. 1894, p. 364.

Spots suborbicular or irregular with a sordid more or less

deciduous center and a broad, shaded, purple margin, 3-15 mm.

in diameter; pycnidia few, epiphyllous, innate-prominent, 75/* in

diameter; sporules elliptical, hyaline, binucleate soon becoming

uniseptate, 5-8 x 2%-3^. On Achlys triphylla.

3 Ascochyta actaeae (Bres.) Davis.

Actinomena actaeae Allesch. Stagonosporopsis actaeae Died.

Marssonia actaeae Bres.

On indefinite, blackened, dying areas of the leaves, the cuticle

on the upper surface of which is sometimes wrinkled in dendritic

lines ; pycnidia mostly epiphyllous, scattered, succineous, globose,

100-130/* in diameter, the walls at first hyphal but at maturity

formed of flat polygonal cells, without ostiolar thickening;

sporules hyaline, cylindrical with rounded ends, straight or

somewhat curved 1- (1-2) septate, 17-24x5-6/* (12-28x6-7^).

On leaves of Actaea rubra.

4 Ascochyta ampelina Sacc. Mich.l :158.

Spots epiphyllous, angular, dark bordered, becoming whitish ;

pycnidia scattered, punetiform, lenticular, ostiolate, 70/* in dia¬

meter; sporules oblong-fusoid, pale olivaceous, uniseptate, not

constricted, 10 x 3/*, rarely 12-15 x 3-3^2/*, 2-3 septate. On Vitis.

5 Ascochyta asclepiadis Ell. & Evht.

Proc. Acad. Nat. Sci. Phila. 1894, p. 364.

Spots amphigenous, suborbicular, grayish with darker zones

and a shaded dark brown border, %-l mm. ; pycnidia epiphyl-

lous-innate, ostiolate, black, 100-110^ in diameter; sporules

oblong-elliptical to ovate-elliptical, hyaline, becoming faintly

uniseptate, 6-8 x 3/*. On Asclepias syriaca.

6 Ascochyta aspidistrae. Massee.

Diseases of Cultivated Plants (1910) p. 431, fig. 133.

Spots large, irregular, bleached ; pycnidia grouped in blackish

streaks which run across the leaf and not along its length ;

sporules narrow-fusiform, uniseptate, 10-11 x 3-4^. On leaves

of Aspidistra lurida.

Davis — North American Ascochytae

657

7 Ascochyta baccae Rostr.

Till. Groenl. Svampe, p. 625.

Pycnidia small, grayish brown; sporules hyaline, guttnlate,

uniseptate, constricted at the septum, 9-12 x iy2-2[jL. On fruit

of Empetrum nigrum.

8 Ascochyta boerhaaviae Tharp.

Mycologia 9 : 106.

Spots suborbicular, dirty brownish grey, 2-4 mm.; pycnidia

epiphyllous-innate, dark brown, globose-depressed, ostiolate,

80-120 x 70-105ja; sporules hyaline, guttulate, uniseptate, 12-14

x 31/2-4/*. On leaves of Boerhaavia erecta.

9 Ascochyta bresadolae Sacc. & Syd.

Sacc. Syll. Fung. 14:948. Ascochyta fagopyri Bres.

Hedwigia, 31 : 40.

Spots alutaceous with a darker border above, pale below, 5-9

mm. in diameter; pycnidia epiphyllous, scattered, subglobose-

ovoid, ostiolate, 130-140/x; sporules cylindric-oblong, sometimes

somewhat curved, uniseptate, constricted at the septum, 16-18 x

6-7/*. On leaves of Fagopyrum esculentum.

10 Ascochyta carthagenensis Sacc.

Mich. 2:144.

On indefinite whitish spots on the branches; pycnidia aggre¬

gated, lenticular, at first covered, ostiolate, 100/x in diameter;

sporules greenish, oblong, obtuse at both ends, uniseptate, con¬

stricted at septum, 7-9 x 3-3%/*. On branches of Manihot

carthagenensis.

11 Ascochyta cassandrae Pk.

38th Report, p. 94.

Spots suborbicular or irregular, reddish-brown or grayish with

a reddish-brown margin; pycnidia epiphyllous, minute, erurn-

pent, blackish; sporules hyaline, oblong-fusiform, acute at each

end, uniseptate, 10-16 x 3-4/*. On leaves of Chamaedaphne

calyculata.

12 Ascochyta cephalanthi Ell. & Evht.

Sacc. Syll. Fung. 3: 392.

Spots orbicular, brownish white with a narrow somewhat

raised margin, 3-6 mm. in diameter ; pycnidia epiphyllous-

42— S. A. L.

658 Wisconsin Academy of Sciences, Arts, and Letters .

innate, irregularly scattered, depressed-hemispherical, 60-7 5 /x in

diameter ; sporules from narrow-elliptical to ovate-oblong,

brownish, uniseptate, 7-9 x 2%-3/*. On leaves of Cephalanthus

occidentalis.

13 Ascochyta cheiranthi Bres.

Hedwigia 39 : 326.

Spots scattered, round to oblong, alutaceous to brownish with

dark margin; pycnidia epiphyllous, arranged in a circle, pale,

100-140/x ; sporules hyaline, oblong to subcylindrical, occasionally

somewhat curved, uniseptate, 7-9 x 21/2-3%/*. On leaves of

Cheiranthus cheiri.

14 Ascochyta chrysanthemi Stevens.

Bot. Gaz. 44:246.

Pycnidia “few, immersed, early erumpent, single or scattered,

round, hemispherical, amber colored, 100-200 mostly about 150 /x,

ostiolum central, small, dark bordered, often raised by a short

neck, surface reticulate; pycnidia on agar media irregular,

often with two ostioles and varying much in size, black in color ;

mycelium abundant, innate, also superficial, aerial, floceose,

richly septate;” sporules “oblong, straight or irregular, 10-20

x 3-6.2/* mostly 6.2 x 10/x, ends obtuse or acute, septum, usually

one, often obscure, rarely 2 or 3, usually without constriction

until germination, protoplasm vacuolate, hyaline or light pink

in mass.” On Chrysanthemum indicum (cult.).

15 Ascochyta citrullina C. O. Smith.

Del. Ag’l Exp. Station Bull. 70.

Diplodina citrullina (C. O. Sm.) Grossenbacher. N. Y.

Ag’l Exp. Station, Tech. Bull. 9:226.

On whitened areas on the stems; pycnidia numerous, de¬

pressed-globose, pale brown, ostiolate, with thin-cellular walls,

90-150/x in diameter; sporules hyaline, oblong to obovate,

ends rounded, uniseptate, becoming constricted at the septum,

14x4^-5/x. On stems of Citrullus vulgaris (cult.).

16 Ascochyta clematidina Thuem.

Pilzfl. Sibir. no. 619.

Spots suborbicular to irregular, brown becoming cinereous

with a blackish brown border ; pycnidia epiphyllous, prominent,

Davis— -North American Ascochytae

659

hemispherical to globose, succineous to light brown, 100-125/x in

diameter; sporules oblong, hyaline, 2-4 guttulate, becoming 1-3

septate, 10-18 x3-7 /*. Wrinkling of the cuticle sometimes gives

the spots the appearance of bearing radiating whitish fibrils.

On leaves of Clematis.

16a Yar. thalictri Davis.

Trans. Wis. Acad. 16: 757.

Pyenidia smaller; sporules 8-10 x 2-3 y. On Thalictrum

dioicum.

17 Ascochyta compositarum Davis.

Trans. Wis. Acad. 19 : 700.

Spots definite, subcircular to irregular, brown, 1-5 cm. long

on large indefinite brown areas ; pyenidia few, innate, succineous

to brown, depressed-globose, ostiolate above, about 100/*. in dia¬

meter ; sporules hyaline, oblong to cylindrical, ends rounded,

4-guttulate, becoming uniseptate, more or less constricted, 14-24

x 4— 6/x. On leaves of Eupatorium urticaefolium} Aster Drum -

mondii and Helianthus strumosus. On the thinner leaves of

Eupatorium the affected areas are lighter colored and less de¬

terminate.

17a var. parva Davis.

Trans. Wis. Acad. 19:701.

Sporules 10-15 x 21/2-S1/2 y. On leaves of Helianthus stru¬

mosus.

18 Ascochyta confusa Ell. & Evht.

Journ. Mycol. 10: 168.

Spots amphigenous, round or irregular, white, thin, almost

transparent with a narrow dark brown raised border, 2-5 mm.

in diameter; sporules ovate or elliptical, smoky-hyaline, 7-12

x 314-41/2^. On leaves of Smilax hispida and sp. indet.

19 Ascochyta cornicola Sacc.

Mich. 1:169.

Spots irregular, white with a red border; pyenidia puncti-

f orm, lenticular, ostiolate, 80/*. in diameter ; sporules olive tinted,

oblong-elliptical, uniseptate, 7-15x3%-6^. On leaves of

Cornus.

660 Wisconsin Academy of Sciences , Arts, and Letters.

20 Ascochyta cycadina Scalia.

Fungi Sicil. orient, ser. Ill, p. 12 (1902).

Spots subcircular, white with a red border; pycnidia

epiphyllous, black, punctif orm, globose-depressed, walls

parenchymatous, composed of small polygonal olive-brown

cells , ostiolate, up to 300/* in diameter; sporules yellowish,

oblong, ends rounded or subacute at base, uniseptate, little

or not at all constricted, 10-13 x 3-4/*, borne on filiform

basidia of about equal length. On leaves of Cycas revoluta.

21 Ascochyta dianthi (A. & S.) Lib.

Sphaeria (Depazea) dianthi Alb. & Schw. Lus. tab. VI,

fig. 2.

Spots indefinite, pale; pycnidia amphigenous, small, dark

brown, ostiolate ; sporules hyaline, long fusiform to clavate-fusi-

form, rounded at ends, with a small appendage, uniseptate, con¬

stricted, 14^16 x 3-4^. On Dianthus.

22 Ascochyta diapensiae Rostr.

Oest. Oroenl. Svampe, p. 28.

On white areas involving the entire leaves ; pycnidia epiphyl¬

lous, globose, minute ; sporules cylindrical, thickened at the end,

often uniseptate, 12-15 x 3-5/*. On leaves of Diapensia lap -

ponica.

23 Ascochyta fragariae Sacc.

Mich. 1:169.

Spots subcircular, becoming white with a reddish black

margin; pycnidia globose-lenticular with thin parenchymatous

subochraceous walls conspicuously thickened about the broad

ostiole, 100/* in diameter; sporules olive-tinted, oblong-fusoid,

straight, uniseptate, not constricted, 12-15 x 3-4^. On leaves

of Fragaria.

24 Ascochyta fremontiae Hark.

Fungi Pacif . 5 : 439.

Pycnidia hypophyllous, scattered, small; sporules brown

tinted, subcylindrical, narrower at the ends, flexuous, 1- (1-3)

septate, 30-40 x 6-12^. On leaves of Fremontia calif ornica.

Davis— -North American Ascochytae

661

25 Ascochyta graminicola Sacc.

Mich. 1:127.

Spots definite, sordid white, purple bordered, oblong to oval,

5-8 mm. long, or none ; pycnidia aggregated, punctif orm, lenti¬

cular, with distinct parenchymatous, fuligenous walls, ostiolate,

100-120/x in diameter; sporules hyaline, fusoid to ovate-fusoid,

10- 20 x 21/2-4/*. On leaves of grasses. There is apparently

some confusion of this with Darluca filum (Biv.) Cast.

26 Ascochyta hanseni Ell. & Evht.

Bull. Torr. Bot. Club 24 : 464.

Spots amphigenous, irregular, definite, livid purple above,

paler and sub-rufous below, 2-10 mm. in diameter; sporules

brown tinted, oblong-cylindrical, obtuse, slightly curved,

1- (1-2) septate, not constricted, 15-20x6/*. On leaves of

Arbutus Menziesii.

27- Ascochyta garrettiana Syd.

Ann. Mycol. 3: 185.

Immaculate; pycnidia on leaves, rarely on stems also, black,

globose, about 175-250/* in diameter ; sporules hyaline, granular,

cylindrical, rounded at the ends, usually straight, uniseptate,

11- 20 x 2y2-S1/2fl. On Orthocarpus Tolmiei.

28 Ascochyta imperfecta Pk.

Report for 1911 pp. 21 and 106. (March, 1912).

Spots amphigenous, variably orbicular, semicircular or sub-

triangular, the larger ones usually terminal or marginal, pale

brown or smoky brown, not sharply defined; pycnidia amphi¬

genous, few, depressed, brown or blackish brown, 300-600/* in

diameter; sporules variable, hyaline, oblong or subcylindrical,

obtuse, continuous or pseudo-uniseptate, 6-15 x 2i/2-4y- On

leaves of Medicago sativa.A6 It may be separated from Ascochyta

medicaginis Bres. by its habitat and smaller peritheeia and

spores. ’ ’

29 Ascochyta infuscans Ell. & Evht.

Journ. Mycol. 5: 148.

Spots indefinite, brown, sometimes faintly zonate or on large

indefinite brown areas on leaves, petioles, branches and stems;

662 Wisconsin Academy of Sciences , Arts, and Letters.

pycnidia innate but often pushing up the epidermis, ostiolate,

120-180/* ; sporules hyaline, oblong, obtuse, constricted, guttu-

late, cytoplasm 1-8 divided, 10-18 x 2 %-6/a. On Ranunculus

abortivus.

30 Ascochyta ledi Rostr.

Fung. Groenl. p. 570.

Pycnidia sphaeroid-lenticular, black, 200-300/* in diameter;

sporules oblong, obtuse, uniseptate, 12-13 x 3/a. On branches

of Ledum groenlandicum.

31 Ascochyta leonuri Ell. & Dearn.

Proc. Canad. Inst. 1897, p. 92.

Spots numerous, round to angular, thin, arid, 1-1% mm. in

diameter, sometimes confluent; pycnidia visible on both sides,

150-170/* ; sporules pale, oblong-cylindrical, uniseptate, 14-17 x

3 %/a. On leaves of Leonurus cardiaca.

Specimens on Lycopus americanus having sporules 8-10 x

4-6/a, uniseptate, constricted, have been referred to this species.

32 Ascochyta lophanthi Davis.

Trans. Wis. Acad. 14: 95.

Spots definite, blackish brown, round to oval, margin often

repand, 5-20 mm.; sporules short-cylindrical, ends rounded,

uniseptate, constricted, 20-30 x 10-12/a. On leaves and some¬

times branches of Agastache scrophulariaefolia.

32 a Var. osmophila Davis.

Ibid. 19:700.

Sporules 12-21 x 3-5/a. On leaves of Agastache Foeniculum.

33 Ascochyta lycopersici Brun.

Champ. Saint. 1887, p. 430.

Spots large, suborbicular to irregular, red to brownish;

pycnidia scattered, black, small; sporules hyaline, oblong, uni¬

septate, constricted, 8-10 x 2%/a. On leaves of Ly coper sicon

esculentum.

34 Ascochyta mali Ell. & Evht.

Bull. Torr. Bot. Club, 27: 56.

* 1 Spots circular, %-l cm. in diameter, concave, of a pale brick

red color, with the margin narrowly free, sometimes becoming

Davis — North American Ascochytae

663

much larger, extending for 2 cm. and nearly surrounding the

limb. These spots appear to be formed from the altered sub¬

stance of the bark which is changed in color and cracks away,

around the margin, from the surrounding bark which remains

in its normal condition ; perithecia at first solitary, a single one

erumpent in the center of the circular disk, finally 2-4 or more

scattered on the same disk; sporules oblong or oblong-elliptical,

smoky-hyaline, uniseptate, 6-8 x On living limbs of

Pyrus malus.

35 Ascochyta medicaginis Bres.

Hedwigia 39 : 326.

(Ascochyta medicaginis Fckl. was referred to Phyllosticta by

Saccardo.)

Spots amphigenous, small, pale, angular, clustered; pycnidia

somewhat flattened at base, apex prominent, pale straw color dry¬

ing black, walls parenchymatous, 200xl60/z; sporules hyaline,

cylindrical, straight or somewhat curved, becoming uniseptate,

16-26 x3%~5/a (‘ ‘ 12-20 x 3-6”)- On leaves of Medicago lupn~

lina.

36 Ascochyta meliloti (Trel.)

Gloeosporium (Marsonia) meliloti Trel. Trans. Wis.

Acad. 6:120 (16); Ascochyta caulicola Laubert;

Ascochyta lethalis Ell. & Barth. F. Col. 1808.

Spots orbicular to elliptical, sordid with a dark purple or

brown margin, 2-5 mm. in diameter, often confluent ; pycnidia

globose, prominent, brown, darker about the ostiole, 100-180 /a;

sporules hyaline, oblong, uniseptate, constricted, straight or

curved, 10-18 x 3%-5%/a. On stems and sometimes leaves of

Melilotus alba.

37 Ascochyta margin at a Davis.

Trans. Wis. Acad. 18 : 263.

Spots circular to subcircular, at first green becoming brown

with a paler central portion and a darker periphery and a dis¬

tinct narrow margin, 5-15 mm. in diameter; pycnidia epiphyl-

lous, scattered, pale brown, irregularly globose with a thin cel¬

lular wall and a dark round ring around the ostiole, about 100 /a ;

sporules hyaline, ovoid to oblong with rounded ends, some of

them uniseptate, 6-12 x 2-3%/a. On leaves of Aralia nudicaulis.

664 Wisconsin Academy of Sciences , Arts , and Letters.

38 Ascochyta menziesii Ell. & Evht. 4 ‘n. sp. in litt. ’ ?

On leaves of Arbutus Menziesii. San Gabriel Mts. Mc-

Clatchie, Flora of Pasadena.

I have seen no description or specimen of this. A de¬

scription, apparently, was never published.

39 Ascochyta menyanthis Oud.

Contrib. FI. Mycol. Pays Bas. 17 : 262.

Spots irregularly scattered, brown, variable in size; pycnidia

amphigenous but more abundant below ; sporules hyaline, cylin¬

drical, ends rounded, 2-4 guttulate, uniseptate, 14-19 x 2-3% /*-•

On leaves of Menyanthes trifoliata.

40 Ascochyta oxybaphi Trel.

Trans. Wis. Acad. 6: 121 (17).

Spots rounded, dark brown, 1-2 mm. ; pycnidia epiphyllous,

brown, blackened about the ostiole, small; sporules hyaline,

uniseptate, sometimes constricted 10-17 x 4/a. On leaves of

Oxybapkus nyctagineus.

41 Ascochyta oxytropidis Schroet.

Pilz. Labrad. :19,

Immaculate ; pycnidia irregularly scattered, black, about 250/* ;

sporules hyaline, long-ellipsoid, nearly bacillary, often arcuate,

ends rounded, uniseptate, 9-11 x 2%-3/a. On dead leaves and

petioles of Oxytropis.

42 Ascochyta parasitica Fautr.

Rev. Mycol. 1891 p. 79.

Spots epiphyllous, white ; sporules 6-9 x 3%-4/a. On leaves

of Althaea rosea.

43 Ascochyta Paulo wniae Sace. & Brun.

Fungi Gall. no. 2241.

Spots epiphyllous, various, brownish grey; pycnidia lenti¬

cular, ostiolate, 90 /a; sporules olive tinted, fusoid, 4-guttulate,

uniseptate, scarcely constricted, 15-18 x 3/*. On leaves of

Paulownia.

44 Ascochyta p&tuniae Speg.

Nov. Add. no. 156.

Spots circular becoming angular, fuligenous, zonate ; pycnidia

black, 100-130/a; sporules hyaline, cylindric-elliptical, unisep¬

tate, little or not at all constricted, 5-8 x 2/a. On leaves of

Petunia.

Davis — North American Ascochytae

665

45 Ascochyta phlogis Vogl.

Ann. R. Ace. Agr. Torin: 51.

Spots oblong to irregular, sordid to white, sometimes with a

brown border ; pycnidia gregarious, somewhat prominent,

conical, black; sporules hyaline, elliptical, becoming uniseptate,

slightly constricted, 10-3/a. On leaves of Phlox Drummondii

(cult.). Fairman described “subspecies phlogina” from Ameri¬

can material as follows: “Spots white, irregular or rounded,

girt by a brown area of discolored leaf tissue ; pycnidia minute,

punctiform, generally clustered in the center of the white spots,

black; spores uniseptate, hyaline, 10-14 x 3/a.” (Ann. Mycol.

8:323).

46 Ascochyta Pirina Pegl.

Contr. Micol. Avell. p. 23.

Pycnidia black, 300/a; sporules hyaline, uniseptate, slightly

constricted, 12-14 x 4-5/*. On fruit and leaves of Pyrus com¬

munis.

Spots alutaceous, at length abscissed and falling away ;

pycnidia with parenchymatous walls thickened about the ostiole,

cylindrical, hyaline or pale honey color, uniseptate, pale

fuligenous, 150-180/a, ostiole 20/a in diameter; sporules

hyaline, uniseptate, not constricted, 12-16 x 4/a borne on

very short, somewhat conical, basidia. On Pyrus arbutifolia

(Saccardo, N. Giorn. Bot. Ital. 23:195).

47 Ascochyta pisi Lib.

Exs. No. 12. Saccardo, F. Herb. Brux. no. 35.

Spots definite, circular, yellowish-brown with a darker

margin, sometimes white sometimes dark in the center ; pycnidia

gregarious, somewhat prominent, depressed-globose, light brown,

ostiolate, 100-200/a; sporules hyaline, oblong, ends rounded,

straight or somewhat curved, 1- (1—3) septate, somewhat con¬

stricted, 14-16 x 4-6/*. On leaves, stems and pods of Pisum and

Vicia and leaves of Lupinus perennis.

48 Ascochyta primulae Trail.

Scot. Nat. 1887, p. 88.

Spots amphigenous, large, white, becoming arid, often with

a yellowish border ; pycnidia epiphyllous, scattered, pale brown,

depressed-globose, ostiolate, 100-110/a; sporules hyaline, cylin¬

drical, obtuse, uniseptate, 5-6 x 2-21/2/*. On leaves of Primula.

666 Wisconsin Academy of Sciences , Arts , and Letters.

49 Ascochyta quercus Sacc. & Speg.

Mich. 1:162.

Spots various, becoming whitish; pycnidia punctiform, sub-

lenticular, 80-90/a; sporules hyaline, oblong-ellipsoid, obtuse,

uniseptate, more or less constricted, 12 x 3-4%/a. On leaves of

Quercus ._ Perhaps the fungus which Trelease reported under

this name as occurring on oak leaves in Wisconsin is not dis¬

tinct from Marssonina martini (Sacc. & Ell.) Magn.

50 Ascochyta quercuum (Cke.) Sacc.

( Sphaerellopsis quercuum Cke., Grevillea 12:23)

Pycnidia hypophyllous, scattered, dark brown, subsup erficial,

subglobose, 150/a ; sporules hyaline, lanceolate, uniseptate, 16 x

4/a. On leaves of Quercus virens.

51 Ascochyta rhei Ell. & Evht.

Proc. Acad. Nat. Sci. Phila., 1893, p. 160.

( Phyllosticta rhei Ell. & Evht. Joum. Mycol. 5:145.)

Spots mostly marginal, subconfiuent, rusty brown, concentri¬

cally zoned, either with or without a definite, slightly darker

limiting line surrounded by a broad border of light yellow, 1-2

cm. in diameter; pycnidia few, visible on both surfaces of the

leaf, slightly prominent, up to 150/a; sporules hyaline, oblong-

elliptical, ends rounded, becoming uniseptate and mostly con¬

stricted, 5-12 x 2%-4/a. On leaves of Rheum.

52 Ascochyta rhynchosiae (Thuem.) Sacc.

Sacc. Syll. Fung. 3 : 398.

Spots irregular, dark brown with a darker margin ; pycnidia

epiphyllous, scattered, immersed, black, globose ; sporules hya¬

line, fusiform, acute at each end, uniseptate, 9 x 3/a. On Rhyn-

chosia simplicifolia.

53 Ascochyta rubi Lasch.

Bot. Zeit. (1848) p. 294.

Spots pale; pycnidia subglobose, blackish brown; sporules

exuded in white cirri. On Ruhus.

54 Ascochyta Sambuci Sacc.

Mich. 1:168.

Spots indefinite, becoming whitish and arid; pycnidia few,

punctiform, ostiolate ; sporules olivaceous, fusoid, uniseptate, not

Davis — North American Ascochytae

667

constricted, 15-18 x3-3 y2fi. On leaves of Sambucus nigra

aurea,

55 Ascochyta silenes Ell. & Evht.

Jonrn. Mycol. 5:148.

Spots pale yellowish, the entire leaf finally assuming the same

color, the spots, which are then hardly discernible becoming

paler; pycnidia not confined to the spots but scattered over the

entire leaf, erumpent, discoid, broadly ostiolate, 120-150/a;

spo rules hyaline, oblong, rounded at the ends, becoming 1- (1-2)

septate, 10-14 x 2y2-~3^. On leaves and stems of Silene antir-

rlnina.

56 Ascochyta sisymbrii Ell. & Kell.

Journ. Mycol. 5:142.

Immaculate; pycnidia amphigenous, scattered, innate, black,

depressed-globose, 200-285/a in diameter, 100-195/a high, ostiole

20-25/a in diameter ; sporules subhyaline, vermiform-cylindrical,

mostly uniseptate, 18-45 x 3!/2-6^, mostly 25-38 x 4-5/a. On

leaves and petioles of Sisymbrium canescens . “Not to be con¬

founded with Septoria sisymbrii Ell. which is on spots and has

smaller spores. ’ ’

57 Ascochyta smilacis Ell. & Evht.

Journ. Mycol. 8: 12. Not A. smilacis E. & M. which is

Stagonospora smilacis (E. & M.) Sacc.

“Spots small (1-4 mm.) of irregular shape, dirty white with

a brown border or large brown areas 1-2 cm. in diameter ; pycni¬

dia scattered, epiphyllous but mostly visible from below, puncti-

form, black; sporules elliptical, obtuse, smoky hyaline, unisep¬

tate, not constricted, 6-8 x 4/a.” On Smilax hispida.

58 Ascochyta Solani-nigri Died.

Hedwigia 42: Beiblatt (166).

Spots scattered, orbicular or oval, arid, whitish with a dark

margin; pycnidia globose, brown, thin walled, ostiolate, about

80/a ; sporules cylindrical with rounded ends, straight or a little

curved, uniseptate, not constricted, 6-8 x 3/a. On leaves of

Solanum Melongena.

668 Wisconsin Academy of Sciences , Arts , and Letters.

59 Ascochyta spartinae Trel.

Trans. Wis. Acad. 6:121 (17).

Spots small, rounded, pale yellow ; spornles hyaline, flesh color

in mass, straight or slightly curved, usually a little narrower

at one end, 1- (1-8) septate, averaging about 35 x 3/*. On leaves

of Spartina Michauxiana.

60 Ascochyta symphoricarpophila Fairman.

Ann. Mycol. 8:323.

Spots irregular, brown, mostly marginal; pycnidia epiphyl-

lous, black, minute; sporules hyaline, elliptical, ends rounded,

uniseptate, not constricted, 6-9 x 3-4/*,. On leaves of Symphori-

carpos racemosus. Said to differ from A. symphoriae Br. &

Har. in the somewhat shorter sporules not being constricted.

61 Ascochyta teretiuscula Sacc. & Roum. (?)

Mich. 2 :621.

Immaculate ; pycnidia innate, punctiform, ostiolate, 100-110/*, ;

sporules hyaline, cylindrical, ends rounded, uniseptate, scarcely

constricted, 10-14 x 2!/2/*,. On leaves of Cyperus.

62 Ascochyta thaspii Ell. & Evht.

Journ. Mycol. 5:148.

Spots amphigenous, suborbicular, dirty brown, with a definite

margin and surrounded by . a narrow yellow border, about 1%

cm. in diameter; pycnidia entirely buried in the substance of

the leaf and scarcely visible, pale, 100-120/*, in diameter ; sporules

cylindrical, ends rounded, 3-4 guttulate, uniseptate, 18-30 x

4-8/*,. On leaves of Thaspium barbinode and Zizia aurea.

62 a var. saniculae (Davis).

(Ascochyta saniculae Davis. Trans. Wis. Acad. 181:105.)

On indefinite, discolored, more or less mottled areas which

may include the entire leaf; pycnidia scattered, innate, globose

to lenticular, light reddish brown with a dark ring around the

ostiole, 100-170^ ; sporules hyaline, cylindrical, usually straight,

quadriguttulate, uniseptate, 20-30 x 4^6/*. The pycnidia are

very inconspicuous. They are most readily seen by transmitted

light when they show as translucent points. On Sanicula

marilandica.

63 Ascochyta treleasei Sacc. & Yogi.

Ascochyta sp. Trelease. Trans. Wis. Acad. 6:121 (17).

Spots circular, brown, about 3 mm. in diameter; pycnidia

Davis — North American Ascochytae

669

epiphyllous, brown, blackened about the ostiole, 100-200/a;

sporules hyaline, ovoid, oblong, or reniform, 2-4 guttulate, be¬

coming uniseptate, frequently constricted, 7-14x5-7/*. On

leaves of Silphium integrifolium and Vernonia noveboracensis .

64 Ascochyta veratrina Ell. & Evht.

Proc. Acad. Nat. Sci. Phila. 1894 p. 364.

Pycnidia scattered, sunk in the substance of the leaf with the

apex and conic-papilliform ostiolum erumpent, about % mm. in

diameter; sporules hyaline, cylindrical, obtuse, 3-4 guttulate,

becoming uniseptate, about 12 x 2%-3/a. On dead leaves and

petioles of Veratrum calif ornicum.

4 'Differs from A. Veratri , Cavarra (Fungi Langobardiae No.

98) in its larger ostiolate perithecia, not on any spots and in its

smaller, straight sporules.’ ’

65 Ascochyta violae Sacc. & Speg.

Mich. 1 :163.

Spots various, becoming whitened; pycnidia gregarious, glo¬

bose-lenticular, walls parenchymatous, blackened about the

ostiole, 180-200 ; sporules hyaline, short-fusoid, uniseptate, not

constricted, 15-18 x 3%-4/a. On leaves of Viola.

66 Ascochyta wisconsina Davis.

Trans. Wis. Acad. 181 :101.

Spots orbicular to elliptical, grey with a narrow black border

and frequently zonate above, brown to olivaceous with a less dis¬

tinct border below, 1-3 cm. long; pycnidia epiphyllous, scat¬

tered, brown, prominent, globose to sublentieular, 85-110/a;

sporules hyaline, ovoid to oblong, 4-8 x 2%-3%/*. Some of the

longer sporules have a medium septum. On leaves of Sam-

bucus canadensis and 8. racemosa.

67 Ascochyta zeicola Ell. & Evht.

Hedwigia 42, Beiblatt (166).

On slightly darker, irregular or sub-elongated areas ; pycnidia

gregarious, suberumpent, ostiolate, 100-150/* ; sporules hyaline,

yellowish in mass, oblong-cylindrical, obtuse, uniseptate, not

constricted, 6-8 x 1%-2/a. On old stalks of Zea Mays. 4 4 Very

different from A. Zeina Sacc. which is on the leaves and has

sporules 18 x 7/a.”

670 Wisconsin Academy of Sciences, Arts, and Letters,

INDEX TO HOSTS

Achlys triphylla, 1, 2

Actaea rubra, 3

Agastache Foeniculum, 32a

Agastache scrophulariaefolia, 32

Althaea rosea, 42

Aralia nudicaulis, 37

Arbutus menziesii, 26,38

Aributus menziessi, 38

Asclepias syriaca, 5

Aspidistra lurida, 6

Aster Drummondii, 17

Boerhaavia erecta, 8

Cephalanthus occidentalis, 12

Chamaedaphne calyculata, 11

Cheiranthus cheiri, 13

Chrysanthemum indicum, 14

Citrullus vulgaris, 15

Clematis, 16

Cornus, 19

Cycas revoluta, 20

Cyperus, 61

Dianthus, 21

Diapensia lapponica, 22

Empetrum nigrum, 7

Eupatorium urticaaefolium, 17

Fagopyrum esculentum, 9

Fragaria, 2 3

Fremontia calif ornica, 24

Gramineae, 25

Helianthus strumosus, 17, 17a

Ledum groenlandicum, 30

Leonurus cardiaca, 31

Lupinus perennis, 47

Lycopersicum esculentum, 33

Lycopus americanus, 31

Manihot carthagenensis, 10

Medicago lupulina, 35

Medicago sativa, 28

Melitotus alba, 36

Menyanthes trifoli-ata, 39

Orthocarpus tolmiei, 27

Oxybaphus nyctagineus, 40

Oxytropis, 41

Paulownia, 43

Petunia, 44

Phlox drummondii, 45

Pisum, 47

Primula, 48

Pyrus arbutifolia, 46

Pyrus communis, 46

Pyrus malus, 34

Quercus, 49

Quercus virens, 50

Ranunculus abortivus, 29

Rheum, 51

Rhynchosia simplicifolia, 52

Rubus, 53

Sambucus canadensis, 66

Sambucus nigra aurea, 54

Sambucus racemosa, 66

Sanicula marilandica, 62a

Silene antirrhina, 55

Silphium integrifolium, 63

Sisymbrium canescens, 56

Smilax, 18

Smilax hispida, 18, 57

Solanum melongena, 58

Spartina michauxiana, 59

Symphoricarpos racemosus, 60

Thalictrum dioicum, 16a

Thaspium fyarbinode, 62

Veratrum californicum, 64

Vernonia noveboracensis, 63

Vicia, 47

Viola, 65

Vitis, 4

Zea mays, 67

Zizia aurea, 62

Davis — Notes on Parasitic Fungi in Wisconsin — IV. 671

NOTES ON PARASITIC FUNGI IN WISCONSIN— IV:

J. J. Davis.

A provisional list of parasitic fungi in Wisconsin was pub¬

lished in the Transactions of the Wisconsin Academy of Science,

Arts & Letters, 172:846-984. Supplementary notes bearing

the title above were issued in the same publication, 181:78-92

(I) 93-109 (II) and 251-271 (III).

Parasitic fungi were less abundant in Wisconsin than usual

in 1915. This may be attributed to a reversal of season in the

spring, a warm April having been followed by a cold May.

In the first number of these notes there was mention of the

occurrence of Plasmopara humuli Miyabe & Takahashi on

Humulus Lupulus at Racine in southeastern Wisconsin. This

seems to be the first, and as yet the only, American locality from

which this Japanese mildew has been reported. In September,

1915 it was collected on the same host near Lynxville on the

Mississippi and at Gays Mills and Petersburg in the Kickapoo

valley in western Wisconsin. At Lynxville the Japanese host

Humulus japonicus was abundant on vacant lots and it was

also observed at Gays Mills in cultivation and as an escape but

the mildew was not found on this species.

Dimer osporium collinsii (Schw.) Thuem. is referred to a new

genus, Apiosporina, by von Hoehnel. (Fragm. zur Mykol. no.

506).

For the 1 ‘ black knot” fungus recorded under the name Plow-

riglntia morbosa (Schw.) Sacc. the new genus Dibotryon is pro¬

posed by Theissen and Sydow. (Ann. My col. 13: 663.)

The fungus recorded in the provisional list under the name

Dotkidell'a ulmea (Schw.) Ell. & Evht. and referred to in

672 Wisconsin Academy of Sciences, Arts, and Letters.

“ Notes” 111:258, as Euryachora ulmea ( Schw. ) Rehm is refer¬

red to Gnomonia by Theissen and Sydow. Yon Thuemen refer¬

red it to this genus in Flora, 1878, p. 178, and Gnomonia ulmea

(Schw.) Thuem. was given in Saccardo’s Sylloge Fungorum

1: 570 in the section Dubiae. Klebahn has shown that PJileos-

pora ulmi (Fr.) Wallr. which Fuckel thought to be a conidial

state of this fungus is really connected with Mycosphaerella.

A form of Phyllactinia corylea (Pers.) Karst, occurs at Madi¬

son and in Buffalo county near Arcadia on Quercus velutina

in which a profuse superficial mycelium is developed.

According to Theissen and Sydow Physalospora ambrosiae

Ell. & Evht. as given in the provisional list is Plnyllachora am¬

brosiae (B. & C.) Sacc. (Ann. My col. 13: 556).

Gnomonia caryae F. A. Wolf has been collected at Madison

on leaves of Carya ovata that had borne Gloeosporium caryae

Ell. & Dearn. the previous year. It occurred both on leaves

lying on the ground and those wintered in a wire cage. We

find the ascospores about 2/*, thick.

Montagnella heliopsidis (Schw.) Sacc. is referred to the genus

Rosenscheldia by Theissen and Sydow (Ann. My col. 13:649).

Plnyllachora junci (Fr.) Fckl. is referred to their genus En-

dodothella by Theissen and Sydow (Ann. Mycol. 13:586). On

the following page they refer to a collection of Endodothella

strelitziae (Cke.) Theiss. & Syd. on Strelitzia angusta made at

Madison by Trelease.

The record of Exoascus cerasi (Fckl.) Sacc. in “Notes” II,

p. 97 seems to have been due to an error. No Wisconsin speci¬

men of this species is in the herbarium.

The name Stagonospora smilacis (E. & M.) Sacc. was used in

the provisional list to designate the fungus that causes orbicular,

sordid-arid, purple or brown bordered spots on leaves of Smilax.

As usually collected the pycnidia contain continuous sporules

varying in different specimens from oblong-fusoid and up to 21a

long to broad oval or subglobose. This is usually distributed

as Phyllosticta smilacis Ell. & Mart, which it doubtless is. As

the leaf tissue included in the spot usually disintegrates I as¬

sume that the sporules seldom reach maturity on the host and

Davis — Notes on Parasitic Fungi in Wisconsin- — IV. 673

as septate sporules are now and then found, that septation comes

with maturity. A collection on Smilax rotundifolia from Lynx-

ville bears ovoid or ovate more deeply tinted smaller sporules

and is perhaps Ascochyta confusa Ell. & Evht. [See Dearness.

Mycologia 9: 359-60.]

Septoria candbina West, of the provisional list should be Sep-

toria cannabis (Lasch.) Sacc. In a specimen from Lynxville

the sporules are 25-45 (mostly 30-36) x2-2 y2fi.

The host given as Rumex altissimus in the provisional list is

probably R. mexicanus.

R. E. Stone finds Septoria ribis Desm. to be genetically con¬

nected with Mycosphaerella grossulariae (Fr.) Auersw. (Phyto¬

pathology 6:109).

The fungus recorded in the provisional list under the name

Cylindrosporium. ribis Davis is evidently conspecific with

Brenekle ?s Fungi Dakotenses 320 which was determined by Sac-

cardo as Septoria sibirica Thuem. Saceardo gives a description

in Annates Mycologici 13:122. This seems quite different from

European material distributed under this name.

For the fungus described by Trelease under the name

Ascochyta salicifoliae and referred to Septoria by Berlese &

Voglino and by Ellis & Everhart I am using the name Cylin¬

drosporium salicifoliae (Trel.) as better expressing the acer-

vular character of the spore body as I find it.

Dr. E. A. Burt of the Missouri Botanical Garden has kindly

examined the type of Gloeosporium ( Mar sonia) meliloti Trel.

and sent mounted sections thereof. It proves to be the

Ascochyta caulicola of Laubert and A. lethalis Ell. & Barth. R.

E. Stone has connected it with an ascigerous form to which he

gave the name Mycosphaerella lethalis Stone. In the descrip¬

tion Trelease designated the spore bodies ‘ ‘ Perithecia ’ ’ which

was changed to “acervuli” in the Sylloge Fungorum doubtless

to conform to the character of the genus to which it was re¬

ferred. The word pycnidium was not then in use.

Examination of type material of Gloeosporium populinum

Pk. received from Dr. H. D. House shows it to be the same as

43— s. A. L.

674 Wisconsin Academy of Sciences , Arts , and Letters.

Marssonina rhabdospora (Ell. & Evht.) Magn. Both specific

names were published in 1893 but Peck’s description probably

was issued later in the year than Ellis & Everhart’s.

As I see it the fungus known as Gloeosporium trifolii Pk.

develops, when perfectly formed, which often it is not, a definite

pycnidial wall and the sporules, when mature, have a median

septum. Occasional sporules develop 2-3 septa as is so fre¬

quently the case in Ascochyta. I have not had the opportunity

to bring them to germination to see if they then become tri-

septate as is the case in Stagonospora dearnessii Sacc. on Tri-

folium repens. What appears to be a state of this, probably

immature, has been collected with sporules but about 8 x 2 y2jif

continuous and what is possibly a spermogonial or microconidial

state occurs frequently with sporules 4-8 x l-l^/q continuous.

In this form the distal portion of the pycnid'ium is imperfect

and it is much like the fungus on Medicago known as Sporonema

phacidioides Desm.

Specimens of Ramularia ionophila Davis collected at Long

Lake in 1915 show that the spots become light yellowish brown

with the death of the included leaf tissue and that the conidia

are often catenulate. The spots are usually 2-5 mm. in dia¬

meter and the limiting veinlets sometimes give the appearance

of a narrow colored margin. It was confined here, as in the

type locality, to the single species of host, Viola canadensis.

When well developed Ramularia nemopanthis Pk. is of the

Ovularia type, the conidia being continuous, catenulate, 7-15 x

3—6/a.

In “Notes” I: 89-90 it was noted that Ovularia asperifolii

Sacc. var. lappulae Davis seems quite similar to var. symphyti-

tuberosi Allesch. Jaap has raised the latter to specific rank

and referred it to Ramularia because of occasional septate con¬

idia (Ann. My col. 14: 41). When conidia are borne in chains

the proximal members are usually longer than the distal and

sometimes septate. I take it that the septum is due to a fail¬

ure of the abstriction process which becomes less active toward

the base of the chain. In such forms the distinction between the

genera is difficult to hold. I am inclined to think that it would

be better to include in Ovularia only species that bear ovoid

conidia singly.

Davis — Notes on Parasitic Fungi in Wisconsin — IV. 675

The fungus referred to Fusicladium radiosum (Lib.) Lind

var. microsporum (Sacc.) Allesch. in “Notes” 111:256, is per¬

haps not distinct from Cladosporium subsessile Ell. & Barth.

The conidia are 12-15 x 4/x, continuous. This has since been

collected at Whitehall.

A specimen on Aster puniceus was collected in Oconto County,

Wisconsin, July 19, 1909, and placed in my herbarium with

Cercosporella cana Sacc. and Aster puniceus was given as a host

of this species in the provisional list. Inside the packet I find

the following description: On angular or indefinite areas that

finally become brown; conidiophores hypophyllous, fasciculate,

cylindrical or tapering upward, denticulate, sometimes branched,

20-35 x 5/* ; conidia hyaline, obclavate, pluriseptate, straight,

or curved, 60-130 x 3 /*. In the absence of definite knowledge of

the relationship of this to Cercosporella cana Sacc. on Erigeron

and to C. reticulata Pk. C. nivea Ell. & Barth., C. ontariensis

Sacc. and C. dearnessii Bubak & Sacc. on Solidago, I am desig¬

nating it Cercosporella cana Sacc. var. gracilis n. var.

Specimens of Cercospora corni Davis collected at Grays Mills

in September show some of the conidia darker, thicker walled

and strongly constricted at the septa, suggesting ultimate di¬

vision into separate globose cells which might perhaps retain

vitality through the winter.

To the original description of Cercospora ageratoides Ell. &

Evht. (Journ. My col. 5: 71) is appended a reference to a form

on Eupatorium album having shorter (40/*) conidiophores and

longer (70-80/*) and narrower (3/*) conidia. In a collection

on Eupatorium urticaefolium from Lynxville the conidiophores

are 20^-0 x 3-6/*, and the conidia up to 100 x 3-41/2/*, effused

over indefinite areas.

Cercospora zebrina Pass, is referred to C. helvola Sacc. as a

variety by Ferraris (FI. Ital. Crypt. 1:8:423.).

TJrocystis waldsteiniae Pk. was inadvertently omitted from

the provisional list. It has been collected but once in Wiscon¬

sin but it was then abundant at the station which was at Plant¬

ing Ground lake near Three Lakes.

676 Wisconsin Academy of Sciences, Arts, and Letters.

A. A. Potter reports that the smut given in the provisional

list as Sphacelotheca sorgini (Lk.) Clinton is S. cruenta (Kuehn)

Potter. (Phytopathology 5:152-3.)

Puccinia caricis-solidaginis Arth., P. caricis-asteris Arth., P.

caricis-erigerontis , Arth., and P. dulichii Syd. are now included

in P. extensicola Plowr. by Arthur ( Mycologia 7 :70 and 80-81.)

I am informed by Dr. Arthur that the rust on Melica striata

that was recorded in “ Notes’’ II under the name Puccinia

melicae (Erikss.) Syd. is P. erikssonii Bubak. It has since

been collected at Solon Springs on the same host.

The rust on Agropyron repens given in the provisional list

under Puccinia rubigo-vera (DC.) Wint. is now believed to be

P. agropyri Ell. & Evht. developing its aecia on Eanunculaceous

hosts. P. tomipara Trel. probably belongs here also. ( My¬

cologia 7:73-5.) It has been collected on Agropyron tenerum

also at Solon Springs where ((Aecidium ranunculacearum”

occurred on Anemone quinquefolia.

Cultures made by Dr. Arthur have shown that Aecidium

nesaeae Ger. is the aecial stage of Puccinia minutissima Arth.

(Mycologia 7:86).

For the rust of which Caeoma abietis-canadensis Farl. is the

aecial form Ludwig makes the new combination Melampsora

abietis-canadensis (Phytopath. 5:279). There is objection by

some mycologists to the extension of aecial specific names to

apply to telial states and the objection is especially cogent when

the name is derived from that of the aecial host of a heteroecious

species. Many rust names are derived from that of the telial

host and it is confusing to have introduced among them an oc¬

casional one taken from that of the aecial host. In the present

case, as in others, the aecial host bears also telia referred to

another species and that is the one that the name would sug¬

gest. To the present day uredinologist this is a matter of

little importance but when one considers the generations of

botanists to come it seems well worth while to remove these ob¬

stacles from a path that is none too smooth. I am using in the

herbarium Melampsora populi-tsugae nom. nov. referring to

it specimens on Populus grandidentata from Gaslyn (II) and

Kacine (II, III), and on Populus tremuloides from Wausaukee,

Davis—Notes on Parasitic Fungi in Wisconsin — IV. 677

For want of another I used in the provisional list the name

Puccinia impatientis Arth. for a species forming uredinia and

telia on Elymus. For this I suggest the designation Puc¬

cinia elymi-impatientis nom. nov. For the rnst given in the

provisional list as Puccinia albiperidia Arth. I am now using the

name Puccinia pringsheimiana Kleb. as there seems to be no rea¬

son for considering the American rust as distinct from that of

Europe.

ADDITIONAL HOSTS

Albugo Candida (Pers.) Kuntze. On Dentaria diphylla.

Laona. Oospores only ; in leaves.

Basidiophora entospora Roze & Cornu. On Erigeron canar-

dense. Long Lake. Monstrous conidia, up to 63 x 30y., with

suppression of conidiophores were found in this collection ( Cfr.

Farlow, Botanical Gazette 7: 311).

Peronospora potentillae D By. On Agrimonia mollis. Lynx-

ville.

Peronospora trifoliorum D By. Collected in small quantity

on Lupinus perennis at Millston.

In “Notes” I, p. 85 mention was made of the collection of

Synchytrium at Athelstane on Rubus Jiispidus and on no other

host. The station was visited again in July, 1915, but the

organism was not found on Rubus. It was found however, in

small quantity, on Viola conspersa and on a single leaf of

Clintonia borealis. In August collections were made at Solon

Springs on Viola conspersa , Halenia deflexa, and in small

quantity on Rubus triflorus. It may be that these represent

more than one species but the effects of stage of development, host

and environment have not been worked out.

SphaerotJieca bumuli fvliginea (Schl.) Salm. On Bidens

cernua. Madison.

MicrospJiaera alni (Wallr.) Wint. On Ostrya virginiana.

Lynxville. Juglans cinerea, Madison. Lonicera Mrsuta, Solon

Springs.

678 Wisconsin Academy of Sciences, Arts, and Letters.

Microsphaera diffusa C. & P. On Symphoricarpos orbiculatus

(cult.) Madison. (Denniston and Trelease.)

Erysiphe graminis DC. Conidia on Poa triflora. Solon

Springs. Peritheeia on Hordeum vulgar e (cult.) Madison (€.

S. Reddy).

Erysiphe cichoracearum DC. On Napaea dioica. Gays Mills.

Epichloe typhina (Pers.) Tul. On Glyceria nervata. Athei¬

st ane.

Exoascus communis Sadeb. “On fruit of wild plum” Madi¬

son. (A. B. Seymour, Econ. Fungi 31) and Racine.

In the preliminary list of parasitic Fungi of Wisconsin Tre¬

lease recorded Exoascus pruni Fckl. “On the fruit of Prunus,”

causing ‘ ‘ plum pockets ” or “ bladder plums. ’ ’ This may have

been, in part at least, what is now known as Exoascus communis

Sadeb. on native plums. Atkinson, however, referred to speci¬

mens on Prunus domestica from Wisconsin {Cornell University

Ag’l Exp. Station bulletin 73: 329).

Taphrina coerulescens (Desm. & Mont.) Tul. On Quercus

ellipsoidalis. Athelstane and Solon Springs.

Taphrina potentillae (Farl.) Johans. On Potentilla cana¬

densis. Merrimack.

Phyllosticta cruenta (Fr.) Kickx. On Polygonatum bi-

florum. Marquette State Park, Grant County. Red border of

spots 1 mm. or less wide ; sporules very large, 18-24 x 6-9 /*.

Phyllosticta minima (B. & C.) E. & E. On Acer saccharinum.

Wisconsin river bottoms opposite Bridgeport. On dark brown

spots which become alutaceous except the peripheral portion.

In specimens of what appears to be Phyllosticta decidua Ell.

& Kell, on leaves of Agrimonia striata collected at Long Lake

the older sporules (7-10 x 31/2— 5^) are distinctly brown. In

another collection on the same host, same locality and same day

the sporules (4-7x3/*) have a fuligineous coloration.

Sept or ia epilobii West. On Epilobium adenocaulon. Lady¬

smith. This is the fungus described under this name by Ellis

& Everhart in Journal of Mycology, 3:81.

Davis — Notes on Parasitic Fungi in Wisconsin — IV. 679

Septoria erigerontis Pk. On Erigeron canadense, Long Lake.

There is much diversity in Septoria on Erigeron. In this col¬

lection the pycnidia are scattered through indefinite, somewhat

paler areas which become confluent and mottled with small

(2-4 mm.) indefinite, dead spots before the death of the entire

leaf. The sporules are subarcuate, 21-38x1 %-2/a and appear

rigid. At the other extreme is Fungi Columbiani 1680 on the

same host species with definite small (1 mm.) white-arid, con¬

spicuously bordered spots bearing each one or two pycnidia

containing sporules that are usually narrow (1-1%/x) lax and

thread-like. I have labeled the Long Lake collection var.

effusa n. var.

Phleospora aceris (Lib.) Sacc. On Acer saccharinum. Wis¬

consin river bottoms opposite Bridgeport.

Gloeosporium nervisequum (Fckl.) Sacc. On Platanus oc¬

cidentals. From a tree on the university campus. (H. R.

Rosen.)

Marssonina castagnei (Desm. & Mont.) Magn. On Populus

balsamifera. Laona.

Cylindrosporium saccharinum Ell. & Evht. On Acer spica-

tum. Athelstane. Sporules 30-40 x crescentic, 3-septate,

borne in imperfect pycnidia. Doubtfully distinct from Phleo¬

spora aceris (Lib.) Sacc.

The fungus that was reported in Notes II under the name

Cylindrosporium vermiforme Davis has been collected at Mills-

ton on Corylus americana. The larger sporules are Qy in

diameter.

Bamularia uredims (Yoss) Sacc. On Populus deltoides.

Madison. On Salix cor dad a. Lynxville. Parasitic, together

with Barium filum (Biv.) Cast., on Melampsora.

Ramularia . multiplex Pk. On Vaccinium Oxy coccus. Solon

Springs.

Septocylindrium concomitans (Ell. & Hals.) Hals. On Bidens

vulgata. Ladysmith.

680 Wisconsin Academy of Sciences , Arts, and Letters.

Ramularia virgaureae Thuem. On Solidago altissima.

Lynxville. Well developed conidia are obclavate and some¬

times attain a length of 10(V This fungus varies from an

Ovularia to a Cercosporella type according to the activity of

the abstriction process.

Entyloma compositarum Farl. On Aster macro phyllus. Laona.

Entyloma polysporum (Pk.) Farl. On Rudbeckia hirta.

Athelstane.

Puccinia eatoniae Arth. A specimen of Spkenopholis obtusata

in the herbarium bears this rust. It Was collected by Lapham

at Milwaukee.

Puccinia pat metis Arth. Aecia on Lactuca spicata collected

at Laona are referred to this species.

Puccinia minuta Diet. On Ccvrex (trichocarpaf), Madison.

Puccinia obscura Schroet. Uredinia on old leaves of Luzula

saltuensis in April. Merrimack.

Puccinia pruni-spinosae Pers. On Prunus cuneata. Millston.

Melampsora arctica Rostr. The uredinial stage has been col¬

lected on Salix at Princeton by M. W. Gardner and determined

by J. C. Arthur. Uredinia and telia have also been collected

on Salix pedicellaris and S. discolor at Solon Springs.

Davis — Notes on Parasitic Fungi in Wisconsin — IV. 681

ADDITIONAL SPECIES

Not hitherto recorded as occurring in Wisconsin.

Synch ytrium cellulare n. sp.

Galls of summer sporangia 130-240/x wide x 110-150^ high,

consisting of a central cell surrounded on the sides bj smaller

(30-40 /i) thin walled, superhemispherical cells which form

an investment about two cells thick ; central cell often

divided by a horizontal septum into an empty basal cell

and a larger upper cell which contains the summer sporangia ;

sporangia 30 or more, yellow, spherical to elliptical, 18-26 x 15-

22/l; resting spores globose to\ elliptical, brown, 50-90 x 40-80/x,

single in simple galls but little larger than the spores, and of¬

ten at the base of the summer galls. Amphigenous on the

leaves and on the petioles of Boehmeria cylindrica. This has

been found only at the bottom of a kettle hole in the glacial

drift at Devils Lake. It was first observed in 1913 on the few

plants at the bottom of the kettle hole. In 1914 the quantity

was less and in 1915 but a single infected leaf was seen which

was not disturbed, but in 1916 no trace of the organism was

found and careful search has not revealed it elsewhere. This

recalls the career of Doassansia ranunculina Davis which was

first collected in the early 90 ’s. It increased in abundance and

range year by year until it could be found wherever the host oc¬

curred in any direction within a radius of five miles or more

from, | the city of Kacine. In about ten years it suddenly dis¬

appeared and has not been seen since nor has it ever been re¬

ported from any other locality. I suspect that its extermina¬

tion was due to freezing weather in late spring that killed the

infected leaves.

Aphanomyces phycophila D By.

On Spirogyra spp. indet. Madison (E. M. Gilbert).

What is probably Sphaeria solidaginis Schw. has been col¬

lected on Solidago altissima at Petersburg and Gays Mills. The

character of this production was discussed by Farlow in the

Bibliographical Index, 270-1.

Phyllachora Wittrockii (Erikss.) Sacc. was collected in an

immature condition on Linnaea borealis americana at Solon

682 Wisconsin Academy of Sciences , Arts , and Letters.

Horizontal optical section of summer sorus of Synchytrium

cellulare n. sp. (above) and vertical section of same (below).

Magnified 775 diameters; lower figure reduced.

Drawn by Mabel M. Brown with the aid of camera lucida.

Davis — Notes on Parasitic Fungi in Wisconsin — IV. 683

Springs. Good specimens were collected on Isle Royale, Michi¬

gan, by Stuntz and Allen in 1901.

Exoascus mirabilis Atk. On Prunus americana (cult).

Mountain. Collected also by Prof. L. R. Jones on wild plum

trees at Albion and Rdgerton. Some of the galls bear Monilia

with conidia mostly about 15 x 7-9/x.

Sporonema phacidioides Desm. (Phyllosticta medicaginis

(Fckl.) Sacc.). On Medicago sativa (cult.) as well as the ascig-

erous stage, Pyrenopezixa medicaginis Fckl. Madison, (F. R.

Jones.)

Phyllosticta ivaecola Ell. & Evht. On Iva xanthifolia. Dres¬

ser Junction.

Asteroma tiliae Rud.

On Tilia americana . Bell Center.

Asteroma ribicolum Ell. & Evht. On Ribes americanum.

Lake Mills, Madison and Gays Mills. It has also been observed

in Kenosha county but always sterile whether on living leaves

or on fallen leaves in the spring. Material wintered outdoors

in a wire cage showed no further development in June.

Perhaps this is not distinct from the European Asteroma

umbonatum Desm.

Stagcmospora atriplicis (West.) Lind.

Of a collection on leaves of Chenopodium (Rlitum) capitatum

made at Laona July 14, 1915, the following characters were

noted: Spots light brown, subcircular to irregular, 3-10 mm.

in diameter; pycnidia epiphyllous, scattered, having a thin cel¬

lular wall which is hyaline below and black above especially

about the 'large ostiole, 120-150^ in diameter ; sporules hyaline,

oblong, straight, or sometimes curved, 15-21 x 7-9/x, 1-3 septate.

This I have referred to Ascochyta chenopodii (Karst.) Rostr.

A collection on the same species of host made at Sturgeon

Bay by R. E. Vaughan, August 21, 1913, has smaller, paler

spots, more uniformly colored pycnidia and sporules but 8-15 x

2^2-3^ with one or occasionally two or three septa. This I have

referred to Septoria chenopodii West. Ellis & Everhart N. A. F.

2nd series 3076 issued under the name Septogloeum atriplicis

Desm. with Phyllosticta atriplicis given as a synonym is the

same fungus. It seems not improbable that these are forms of

a single species. [Since this was written I have observed that

684 Wisconsin Academy of Sciences , Arts, and Letters.

Lind unites these, with ( other forms, under the name Stagonos-

pora atriplicis (West.) Lind. (Danish Fungi 2387 p. 444.]

Grove uses Septovia chenopodii West: for the group. ( Journ .

of Bot. 55 : 348)

Stagonospora typhoidearum (Desm.) Sacc. On leaves of

Typha latifolia. Mountain. Sporules 15-20 x 4-5/a about

4-guttulate. Cytoplasm 1-3 times divided when treated with

iodine. Hendersonia typhae Oud. which has been collected on

Typha at Madison is perhaps parasitic.

Stagonospora dearnessii Sacc. On Trifolium repens. Madi¬

son and Athelstane. In these collections the sporules are 1-sep-

tate with occasional 2-3 septate ones. The young sporules con¬

tain 6-8 small guttulae which are larger and 4 in number when

the septum is formed and probably disappear at maturity. I

find the sporules to be uniformly triseptate when brought to

germination. In the original 'description (Stagonospora trifolii

Ell. & Dearn. Phila. Acad. Sci., 1891, p. 82) the sporules are

given as 2-4 nucleate but nothing is said of septa. Since this

was written a collection has been made on Trifolium hybridum

(Hixton, July 7-1916) with sporules 9-14 x 3/a, uniseptate,

rarely biseptate. They are somewhat fusoid while those that

I have seen on T. repens are cylindrical or even somewhat nar¬

rowed in the middle. Of what I take to be a state of this

fungus the following notes were made : Spots lethal brown, im-

marginate, elliptical to oblong or triangular, sometimes con¬

fluent, 3-10 mm. long, the long axis being parallel to the veins ;

pycnidia hypophyllous, scattered, succineous, widely open,

about 100/a in diameter ; sporules mostly bacillary, 3-6 x 1-1%/*

but occasionally ovoid, 2-3x1%/*. Oconto Co., June 25, 1915.

It may be that Phyllosticta trifolii Rich, and Phyllosticta Trifo-

tiorum Barbarine were founded upon something like this which I

take to be a spermogonial condition very similar to Sporonema

phacidioides Desm. on Medicago.

Gloeosporium trifolii Pk. (See p. 674) and Stagonospora

dearnessii Sacc. I take to be congeneric if indeed they are not

more closely related as they may be to the following forms on

clover that have been described: Phleospora trifolii Cav. with

sporules 16-18 x 4-5/a, continuous or with 1-3 indistinct septa

and var. recedens C. Massal. 16-24 x 5-5%/a 1-3 septate;

Ascochyta trifolii Siemaschko, 18-20 x 5-6/* with one or rarely

2-3 septa; Ascochyta trifolii Boud. & Triouss. and Ascochyta

confusa Bubak said by Jaczewski to be probably conspecific

with the foregoing; Stagonospora trifolii Fautrey, 16-22 x 3-4/a,

Davis — Notes on Parasitic Fungi in Wisconsin — IV. 685

3-septate; Stagonospora compta (Sacc.) Died. (Septoria

compta Sacc.) 15-25x4-5/*, pluriguttulate or 4-5 septate.

The economic importance of the clovers js such that we may

anticipate that intensive work will be given to their diseases

and the nomenclature may perhaps be allowed to rest until that

is done.

Septoria sigmoidea Ell. & Evht. On Panicum virgatum.

Lynxville. In these specimens the pycnidia are borne in long

dead leaf areas. The sporules have a fuligenous tint and are

little more than 3/* thick.

Septoria glumarum Pass. On dead, rusted leaves of Triticum

vulgar e (cult.) Athelstane. Sporules 15-36 x 2%-3/a, 1-3

septate as shown by staining. In a collection made at Inde¬

pendence July 29, 1916, the pycnidia are sometimes accompanied

by perithecia that seem referable to Sphaerulina.

Septoria nematospora n. sp. Spots lamphigenous, indeter¬

minate, pale yellow becoming brown, 3-6 mm. long and

of the width of the leaf, often confluent ; pycnidia hypophyllous,

intervenular, dark brown, ostiolate, globose to elliptical, 75-150

x 75-100/a; sporules filiform, somewhat curved, lax, continuous,

eguttulate, 37-55 x 1/2-V* On leaves of Car ex pennsylvanica.

Ladysmith, Wisconsin, July 31, 1915. This was referred to in

“Notes” III, p. 246. While examining the Ladysmith col¬

lection a pycnidium was observed which contained sporules

18-20 x 3-4/*, 3-septate like those noted in the same reference.

Septoria anemones Desm. On Anemone quinquefolia.

Racine. On longitudinal blackish brown areas associated with

an immature Sphaeriaceous fungus.

On looking over some unidentified collections I find one on

cultivated Chrysanthemum made at Racine May, 1894, by F.

L. Stevens which I refer to Septoria rostrupii Sacc. & Syd.

The spots are mostly green, the black, epiphyllous pycnidia

about 90/a in diameter and the sporules 42-48 x 1-2/*, subflexuose^

This is given as a synonym of Septoria chrysanthemella Cav. on

the label of Vestergren’s Micromycetes rariores selecti 1646.

Specimens from an elm in a city lot at Platteville bear

Sacidium ulmi-gallae Kell. & Sw. They were sent by Mr. S.

E. Livingston. The sporules are mostly oval to ovate, 6-9 x4/*.

The host is Ulmus fulva and the accompanying galls are those

caused by Schizoneura americana as I am informed.

686 Wisconsin Academy of Sciences , Arts , and Letters.

Myrioconium comitatum n. sp.

On dead areas that often include the entire leaf. From a

thin, pale, discoid stroma arise erect, simple, hyaline, crowded

basidia, 10-15 x l-iy2^ on which are borne apical, globose*

hyaline sporules 2-3 /a in diameter. These sporules exude m drop¬

let-like masses which dry on the surface of the leaf. The acer-

vuli are usually nervisequent and variable in size sometimes ex¬

ceeding 1 mm. in length. On Populus tremuloides. Mountain,

Long Lake, Wausaukee and Athelstane. On Salix discolor, Athel-

stane. On Salix longifolia , Suring. On Populus the acervuli

are hypophyllous, on Salix epiphyllous. On Populus tremu-

loides this fungus was invariably associated with Sclerotium bi-

frons Ell. & Evht. The midribs of the attacked leaves of Salix

longifolia are black. I am separating the form on Salix as var.

salicarium n. var.

What I take to be a microconidial state of Marssomna

castagnei (D. & M.) Sacc. occurs also on Populus tremuloides

in scattered groups having sporules about 4 x 1/a.

There were collected on leaves of Astragalus canadensis at St.

Croix Falls August 27th, 1914, specimens that have been filed

in the herbarium under the name Gloeosporium astragali ad

interim. The following notes were made: Spots circular,

alutaceous, often zonate, about y2 cm. in diameter; acervuli

epiphyllous, yellowish, 150/a in diameter; sporules ovoid to ob¬

long, hyaline, 4^-8 x 3/a. The sporules are much like those of

Gloeosporium davisii Ell. & Evht. on fruit of Vida americana.

It was not abundant. No Gloeosporium was collected on any

other host in the vicinity. I think it best to consider this as

merely a herbarium name for the present.

Collet otrichum nigrum Ell. & Hals. On Capsicum (cult.)

Milwaukee (R. E. Yaughan).

COLLETOTRICHUM SIEPHII n. Sp.

Spots definite, orbicular, light brown becoming cinereous,

margin darker above, y2~l cm. in diameter, sometimes confluent ;

acervuli epiphyllous, scattered, little or not at all prominent,

about 75/a wide; sporules hyaline, continuous, arcuate, acute at

both ends, 22-27 x 2%-3/a ; setae brown black, sometimes sub-

flexuose, occasionally bent, sometimes 1-2 septate, 36-75 x 4^.

On leaves of Silphium perfoliatum. Lynxville, Wisconsin, Sept.

9, 1915.

Davis — Notes on Parasitic Fungi in Wisconsin — IV. 687

Cylindrosporium eminens n. sp.

Spots suborbicular, brown usually with more or less of a

reddish halo above, dark grey below, 1-2 mm. in diameter;

acervnli epiphyllous, more or less prominent, j75— 100/x wide;

sporules hyaline, straight or curved, becoming pluriseptate, 25-

75 x 2-3 ix. On leaves of HeliantJiemum canadense. Solon

Springs, Wisconsin, Sept. 7, 1914.

Septocylindrium caricinum Sacc. On Car ex grisea. Blue

Mounds.

Ramularia aromatica (Sacc.) Hoehn. (Septocylindrium aroma -

ticum Sacc.). On Acorus Calamus in the experimental drug

garden at Madison.

Ramularia lucidae n. sp.

Spots orbicular to elliptical to angular, castaneous with a

darker periphery and a raised margin, paler and more livid be¬

low, 3-6 mm. in diameter; conidiophores amphigenous but

mostly hypophyllous, densely fasciculate, straight, hyaline,

20-40 x 2-3/a; conidia cylindrical to fusoid-cylindrical, usually

straight, hyaline, guttulate, occasionally showing a median di¬

vision of the cytoplasm, 23-42 x 21^-3/*. On leaves of Salix

lucida. Laona, Wisconsin, July 12, 1915. This differs from

Ramularia rosea (Feld.) Sacc. in the fewer and more definite

spots and the longer conidia.

Heterosporium gracile (Wallr.) Sacc. On Iris (cult.) Madi¬

son (H. W. Browning).

Cercospora nasturtii Pass, was collected on Radicula Nastur-

tium-aquaticum in the Fox river above Burlington in 1908.

Cercospora saniculae n. sp.

Spots angular, limited by the veinlets, at first light sordid

brown, 1-2 mm. in diameter, becoming confluent and blackish

brown; conidiophores hypophyllous, scattered or in small fas¬

cicles of 2-4, straight, simple, continuous, or rarely with 1 or 2

septa, denticulate or subtorulose near the apex, brown, 15-45 x

31/2-6^ ; corQdia narrow obclavate, tapering from near the base,

subolivaceous, indistinctly guttulate, straight or somewhat

curved, 50-110 x 314-4%/a. On Sanicula gregaria. Gays Mills,

Wisconsin, Sept. 15th, 1915.

688 Wisconsin Academy of Sciences, Arts, and Letters.

Ramularia variata n. jsp.

Spots amphigenous, angular, limited in part by the veins,

yellowish brown becoming black, cm. in diameter; coni-

diophores hypophyllous, fasciculate, hyaline, simple, straight or

apical portion oblique, continuous or indistinctly septate, denti¬

culate, 25-45 x 2%-3/a; conidia subapical, catenulate, hyaline,

ovoid to fusoid to cylindrical, continuous or the longest 1-sep-

tate, 10 x 5-30 x 3/a. On Monarda fistulosa. Lynxville, Wiscon¬

sin, Sept. 3, 1915. This is very similar to Ramularia lamiicola

C. Massal. but in the absence of knowledge as to the cause of the

resemblance I am considering the American form on Monarda

as specifically distinct.

In Farlow’s Host Index Mentha canadensis is given as a host

of Ramularia menthicola Sacc. and in the provisional list collec¬

tions on this host were recorded under that name. The Wis¬

consin specimens however as well as those collected in Montana

by E. T. and E. Bartholomew and issued in Fungi Columbiani

4380 I am now referring to the species described above. They

differ from R. menthicola Sacc. as described, in the character of

the spots and in the shorter conidiophores. In the Montana

specimens the spots apparently do not become black as they do

in the Wisconsin ones. It may be that this is not distinct from

Ramularia lycopi Hollos which I have not seen. A word as to

the Monarda host : as it occurs in Wisconsin the under surface

of the leaves bears very^. short (30-40/a), conical, erect hairs that

form a pile that is somewhat velvety to the touch. With these

are much longer white, pilose hairs that are usually few but in

some specimens more abundant.

Cercospora depazeoides Sacc. On Sambucus canadensis.

Grant County opposite Bridgeport.

Cercospora gentianicola Ell. & Evht. On Halenia deflexa.

Solon Springs. The following notes were made from this col¬

lection: Spots dark, indefinite, becoming confluent; conidio¬

phores hypophyllous or epiphyllous, fasciculate from small black

stromatic tubercles, fuligenous to dark brown, straight or more

often more or less flexuose, continuous, entire or denticulate, 10-

40 x 3-4/a; conidia hyaline, obclavate-cylindrical, straight or

curved, becoming tri-sep tate, 40-72 x 3-5/a. I take Cercospora

gentianae Pk. to be a synonym.

Davis — Notes on Parasitic Fungi in Wisconsin — TV. 689

Cercospora crassa Sacc. On Datura Stramonium and Datura

Met el and other species in the experimental drug garden at

Madison. The type of Cercospora daturae Pk. was collected

in June and appears to be a somewhat immature condition of

the same fungus. In the Madison material zonation of the

spots is conspicuous and vertical septa in the conidia are well

developed and the fungus should be referred to Alternaria

[This is Alternaria crassa (Sacc.) Rands. Phytopathology

7:337].

Macrosporium saponariae Pk. which occurs in Wisconsin on

leaves of Saponaria officinalis has not been recorded in any of

the state lists of parasitic fungi.

Ustilago violacea (Pers.) Fekl. was reported in the 4th sup¬

plementary list but was unintentionally omitted from the pro¬

visional list. It has been collected at Racine, Madison, and in

Kenosha county in the anthers of Arenaria lateriflora.

Puccinia uniporula Orton. On Carex gracillima. Racine.

Puccinia karelica Tranz. On Carex paupercula irrigua. Price

and Sawyer counties.

The above species on Carex were determined by Dr. J. C.

Arthur.

SCLEROTIUM DECIDUUM n. sp.

Mycelium hypophyllous, white, branched, continuous (?)

3-4m in diameter, at first effused but soon aggregated into

rounded masses 0.1-3 mm. in diameter. The larger of the

mycelial masses become compacted into grey, globose to elliptical

sclerotia about 2 mm. in diameter which usually fall away be¬

fore mature. The affected leaf areas become pale and dead and

usually studded with brown dots that mark the location of the

mycelial ganglia. This was referred to in the supplementary

list of parasitic fungi of Wisconsin, No. 495, as occurring on

“Silphium, Helianthus, etc.” at Racine. The following hosts

are represented by specimens in our herbaria : Adiantum peda-

tum, Pteris aquilina , Aralia nudicaulis, Mitella diphylla, Dier-

villa Lonicera, Steironema ciliatum, Solidago “canadensis,”

Silphium terebinthinaceum. The paucity of specimens is be¬

cause of falling away of the sclerotia.

UNIVERSITY OF WISCONSIN HERBARIUM,

MADISON, WISCONSIN, APRIL, 1916.

44— S. A. L.

690 Wisconsin Academy of Sciences , Arts , and Letters.

NOTES ON PARASITIC FUNGI IN WISCONSIN— V.

J. J. Davis.

Plasmopara humuli Miyabe & Takahashi which has been re¬

ported as occurring in Racine and Crawford counties was found

in 1916 in Monroe County also. It appears to be indigenous

to Wisconsin.

R. E. Stone has described Mycosphaerella aurea n. sp. as the

ascogenous stage of Septoria aurea Ell. & Evht. {Phytopath.

6:424.)

Hendersonia typhae Oud. is referred to Scolecosporium by von

Hoehnel ( Fragm . zur My hoi. no. 268).

Septoria salicina Pk., as I understand it, appears first as

small scattered round or subangular black spots which increase

in size (2-5 mm.) and more or less of the central portion be¬

comes grey and arid. In this central portion the few hypophyl-

lous pycnidia appear. The deeply lying ones are globose but

those that impinge upon the unyielding epidermis of the host

are flattened thereby so that sometimes they resemble acervuli.

The sporules are arcuately curved, acute, 25-52 (mostly 30-

45) x 2-3//,. They have usually a single median septum but

some of the longer ones have 2 or 3 or even 4. I have seen

this in Wisconsin on Salix lucida only and the herbarium speci¬

mens are on this host or on Salix Fendleriana except North

American Fungi , 2nd series 3064 which is labeled Salix cordata.

Fungi Columbiani 3872 bears much larger zonate spots due

perhaps to the unusual thinness of the leaves of the host.

Gloeosporium boreale Ell. & Evht. (N. Am. Fungi 3279) ap¬

pears to be a small spored form of the same fungus. N. Am.

Fungi 2nd series 3472 issued as Septogloeum salicinum (Pk.)

Sacc. does not seem to differ from Septoria albaniensis Thuem.

Davis — Notes on Parasitic Fungi in Wisconsin — V. 691

which, in the provisional list was included in Septoria salicina

Pk. as a short spored form. Fungi Columbiani 3872 issued as

Septogloeum salicinum (Pk.) Sacc. I would refer to Septoria

salicina Pk. although as noted above the spots are much larger.

N, Am. Fungi 2nd series 3064, F. Col. 3779 & 4387 I would re¬

fer also to this species. They were issued as Septoria solids

West, which I have not' seen but with the description of which

the American specimens do not agree in any respect. None

of the specimens that I have examined bear sporules as long

as is indicated in the description unless they are measured

along the curve. In type material the longest sporule that I

saw was 52** in a straight line connecting the extremities.

[See Dearness, Mycologia 9:359].

Gloeosporium cylindrospermum (Bon.) Sacc. which was re¬

corded as occurring on Alnus incana in Wisconsin in “ Notes’ ’

II is referred to Leptothyrium alneum (Lev.) Sacc. by Diedicke

(Krypt. fl. M. Brandenburg, Pilze 7: 707-8). Klebahn has shown

its connection with Gnomoniella tubiformis (Tode) Sacc.

A fungus on Acer Negundo collected at Whitehall on samaras

and leaves and referred to Gloeosporium apocryptrum Ell. &

Evht. bears sporules 12-15 x 5-6/a.

Pestdlozzia kriegeriana Bres. is placed in the genus Hyaloceras

by Diedicke {Krypt. fl. M. Brand.: Pilze 7: 877).

In the provisional list Ramularia modesta Sacc. was recorded

as occurring in Wisconsin on Fragaria virginiana. The refer¬

ence to this species was because of the small size of the conidia.

In July, 1916, a collection was made on Fragaria virginiana at

Whitehall from examination of which the following notes were

made: Spots suborbicular to angular, brown, paler below,

immarginate, 5-8 mm., sometimes confluent; conidiophores

hypophyllous, fasciculate from a black stromatic base, straight,

simple, septate, tapering upward, olivaceous-brown, 45-75x3 /a;

conidia hyaline, catenulate, 5-11 x 1% x The entry in

the provisional list was based on specimens collected at Spooner

and on referring to them I found the following notes in one of

the packets : ‘ ‘ Hyphae hypophyllous, olivaceous-brown, rigid,

40-70 x 4/a; conidia hyaline, obtuse, catenulate, 6-12 x 2-3/a.

Cercospora vexans C. Massal?” The reference to that species

692 Wisconsin Academy of Sciences , Arts, and Letters.

seems warranted by the description and I have so labeled the

specimens. Ramularia modesta Sacc. should therefore be elided

from the list.

The fungus on Aster given in the provisional list as Ramu¬

laria asteris (Trel.) Barth, appears to be conspecific with Fusi-

dium (?) Asteris Phil. & Plowr. ( Grevillea 6:23) which has

been referred to Ramularia by Bubak (Ann. My col. 6:27). The

name should therefore be written Ramularia asteris (Phil. &

Plowr.) Bubak, as is done by Vestergren in Micromycetes

rariores selecti 1094 except that he followed Saccardo and Bubak

in transposing the names of the authors of the specific name.

By some oversight Urocystis anemones (Pers.) Schroet. was

omitted from the provisional list. I am indebted to Professor

J. Gr. Sanders for calling my attention to the omission. The

smut is common on Hepatica triloba, H. acutiloba and Anemone

quinquefolia and was reported by Trelease in the preliminary

list as occurring on Anemone canadensis.

Aecia of TJromyces were collected on Trifolium pratense and

T. hybridum at Madison by W. H. Davis. They have also been

collected on the latter host at Melvina.

Puccinia bartholomaei Diet, was included in the provisional

list because of an Aecidium on Asclepias syriaca which occurs

in the state which proves however to be connected with Puc¬

cinia seymouriana Arth. instead. (Arthur, Mycologia, 8:134).

My observations both at Bacine and Madison lead me to be¬

lieve that this rust may overwinter on Spartina probably as

mycelium.

Specimens of the Roestelia stage of Gymnosporangium globo-

sum Farl. on Crataegus collected at Maiden Bock and St. Croix

Falls in 1916 have peridial cells but 40-60/* long. Perhaps

the dwarfing was due to the unusually hot weather.

Peridermium comptoniae (Arth.) Orton & Adams was ob¬

served in June 1916 at Millston in Jackson County. Its pres¬

ence is most easily detected after a rain when the fresh son

appear. I find it usually on the east side of the trunk near the

base. In this region rain is usually preceded by easterly winds

hence the fresh sporidia are most likely to be lodged on the east

Davis — Notes on Parasitic Fungi in Wisconsin? — V. 693

side of the trunk when moisture conditions are favorable for

infection. After a rain the basal portion of the trunk remains

moist long after the higher portions have dried off. This has

since been collected in Adams and Juneau counties and its

range in "Wisconsin probably approximates that of the host

Pinus Banksiana.

Peridermium pyriforme Pk. was collected during the same

month at Melvina, Monroe County, and at Millston. As usual,

in my experience in collecting this rust, but a single specimen

was found in each locality.

ADDITIONAL HOSTS

A very scanty development of Bremia lactucae Kegel was ob¬

served at Arcadia on Krigia amplexicaulis.

Plasmopara Jnalstedii (Farl.) Berl. & De Toni on Artemisia

ludoviciana. Taylor.

Peronospora potentillae D By. On Agrimonia striata . Ar¬

cadia.

Peronospora rubi Rabh. On Bub us hispidus. Millston. But

little of the mildew was seen on this host.

JJncinula macrospora Pk. On JJlmus racemosa. St. Croix

Falls.

Taphrina coerulescens (Desm. & Mont.) Tul. On Quercus

macrocarpa Granville. (I. A. Lapham, 1867.)

PJiyllosticta decidua Ell. & Kell. On Agrimonia gryposepala.

Arcadia. Sporules 4-5 x 2%-4/*, fuligenous tinted.

Ascochyta wisconsina Davis. On Sambucus racemosa. Lynx-

ville.

Diplodia uvulariae Davis. On Uvular ia grandiflora. Maiden

Rock. This collection bears mostly pycnidia containing

sporules 4-5 x lv which I take to be a spermogonial state. The

Diplodia is immature, the sporules being still hyaline and but

few of them septate.

694 Wisconsin Academy of Sciences, Arts, cmd Letters .

Septoria graminum Desm. On leaves of Bromus altissimns.

Maiden Rock.

Septoria polygonorum Desm. On Polygonum pennsylvanicum.

Lynxville. Spornles np to 60 fi long.

Septoria lepidiicola Ell. & Mart. On leaves of Lepidium

apetalum. Sparta.

Septoria solidaginicola Pk. On Aster azureus. Danbury.

In “Notes” III p. 259, reference was made under Gloeospor-

ium caryae Ell & Dearn., to an epiphyllous form on Cary a cordi-

formis and I find a collection of the same kind made at Rich¬

land Center on Carya alba by R. A. Harper & 0. M. Reed.

This is Phyllosticta caryae Pk. but in both the Wisconsin and

New York material the sporules arise from a subcuticular stroma.

Colletotrichum lagenarium (Pass.) Ell. & Hals. On Cucur¬

bit a Melo (cult.) Madison. On Cucumis sativus (cult.) Prince¬

ton (M. W. Gardner.)

Cylindrosporium vermiforme Davis. On Corylus rostrata.

Cameron. A collection of this fungus from Danbury shows

globose swellings up to 20^ in diameter in the continuity of the

conidia. These vesicles are rich in cytoplasm and suggest

chlamydospore formation.

j Ramularia desmodii Cke. On Desmodium pawiculatum.

Maiden Rock.

Ramularia lysimachiae Thuem. On Steironema lanceolatum.

Lynxville.

Cercospora circumscissa Sacc. On Prunus pennsylvanica.

Neopit and Blair. On Prunus serotina. Athelstane and Alma.

Entyloma australe ' Speg. On PJiysalis pubescens (cult.)

Waupaca. (R. D. Rands).

Entyloma polysporum (Pk.) Farl. On Ambrosia trifida.

Maiden Rock. Forming definite, orbicular, yellow, somewhat

thickened spots about 5 mm. in diameter.

Uromyces proeminens DC. On Euphorbia dentata. Lynx¬

ville. This is Z7. poinsettiae Tranz.

Davis — Notes on Parasitic Fungi in Wisconsin — V. 695

Puccinia coronata Cda. On Cinna arundinacea. Lnck.

Puccinia graminis Pers. On Bromus secalinus. Independence.

Puccinia koeleriae Arth. Aecia (Aecidium liatridis Ell. &

And.) on Liatris scariosa. Solon Springs, Millston and Hixton

and in small quantity on Liatris cylindracea at Millston. Ure-

dinia and telia on Koeleria crist at a Millston. In the description

the aecial host was given as Mahonia but Bethel has established

the connection here given.

Puccinia patruelis Arth. Uredinia and telia on Car ex siccata.

Black Biver Falls. Field observation indicated that the aecia

connected with this collection were borne on Krigia amplexi-

caulis.

ADDITIONAL SPECIES

Plasmopara acalyphae G. W. Wilson.

Because of the discovery of a trace of this mildew Acalypha

virginica was interrogatively given as a host of Peronospora

euphorbiae Fckl. in the provisional list. As stated in “Notes”

II (1914) but a single additional conidiophore had been found

up to that time. In 1915 however, enough was secured to show

that it is an undescribed species of Plasmopara and it was sent

to Prof. Guy West Wilson, who has given special attention to

the Peronospordles, for description and publication. In 1916

still further material was secured. [See Mycologia 10:169.]

In “Notes” III, p. 252, mention was made of a Lophodermium

on Pinus Banksiana differing from L. pinastri (Schrad.) Chev.

A number of collections of this were made in 1916 which show

that it is constant and distinct, differing from Hypodermella, as

characterized by Lagerberg, only in the broad perithecia.

Lophodermium amplum n. sp.

On sordid spots or terminal leaf areas; perithecia amphi-

genous, prominent, black, elliptical, y2- 1 mm. long; asci cylin¬

drical to clavate-eylindrieal, narrowed at the apex, sometimes

696 Wisconsin Academy of Sciences , Arts, and Letters.

curved, 90-165 x 18-30/a; spores embedded in mucus, overlap¬

ping, hyaline, continuous, attenuate at base, clavate-cylindri-

cal, rarely fusoid-cylindrical, 30-72 x 3-6/a; paraphyses num¬

erous, filiform, a little longer than the asci. On leaves of Pinus

Banksiana. Museoda, Sparta, Millston, Black River Falls,

Taylor, Gordon. May to July. Lophodermium pinastri

(Schrad.) Chev. occurs on this host in Wisconsin, on dead, fallen

leaves, while L. amplum develops on leaves that are, in part,

living or that are in situ. What relation this bears to the Hy-

poderma desmazieri Duby reported by Peck as occurring on

leaves of Pinus rigida in New York I do not know.

Lophodermium linear e Pk. On Pinus Strobus. Pembine.

Coccochora rubi sp. nov. Stromata epiphyllous, scat¬

tered, black, shining, prominent, suborbicular, subcuticular,

%-! mm. in diameter ; loculi one to several, 45-60/a high, 60-90/*

wide, opening at the apex; asci cylindrical, more or less curved,

45-50 x 7-9/*, octosporous ; spores brown, clavate-oblong, with a

single septum which is more or less submedian, not constricted,

11-15 x 4—6/* ; paraphyses filiform, inconspicuous. On leaves of

Rubus hispidus, Millston, Wisconsin, August 19, 1915, and July

19, 1916. Small stromata containing but a single locule are

subhemispherical, the larger compound ones, which are some¬

times circinate, are tuberculate. The adnate clypeus is large

and merges into the normal cuticle at the edge. This fungus

suggests Asterina rubicola Ell. & Evht. when seen in the field.

In the provisional list hosts were not enumerated under Phyl-

lachora graminis (Pers.) Fckl. In Annates Mycologici 13:436

et seq. Theissen and Sydow have divided this into a large

number of species. More knowledge of their biological rela¬

tions is needed for a satisfactory classification of the North

American forms. It may be of service to give some notes of

measurements of asci and spores taken from Wisconsin speci¬

mens.

Elymus: Asci 66-75 x6-7/a; spores 8-9x4%-6/a. Theissen

& Sydow take a specimen on this host genus as the type of

Phyllachora graminis (Pers.) Fckl. with characters with which

these measurements agree except that the asci of the type are

thicker (8-10/a).

Hystrix patula: Asci 66-79 x 6-9/a; spores 8-12 x 5-6/*. This

Davis— Notes on Parasitic Fungi in Wisconsin — V. 697

seems to be so like the form on Elymus as to indicate specific

identity. There is a Phyllachora asprellae Roum. & Fantr. in

France the asci and spores of which are described as being larger.

Panicum latifolium: Asci 65-80x9 /a; spores 8-9 x 4-5/*. A

later collection : Asci 60-70 x 8-12/* ; spores 9-11 x 5-6//,.

Panicum huachucae: Asci 50-60 x 6-9/a; spores 8-9 x 4-5/*.

Panicum sp. indet. : Asci 57-63 x 9/a ; spores 7-9 x 5/*. The

Panicum specimens appear conspecific and are what has been

distributed in this country as Phyllachora graminis var. panici

(Schw.) Shear. If they belong with any of the species de¬

scribed by Theissen & Sydow as occurring on Panicum it is

probably thq South American Phyllachora panici (Rehm).

Muhlenbergia: Asci 50-67x5-6/*; spores 6-8 x 4/a. This is

probably Phyllachora vulgata Theiss. & Syd. (loc. cit. 450).

Agropyron repens: Asci 60-80x6-8/*; spores 8-12 x 4-5/a.

Calamagrostis canadensis: Asci 51-72 x 5-6/a; spores 7-9 x

5-6/*. Phyllachora has been observed in northern Wisconsin on

Oryzopsis asperifolia but no mature specimens have been pre¬

served. This is presumed to be Phyllachora oryzopsidis Theiss.

& Syd. (loc. cit. 451).

Taphrina coryli Nishida. On leaves of Corylus americana.

McFarland, Madison, Sparta, Melvina, Hixton, Taylor, Blair,

Whitehall. In 1916 this was found scattered about through

the woods in western Wisconsin in a way that left no room for

doubt as to its being indigenous. The appearance in the field

suggests Microsphaera.

Of a collection on leaves of Echinocystis lobata made at White¬

hall, July 28, 1916, the following notes were made: “ Spots

suborbicular, immarginate, pale brown, y2-l cm. in diameter;

pyenidia scattered, lenticular, succineous, ostiolate, 75-100/a;

sporules hyaline, oval to oblong, 4-8 x iy2-S^. Accompanying

Plasmopara australis (Speg.) Swingle and perhaps secondary.”

I have referred it to Phyllosticta orbicularis Ell. & Evht.

Sphaeropsis betulae jCke. var. 'foliicola n. var. On large,

light brown dead leaf areas; pyenidia mostly epiphyllous, scat¬

tered or aggregated, blackish brown, depressed-globose, black¬

ened about the ostiole, 100~150/a; sporules oblong with rounded

698 Wisconsin Academy of Sciences , Arts , and Letters.

ends, usually straight, continuous, fuligenous to brown, 18-24

x9/*. On leaves of Betula alba papyrifera. Maiden Rock,

Wisconsin, August 5th, 1916.

Ascochyta graminicola Sacc. On leaves of Calamagrostis

canadensis. Maiden Kock. Of this collection the following

notes were made: Spots definite, sordid white, purple bor¬

dered, oval to oblong, 5-8 mm. long, sometimes confluent;

pycnidia numerous, depressed-globose, wall thin, parenchyma¬

tous, ostiole surrounded by a black ring, about 120/a in diameter ;

sporules hyaline, fusiform, acute, at both ends, uniseptate, 15-20

x 21/2-3/*. The sporules resemble those of Darluca filum (Biv.)

Cast.

Specimens on Actaea rubra collected at Blair, July 17, 1916,

have the following characters : On indefinite, blackened, dying,

areas of the leaves the cuticle on the upper surface of which is

sometimes wrinkled in dendritic lines ; pycnidia mostly epiphyl-

lous, scattered, amber colored, globose, about 100/a in diameter;

sporules hyaline, cylindrical, uniseptate, 17-24x5-6/*. The

pycnidial wall is at first hyphal but at maturity consists of a

single layer of flat polygonal cells and is not thickened around

the ostiole. This appears to be Actinonema actaeae (Allesch.)

Died. Stagonosporopsis actaeae (Allesch.) Died, and probably

Mar sonia actaeae Bres. which is Marssonina actaeae (Bres.)

Magn. It differs from Ascochyta clematidina Thuem. in the

size of the sporules as the latter does from the form on Thalic-

trum that I have called var. thalictri (Trans. Wis. Acad.

16:557). I have labeled the specimen Ascochyta actaeae

(Bres.) n. comb. These three forms are so similar that it seems

to me that it would be proper to indicate the fact by group¬

ing them in a single species. On Thalictrum the sporules are

8-10 x 2-3/a, on Clematis 10-15 x 3/*, on Actaea , 17-24 x 5-

6/*. Such series on the same or on related hosts seem to be not

uncommon, but there appears to be no way in the present state

of taxonomy to indicate the relationships by grouping them,

especially as increased spore length often brings increased septa-

tion and thereby passes generic limits as now understood.

Ascochyta imperfecta Pk. On Medicago sativa (cult.) Madi¬

son. Sporules 8-11 x 3-3%/a.

Davis — Notes on Parasitic Fungi in Wisconsin — V. 699

Ascochyta cucumis Fautr. & Roum. On Cucumis sativus

(cult.) Platteville. (E. Carsner, com. M. W. Gardner.)

There are in Wisconsin a number of foliicolous Sphaerioi-

daceae that constitute a definite group as seen in the field. They

cause blackish brown spots of subcircular form but irregular

outline with more or less black crustaceous thickening of the

upper surface. The pycnidia are innate, inconspicuous, few,

scattered, pale, thin walled with the ostiole directed toward

the upper surface of the leaf, 100-150/* in diameter and can

often be distinguished with a strong hand lens and good trans¬

mitted light, especially if the leaf is wet. The sporules are

cylindrical with rounded ends and septate. It is in the size

and septation of the sporules that variation occurs. What the

relation of these forms to each other may be is for the future

to disclose through field observation and artificial infection.

In the meantime some means of designation is needed and I

have tentatively arranged them as follows :

Stagonospora apocyni (Pk. ?) n. comb. Spots definite, im-

marginate, subcircular, reddish brown, somewhat paler below,

1-2 cm. in diameter ; pycnidia few, scattered, epiphyllous-innate,

globose, succineous, thin walled, becoming more or less thickened

and blackened about the ostiole; sporules hyaline, fusoid-cylin-

drical, 3^-7 septate with a large droplet in each cell, 33-50 x 6/*.

On leaves of Apocynum androsaemifolium. This is the fungus

recorded under the name Septogloeum apocyni Pk. in the provi¬

sional list. The material at hand of that species, on Apocynum

cannabinum does not enable me to determine whether that is also

a Stagonospora. Certainly the sporules are similar.

Next comes a form on Cirsium.

Stagonospora cirsii n. sp.

On circular brown or cinereous spots, often with a whitened

center y2-l cm. in diameter or on large brown areas; pycnidia

few, scattered, innate, depressed-globose, brown, ostiolate, 125-

150/* in diameter; sporules cylindrical, ends rounded, straight

or slightly curved, hyaline, 2-5 septate, not constricted, 20-32

x 5-6/x. On Cirsium altissimum. Maiden Rock, Wisconsin,

August 7th and 16th, 1916.

Next is Ascochyta lophanthi Davis (Trans. Wis. Acad. 14:95)

on Agastache scrophulariaefolia with uniseptate sporules 20-30

x 10-12/*.

700 Wisconsin Academy of Sciences , Arts, and Letters.

var. osmophila n. var.

Spots like those of the type ; sporules uniseptate 12-21 x 3-5/a.

On Agastache Foeniculum. Danbury.

var. lycopina n. var.

#

Spots suborbicular to angular, blackish brown above, lighter

below, immarginate, 3-10 mm. in diameter; pycnidia few, scat¬

tered, innate, ostiole directed toward the upper surface of the

leaf, very inconspicuous; sporules hyaline or smoky tinged,

cylindrical with rounded ends, uniseptate, 16-24 x 7-8/*. On

Lycopus uniflorus. Shiocton, Wisconsin, August.

Collections on Sanicula marilandica having uniseptate

sporules 20-30 x 4-6/a were described in Trans. Wis. Acad.

181:105, under the name Ascochyta saniculae n. sp. The af¬

fected leaf areas are usually larger and less definite in the form

on this host. This has also been collected on Zizia aurea at

Melvina. On this host definite orbicular to elliptical olivaceous

spots y2-l cm. long occur. Both of these probably should be

referred to Ascochyta thaspii Ell. & Evht. the sporules of which

were described as being 25-30 x 6-8/*. In the Wisconsin speci¬

mens on Zizia the sporules are 18-25 x 4—6/a and are perhaps

immature.

Next comes a form that may be designated

Ascochyta compositarum n. sp. Forming large indefinite

brown areas and also smaller more definite spots about

1 cm. in diameter; pycnidia as in the previously mentioned

forms ; sporules hyaline, uniseptate, 15-22 x 4-6/a. On Eupa-

torium urticaefolium, Helianthus strumosus and Aster Drum-

mondii. Of one specimen on the former host it was noted

“ sporules not well developed, 12-16 x 3-4/a.’ 9

Yar. parva n. var.

Character of the species except that the sporules are but

about 10-15 x 2^-3%/*, uniseptate. On Helianthus strumosus.

Maiden Rock. t

It is probable that this species occurs upon other Composites

and that A. thaspii E. & E. will be found on other TJmbelliferae.

Indeed I have seen the latter on Cicuta maculata but did not

secure enough, for a specimen.

Ascochyta, treleasei Sacc. & Yogi, the types of which were

collected in Wisconsin on Silphium and Vernonia I have not

Davis— Notes on Parasitic Fungi in Wisconsin — V. 701

seen but the small spots and proportionately broader sporules

described have deterred me from referring these collections to

that species.

Stagonospora zonata n. sp. Spots orbicular, clay colored

with concentric dark lines, y2- 2 cm. in diameter; pycni-

dia few, epiphyllons-immersed, depressed-globose, honey color,

ostiolate, 120-180/* in diameter; sporules oblong to cylindrical,

hyaline, 4-guttulate becoming 3-septate, not constricted, 12-25

x 3^-6/*. On living leaves of Asclepias syriaca. Indepen¬

dence, Wisconsin, July 29, 1916; Arcadia, Wisconsin, July 31st,

1916. Perhaps this is a better developed state of Ascochyta

asclepiadis Ell. & Evht.

Septoria mitellae Ell. & Evht. On <(Mitella or Tiarella.”

Merrimack. Name of collector not given.

Septoria stachydis Rob. & Desm. On Stachys tenuifolia. Mel-

vina.

Septoria krigiae Dearn. & House. Spots definite, suborbicu-

lar, reddish brown, paler in the center, 3-8 mm. ; pycnidia epiph-

yllous, scattered, black, prominent, 50-75/*; sporules hyaline,

straight or sometimes curved, 18-27 x %-l /*. On leaves of

Krigia amplexicaulis. Arcadia.

Cytodiplospora elymina n. sp. Pycnidia in the loculi

of Phyllachora , spherical to elliptical, 100-135/*; sporules

oblong, hyaline, often 4-guttulate, becoming uniseptate, 7-10

x 23/2-3/*. On leaves of Elymus virginicus. Madison. This

is doubtless a spermogonial state of the Phyllachora.

Gloeosporium leptospermum Pk. On Pteris aquilina; accom¬

panying Phyllachora. Whitehall. The longest sporules attain

30/* and the thickest 5/*.

Collet otrichum circinans (Berk.) Yogi. Reported as occur¬

ring on onion bulbs in Wisconsin. ( J. C. Walker)

Marssonina rubiginosa Ell. & Evht. On Salix sp. indet.

Madison.

Monilia corni Reade. On petioles, midribs and peduncles of

Cornus paniculata. Melvina. The fungus is apparently locally

abundant on this species of host but I found conidia but once.

702 Wisconsin Academy of Sciences , Arts , and Letters.

Ovularia rigidula Delacr. On Polygonum erect urn. Black

Elver Falls and Sechlerville.

In the Wisconsin collection I find the conidiophores 24-70 x

3-4/*. Ovularia avicularis Pk. does not seem to be separable.

I find amphigenous conidiophores- on European material (Jaap,

F. selecti exsic. 291).

Eamularia dispar n. sp. On small indeterminate leaf

areas which become yellowish and finally dead and brown ; coni¬

diophores hyaline, lax, mycelioid, often ascending the trichomes ;

conidia lateral in branched chains, hyaline, cylindrical, suba¬

cute, becoming 1-3 septate, 18-33 x 2y2-3y2fi. On leaves of

Eupatorium purpureum. Danbury, Wisconsin, August 30,

1916. This is of the aberrant character of Cercosporella tricho-

phila Davis and suggests Sporotrickum in habit.

Cladosporium humile n. sp. Spots dark reddish brown above,

plumbeous below, suborbicular to polygonal, 2-10 mm. in

diameter, sometimes confluent ; conidiophores epiphyllous,

most arising from small black pseudostromata of loose

texture, erect or assurgent, dark brown, usually septate and

often constricted at the septa, straight, flexuous or geniculate,

10-35 x 3-5/* ; conidia fuligenous, catenulate, oblong to fusoid-

cylindrical, usually straight, becoming, in part at least, unisep-

tate, 15-37 x 4/*. On leaves of Acer rubrum. Luck, Wiscon¬

sin, August 25, 1916. The spots appear to be made up of small

black intervenular areas some of which are apparent at the

periphery and others altogether detached. It may be that this

fungus is secondary. [This has since been collected on Acer

saccharinum at Plover and Arcadia] .

Cercospora velutina Ell. & Kell. On Baptisia leucantha.

Lynxville. In these specimens the conidiophores are borne on

the lower surface of orbicular spots 3-10 mm. in diameter which

are sometimes confluent and the tubercles are scarcely present.

The conidiophores are 30-60 x 2-3 /x, fasciculate from a stromatic

base and usually somewhat curved.

Cercospora longispora Pk. On Lupinus perennis, Millston.

Cercospora polytaeniae Ell. & Kell. On Polytaenia Nuttallii.

Sparta. The conidiophores of this species were described as

4 ‘very short. ’ ’ In this collection I find them 30-60 x 5/x, flexuous

Davis — Notes on Parasitic Fungi in Wisconsin — V. 703

or geniculate, becoming denticulate and developing one or two

septa.

Alternaria soncki Davis. Parasitic on leaves of Sonchus asper.

Madison. The description was published by John A. Elliott

in the Botanical Gazette, 62: 416 (1916).

TJromyces murrillii Ricker. The aecial stage, Aecidium hous-

toniatum Schw., has been collected on Houstonia longifolia at

Solon Springs and Millston but the further stages on Sisyrin -

chium have not yet been detected in Wisconsin. This is TJromy¬

ces houstoniatus J. L. Sheldon, a name that violates the rule that

I am following.

TJromyces- striatus Sehroet. Uredinia on Medicago sativa

(cult.) Weirgor. (F. R. Jones).

Puccinia eriophori Thuem. Following field observations by

Dr. House it has been shown by Dr. Arthur by means of in¬

oculation that the rust on Eriophorum is distinct from that on

species of Scirpus and known as Puccinia angustata Pk. and

that it developes aeeia on Senecio. Aecia on Senecio aureus

have been collected in widely separated localities in Wisconsin

and Dr. Arthur reports a collection of the rust on Eriophorum

virginicum at Elm Grove by Dr. C. L. Shear.

Cronartium ribicola Fisch. de Waldh.. The dreaded white

pine blister rust has been found on Pinus Strobus in Polk

County. Specimens of the aecial stage were collected by Moody,

Sanders & Pierce in May, 1916, and Professor J. G. Sanders

kindly furnished specimens of uredinia on Ribes cynosbati col¬

lected in June.

Aecidium uvulariae Schw. On Oakesia sessilifolia. Melvina

and Hixton. I suspect that this is not distinct from Aecidium

majanthae Schum. and that it is connected with Puccinia ses-

silis Schneid.

In the 3rd supplementary list (Trans. Wis. Acad. 14:92)

reference was made to the occurrence of a Doassansia on Sagit -

taria heterophylla that was referred to Doassansia sagittariae

(West.) Fisch as forma conftuens with the statement that it ap¬

peared to be physiologically distinct which opinion has been

supported by subsequent observation. Morphologically, however,

704 Wisconsin Academy of Sciences , Arts , and Letters.

I am not able to distinguish it from forms on Sagittaria latifolia,

S. arifolia and S. sagittifolia with crowded and distorted sori.

In the summer of 1916 collections were made of what proved to

be a quite different type on Sagittaria keterophylla.

Doassansia (doassansiopsis) furva n. sp.

Spore balls in the leaf blades, loosely clustered, discrete,

brown-black, spherical to oval, 100-150/* long ; spores in a single

layer surrounding the sterile parenchymatous central portion,

rounded-cuboidal, 8-10 /a long ; cortical cells inconspicuous,

plano-convex to flattened, 6-9/* wide by 1-3/a high. In leaves

of Sagittaria heterophylla. Arcadia, Wisconsin, July 31st and

August 2nd, 1916. This differs from Doassansia martianoffiana

(Thuem.) Schroet. in the darker color, habitat and probably in

the absence of conidia; from D. deformans Setch. in the much

darker sori, part of the host attacked and in not causing hyper¬

trophy. In color and to some extent in structure it recalls

Doassansia zizaniae Davis (Bot. Gaz. 26:353) which was re¬

ferred to Sclerotium in the provisional list and suggests that

that is also a member of this group.

UNIVERSITY OF WISCONSIN HERBARIUM,

MADISON, WISCONSIN, APRIL, 1917.

Davis — Notes on Parasitic Fungi in Wisconsin — VI. 705

NOTES IN PARASITIC FUNGI IN WISCONSIN-VI

J. J. Davis.

A provisional list of parasitic fungi in Wisconsin was pub¬

lished in the Transactions of the Wisconsin Academy of Sciences

Arts and Letters 172 : 846-984 [1914]. Notes bearing a supple¬

mentary relation thereto were issued through the same medium :

181: 78-109 and 251-271 [1915] : 19:

In the provisional list Urophlyctis major Schroet. was given

as occurring on Rumex verticillatus. All of the Wisconsin

specimens appear to be on R. Britannica.

Peck should be cited as the author of the binomial Phyllosticta

hamamelidis, not Cooke as given in the provisional list.

The merging of Marssonina castagnei (Desm. & Mont.) Magn.

with M. populi (Lib.) Magn. by Lind ( Danish, Fungi , 2761) did

not surprise me and I am now using the latter name, instead

of the former.

The classification of Septoria on Solidago, Aster and Erigeron

is in an unsatisfactory state and probably will remain so until

aided by the results of investigation by inoculation methods. A

collection on Solidago serotina (Adams, June 21, 1917) that I

have referred to Septoria davisii Sacc. bears sporules 42-75 x

1%-2/a.

The sporules of Septoria bacilligera Wint. as it occurs in Wis¬

consin are not typical. I find them to vary from 10-50 x 1-2/x.

Haymaker who has made studies of Monilia at the University

of Wisconsin considers the forms on Prunus serotina and P. vir-

45 — S. A. L.

706 Wisconsin Academy of Sciences , Arts, and Letters .

giniana in the vicinity of Madison identical, conforming to the

description of Monilia angustior (Sacc.) Reade.

The Monilia on plum fruit given as M. fructigena Pers. in

the provisional list is now referred to M. cinerea Bon. It is

sometimes abundant on “plum pockets” on Prunus americana

and P. nigra.

The Mucedine on Ranunculus abortivus recorded as Sep -

tocylindrium ranunculi Pk. in the provisional list I am now

referring to Ramularia aequivoca (Ces.) Sacc. together with

specimens on Ranunculus septentrionalis from Madison and St.

Croix Falls. On the latter host the conidiophores are in larger

fascicles from a stromatic base as in the type of Septocylind-

rium ranunculi Pk. and Ramularia acris Lindr. Both of these

are on Ranunculus acris and they seem to be identical. Fer-

raris (FI. Ital. Crypt.: Hyphales: 800) distinguishes R. acris

Lindr. from R. aequivoca (Ces.) Sacc. by the longer (30-60/0

conidiophores but the distinction does not hold in Mycotheca

Germmica, 1286. I have seen no specimen of Ramularia sceler-

ata Cke.

In the description of Cercosporella filiformis Davis (Trans.

Wis. Acad. 181: 266) the maximum length of the conidia should

be increased to 100/x as shown by specimens collected at Hixton

in July 1916.

Instead of Cercospora leptosperma Pk. or Cylindrosporium

leptospermum Pk. I am now using Cercosporella leptosperma

(Pk.).

Fusarium Jieterosporum Nees is referred to F. graminum Cda.

by Ferraris (FI. Ital. Crypt.: Hyphales : 90) .

Puccinia claytoniata (Schw.) Syd. (P. mariae-wilsoni Clint.)

seems also to have been omitted from the provisional list. Aecia

and telia occur in Wisconsin on Claytonia virginica as was stated

in the supplementary list.

Davis— Notes on Parasitic Fungi in Wisconsin— VI. 707

ADDITIONAL HOSTS.

Albugo Candida (Pers.) 0. Kuntze. On Arabis canadensis .

Friendship.

Plasmopara halstedii (Farl.) Berl. & DeToni. On Ambrosia

psilostackya. Adams.

Peronosporai trifoliorum D By. On Lupinus perennis. Mill-

ston.

Lophodermium pinastri ( Schrad. ) Chev. On Finns resinosa.

Black River Falls.

Pseudopeziza autumnalis (Fckl.) Sace. On Galium Claytoni.

Shioeton. This fnngns was erroneously listed as Ps. repanda

in the provisional list.

Exoascus communis Sadeb. On fruit of Prunus pumila.

Two Rivers.

Phyllosticta cruenta (Fr.) Kickx. On Polygonatum com -

mutatum. Darwin. In this collection the sporules are 13-21 x

A-6/x. The spots appear to have been caused by leaf miners and

have a very narrow border.

Phyllosticta decidua Ell. & Kell. On Galeopsis Tetrahit ac¬

companying Septoria galeopsidis. Kewaunee. That this is dis¬

tinct from species that have been described as occurring on

Labiates in Europe seems open to question. In this collection

the sporules are 6-9 x 2^-3^ often contain 2 or 3 guttulae and

not infrequently there is a median division of the cytoplasm.

On Humulus Lupulus. Black River Falls.

Ascochyta thaspii. E. & E. var. lycopina*

Spots suborbicular to angular, blackish brown above, lighter

below, becoming paler in the center, immarginate, 3-10 mm. in

diameter; pycnidia few, scattered, usually innate, ostiole di¬

rected toward the upper surface of the leaf, very inconspicuous ;

sporules hyaline or smoky tinged, cylindrical with rounded ends,

uniseptate, not constricted, 16-24 x 7-9^. On leaves of Ly copus

uniflorus. Two Rivers, July, Shioeton, August, 1917.

Darluca filum (Biv.) Cast. In telia of Kuehneola uredinis

on Rubus hispidus , Millston and those of Puccinia curtipes Howe

on Heuchera hispida. Hixton. These are the only exceptions

* Duplication of v. 700.

708 Wisconsin Academy of Sciences, Arts, and Letters.

that I have seen to the rule that this parasite is confined to ure-

dinia.

Stagonospora smilacis (Ell. & Mart.) Sacc. On Smilax

ecirhata. Shiocton. Immature. Sporules continuous, 10-12 x

5-6/a.

Specimens on leaves of Triticum vulgar e (cult.) collected at

Madison seem to me to be referable to Septoria agropyri Ell. &

Evht. The pycnidia are globose to oval, 75-100 x 60-90/a;

sporules 15-40 x 1-1 %/a.

A Septoria on leaves of Secale cereale (cult.) collected at Lyn¬

don Station I have referred to S. passerinii Sacc. The pycnidia

are scattered over more or less elongated, light yellow areas, are

black and about 100/a in diameter; sporules straight or curved,

acute, continuous, 30-42 x 1%/a. The distinctness of this and

the preceding seems to be questionable.

Septoria caricinella Sacc. & Roum. On Car ex cephalophora.

Seymour.

Phleospora aceris (Lib.) Sacc. On Acer saccharinum. Grant

county and Shiocton.

Leptothyrium dryinum Sacc. On Quercus ellipsoidalis. Lyn¬

don Station. Sporules about 17 x 9/a.

Gloeosporium confluens Ell. & Dearn. On Sagittaria arifolia.

Shiocton.

Collet otrichum graminicolum (Ces.) Wilson. On Calama-

grostis camadensis. Spooner. Bromus altissimus. Plover.

Septogloeum salicinum (Pk.) Sacc. On Salix rostrata. Dan¬

bury. Salix discolor . Shiocton. What I take to be a micro-’

conidial state, bearing sporules 4-8 x 1/a, has been collected at

Danbury.

Monilia has been collected at Madison on Amelanckier ob-

longifolia with conidia 8-15 x 6-12/a. Its relationships are not

clear.

Eamularia alismatis Fautr. On Sagittaria heterophylla. Ar¬

cadia. While this mucedine is not uncommon on Alisma and

Alisma and Sagittaria frequently grow together I have seen the

parasite on Sagittaria but once and then not in abundance.

Cercospora dubia (Riess) Wint. On CJienopodium capitatum.

Shiocton. I do not find that the distinctions drawn by Bubak

between this species and C. chenopodii Fresen. {Ann. Mycol.

Davis — Notes on Parasitic Fungi in Wisconsin — VI. 709

6:28) hold in Wisconsin. The collection on this host is more

of the G. chenopodii type.

Cercospora absinthir (Pk.) Saec. On Artetinisia Absinthium.

Casco.

Doassansia sagittariae (West.) Fisch. On Sagittaria arifolia

Shiocton and Racine.

Gymnoconia peckicma (Howe) Trotter. Caeoma on Rubus

hispidus. - Necedah.

Cronartium quercus (Brondeau) Schroet. Uredinia on Quer-

cus bicolor and Q. ellipsoidalis. Necedah. Telia on Q. macro-

carpa, Q. rubra and Q. ellipsoidalis. The latter is the most com¬

mon host of the telia in Wisconsin.

Peridermium comptoniae (Arth.) Orton & Adams. On Pinus

austriaca in the state nursery on Trout lake in Vilas county.

ADDITIONAL SPECIES.

Physoderma vagans Schroet. To this species I am provision¬

ally referring specimens on leaflets of Sium cicutaefolium col¬

lected in August, 1917 at Shiocton. The galls are round to el¬

liptical, prominent, 1-2 mm. long; the resting spores 1-8 in

each cell, globose to elliptical, 18-21 x 14-18/* with walls about

3/* thick. The host cells become inflated and rounded (up to

70 x 50/*) the walls thin, fuscous and having a chitinoid appear¬

ance.

Plasmopara cephalqphora n. sp. Conidiophores hypophyl-

lous, effused, stout, straight, often clavate, 150-270 x 6-14/*, sim¬

ple to the apex which is divided into a few short (6-15/*) stout

branches which are irregularly divided into the ultimate branch-

lets which are terete, straight, truncate sometimes swollen at the

apex; conidia hyaline, elliptical to oblong-fusoid, more or less

acute at each end, flattened on one side, stipitate, furnished with

an apical papilla, 45-70 x 20-33/*. On leaves of Physostegia

pwrviflora. Shiocton, Plover and Dexterville, August, 1917. The

conidia are imbricated in a compact head, bending of the pedicel

(about 3/* long) allowing adjustment of position under pressure.

The flattening of the conidia is perhaps the result of crowding ;

at least it facilitates close packing.

710 Wisconsin Academy of Sciences, Arts, and Letters.

This mildew is near Basidiophora which it resembles in the

position of the conidia and the character of the basidia but dif¬

fers in the apical portion of the conidiophore not being abruptly

swollen and rounded, but branched or cleft. In the Dexterville

collection immature oospores of the ordinary Plasmopara type

were found.

Plasmopara cephalophora n. sp. 1. Conidiophore. 2 and 3 side and face views of

conidium. Magnified 775 diameters and reduced one-half. Drawn by Mabel M1. Brown

with aid of camera lucida.

Peronospora silenes Wilson. On stems, leaves and fructifica¬

tion of Silene antirhina. Necedah. Oospores especially abun¬

dant in the capsules.

Peronospora linariae Fckl. On leaves and stems of Linaria

canadensis. Lyndon Station. With oospores.

Of a collection on living leaves of TJrtica the following notes

were made : Spots immarginate, round to oval, blackish brown

becoming cinereous above, olivaceous becoming brownish below,

1-2 y2 cm. long, often confluent; perithecia hypophyllous, scat¬

tered, prominent, about 120, u in diameter; asci clavate-cylind-

rical, incurved, octosporous, 40-60 x 7-9/x; ascospores hyaline,

fusoid, obtuse, becoming triseptate, 16-21 x 4-5^; paraphyses

filiform, very slender. On living leaves of TJrtica gracilis.

Davis — Notes on Parasitic Fungi in Wisconsin — VI. 711

Whitehall, Wisconsin, July 27, 1916. I have referred this, with

some doubt, to Metasphaeria chaetostoma Sacc. var. urticae

Rehm.

Keithia tsugae Farl. occurs on Tsuga canadensis in Wisconsin

but has not been included in these lists because of doubt as to

its parasitism. It has been found only on dead leaves at¬

tached to dead twigs. More favorable opportunities for ob¬

servation however lead me to surmise that the death of the twigs

is caused by the organism that sporulates on the leaves. The

appearance of an infected tree reminds one of fire blight. It

was especially abundant at Two Rivers in 1917.

Lophodermium juniperinum (Fr.) De Not. On Juniperus

communis depressa. Two Rivers.

Phyllosticta boehmeriicola n. sp. Spots suborbicular,

olivaceous with a darker margin and pale, sordid, central por¬

tion, 3-10 mm. in diameter; pycnidia epiphyllous, scattered,

lenticular, succineous, ostiolate, 100-150/x; sporules oval to ob¬

long, fuligenous tinted, 4-7 x 2-3 y. On leaves of Boehmeria

cylindrica. Shiocton. August 1917.

Phyllosticta minutissima Ell. & Evht. On Acer saccharinum ;

accompanied by Phloeospora aceris. Shiocton.

Phyllosticta ulmicola Sacc. Under this name I am recording

the occurrence of a fungus having the following characters:

Spots definite, immarginate, orbicular, light brown becoming

cinereous above and lacerate, finally falling away in fragments,

3-7 mm. in diameter, sometimes confluent ; pycnidia epiphyllous,

scattered, black, globose to depressed-globose, 60-80/x; sporules

globose to elliptical, olivaceous-hyaline, continuous, 3-6 x 2-3 y.

On TJlmus americana. Tisch Mills August 3, 1917. Ulmus

racemosa August 5, 1917. This is probably a member of a

group to forms of which various names have been applied in

Europe and America.

Phyllosticta mitellae Pk. On Mitella diphylla. Melvina.

In the collection that I am provisionally referring to this species

the pycnidia are light brown and the sporules oblong to ellipti¬

cal, 4-6 x 2-3 fx. Occasional sporules have a median septum.

Ascochyta nepetae n. sp. ad interim. Spots orbicular to

elliptical, olivaceous usually with a narrow darker margin, 4-10

712 Wisconsin Academy of Sciences, Arts, and Letters.

mm. long; pycnidia epiphyllous, few, scattered, depressed-glo¬

bose, suecineous with a dark ostiolar ring; sporules hyaline, ob¬

long, uniseptate, not constricted, 10-14 x 3^. On leaves of

Nepeta cataria. Shiocton, August 1917.

Septoria sedi West. On Sedum purpureum. Plover. This

is the fungus issued under this name in Fungi Columbiani 3081

and described by Peck as Septoria sedicola n. sp. (Report 1909

p. 29). I have not seen European material.

Septoria chamaecisti Yestergr. On leaves of Lechea inter¬

media. Plover.

Septoria acerina Pk. On Acer spicatum. Casco. This ap¬

pears to be a member of the Phloeospora aceris group referred

to in 1 1 Notes ” I, pp. 80-81 and the spore body as I have seen

it is an acervulus. Inoculation work seems to be required to

define the relationship of the members of this group.

Septoria purpurascens Ell. & Mart. On Potentilla arguta.

Lyndon Station. This is the form with epiphyllous pycnidia

distributed in Fungi Columbiani 3487 and F. Exot. Exsicc. 143.

I have not seen S. potentillica Thuem. the description of which

suggests similarity.

Septoria delphinella Sacc. Spots orbicular to linear, brown

to umber, 3-12 mm. long; pycnidia amphigenous but more

numerous above, globose, with dark brown wall about 3/jl thick,

60-90/x in diameter; sporules acicular, straight or Curved, 35-

50 x lp. On leaves of Delphinium Penardi. Hixton, July,

1916. This often causes the death of the portion of the narrow

leaf lobe which is distal to the spot. The fungus is allied to

Septoria hepaticae Desm. and S. aquilegige Ell. & Kell.

Septoria araliae Ell. & Evht. On Panax trifolia. Millston.

Septoria menthicola Sacc. & Let. On Mentha arvensis.

Madison. Pycnidia globose, about 60^ in diameter; sporules

curved, 18-33 x 1-1 y2fi.

Septoria lupincola Deam. On Lupinus perennis. Black

River Falls.

Typical specimens of Septoria pauper a Ellis have been col¬

lected in Wisconsin but I have not been able to divide the speci¬

mens on Helianthus satisfactorily.

Davis — Notes on Parasitic Fungi in Wisconsin — VI. 713

Specimens on Lactuca Scariola integrata collected at Madison

September 30, 1916 bear orbicular, cinereous spots with a pro¬

nounced dark border; the pycnidia are innate and the sporules

24—30 x 1-1 y2fi. This seems to be Septoria unicolor Wint. A

collection on Lactuca Scariola made at the same station October

6, 1916 has the spots somewhat angular, definite but not mar¬

gined, sometimes confluent and sporules about 30 x 1/a.

Colletotrichum salmonicolor O’Gara ( Mycologia , 7: 40) Of a

collection that seems referable to this species the following notes

were made.

Spots numerous, scattered, subcircular, black, about 1 mm. in

diameter, sometimes confluent ; acervuli hypophyllous and cauli-

colous, flat, 60-120/a wide, usually solitary in the center of the

spot, soon exposed, the spore masses bright salmon color ; sporules

hyaline, as seen singly, with thin walls and granular contents,

cylindrical, usually straight, 18-27 x 3%-6/a borne on similar but

smaller (10-15 x 3/a) basidia. On leaves of Asclepias syriaca.

Arcadia, Wisconsin, September, 1917. On the midribs and stems

the spots are longer and acute at each end. Black setae occur in

the acervuli occasionally. This differs from Hainesia only in the

thick sporophore and occasional setae. It was abundant at

the station where observed. It may be that this is not distinct

from the fungus described by Saccardo as Gloeosporium mol-

lerianum Thuem. var. folliculosum which occurred on follicles

of Asclepias verticillata in a botanical garden in Portugal. (FI.

Myc. Lusit. 11: 13 [1903], Syll. Fung. 18: 458) of which I have

not seen specimens.

In July 1916 Gaylussacia baccata bushes were noticed at Hix-

ton that had the appearance of having been attacked by Monilia

and on examination a few broad-limoniform conidia were found

which measured 24-27 x 18-20/a. The material hardly warrants

a determination but has been filed under the label Monilia pecki-

ana Sacc. & Yogi.

Rhynchosporium secalis (Oud.) n. comb. (Mar sonia secdlis

Oud. Rhynchosporium graminicola .Heinsen). On Hordeum

vulgare (cult.) Madison.

Septocylindrium acutum n. sp. Spots definite, elliptical,

brown becoming grey, often confluent, 1-8 mm. long; conidia

amphigenous but more abundant above, hyaline, lance-fusoid,

714 Wisconsin Academy of Sciences, Arts, and Letters.

catenulate, becoming uniseptate, straight or somewhat curved,

15-39 x 3 /a. On leaves of Agrostis alba. Black River Falls,

June 30, 1916. The septa are thin and not conspicuous.

Ovularia pidchella (Ces.) Sacc. var. agropyri n. var.

Spots linear to oblong, dark brown becoming paler in the cen¬

ter, usually surrounded by a yellowish discoloration of the leaf,

2-5 mm. long, sometimes confluent; conidiophores amphigenous

in small tufts or scattered, hyaline, straight or geniculate, 40-

65 x 2-3 fx ; conidia acro-pleurogenous, spherical to oval, hyaline,

9-12 x 6-9/a. On leaves of Agropyron tenerum. Hixton, July

7, 1916.

In the supplementary list, p. 173, a Ramularia on Fagopyrum

was noted under Ramularia rufomaculans Pk. but it was not

included in the provisional list. It has been described as Ram¬

ularia anomala n. sp. by Peck in the Report of the State Bot¬

anist for 1912, p. 47.

Ramularia umbrina n. sp.

Spots orbicular to elliptical to angular, umber colored with a

narrow, dark, raised margin and surrounded by more or less

purple discoloration of the upper surface of the leaf, 2-5 mm.

in diameter; conidiophores mostly hypopyllous in small tufts,

subulate to terete, hyaline, straight, simple, continuous, often

denticulate near the apex, 9-17 x 2-3/a ; conidia hyaline, straight,

catenulate, fusiform to cylindrical, sometimes uniseptate, 5-16 x

1%-2/a. On leaves of Diervilla Lonicera. Millston, Wisconsin,

June 27, 1916. Hixton, Wisconsin, July 5, 1916.

Cercospora violae Sacc. On Viola sp. indet. Monroe (Cope¬

land, 1901).

Cercospora panici n. sp.

Spots fusoid, ferruginous, central portion sordid white, 2-4 x

1-2 mm. Conidiophores amphigenous, caespitose, fuliglueous,

straight or more or less flexuose and nodulose, 30-40 x 3/a ; con¬

idia hyaline, cylindrical, straight or curved, catenulate (?),

30-40 x 2-3/a. On leaves of Panicum latifolium. Shiocton,

Wisconsin, August 15, 1917.

Fusarium sphaeriae Fckl. var. robustum n. var. Conidia

7-11 septate, 60-75 x 5-6/a. On perithecia of Apiosporina col-

linsii. Hixton, July 4, 1916.

Davis — Notes on Parasitic Fungi in Wisconsin — VI. 715

\

Cercospora cichorii n. sp.

Spots suborbicular, light brown to alntaceons to cinereous,

more or less marked by concentric lines, 2-6 mm. in diameter,

sometimes confluent; conidiophores mostly epiphyllous in small

spreading tufts, brown, straight, curved or somewhat flexuose,

terete or torulose and denticulate, continuous or septate, 20-75 x

3-6 /x ; conidia hyaline, obelavate-cylindrical, straight, septate,

90-150 x 4 -6/a. On leaves of Cichorium Intybus. Madison,

Wisconsin. September and October. If no Cercospora occurs

on chicory in Europe one would suspect that this is an Ameri¬

can species that has passed over from some related host but if

so I do not know what it is.

Entyloma parvum n. sp.

Sori on the upper portion of the culm, black, linear, about

y2 mm. long; spores aggregated, compacted, fuligenous, sub-

globose or sometimes oval or ovate, smooth, 7-10 /x long. On

Eleocharis acicularis. Plover, Wisconsin, August 1917, Madi¬

son, Wisconsin, August 1892, (Cheney) Cambridge, Mass. 1906.

(Grossenbacher, com. Farlow). This is most nearly allied to

Entyloma lineatum (Cke.) Davis.

All collections of Caeoma nitens were tested as to spore ger¬

mination in 1917. Of them one, from blackberry in the horti¬

cultural garden, developed promycelia and sporidia. This was

the earliest collection of the season. All the others formed germ

tubes. Arthur proposed the genus Kunkelia for the short cycled

form in which the spores germinate as teliospores. ( Bot . Gaz.

63:4 [1917].

University of Wisconsin Herbarium.

Madison, Wisconsin, April 1918.

716 Wisconsin Academy of Sciences , Arts , and Letters ,

INDEX TO HOSTS

IN “NOTES” IV, V, and VI.

Acalypha virginica: v, 695

Acer negundo: v, 691

Acer rubrum: v, 702

Acer saccharinum: iv, 678; v, 702;

vi, 708, 711

Acer spicatum: iv, 679; vi, 712

Acorus calamus: iv, 687

Actaea rubra: v, 698

Adiantum pedatum: iv, 689

Agastache foeniculum: v, 700

Agastache scrophulariafolia: v, 699

Agrimonia gryposepala: v, 693

Agrimonia mollis: iv, 677

Agrimonia striata: iv, 678; v, 693

Agropyron repens: iv, 676; v, 697

Agropyron tenerum: iv, 676; vi, 714

Agrostis alba: vi, 714

Allium cepa: v, 701

Alnus incana: v, 691

Ambrosia psilostachya: vi, 707

Ambrosia trifida: v, 694

Amelanchier oblongifolja: vi, 708

Anemone canadensis: v, 692

Anemone quinquefolia: iv, 676; 685;

v, 692

Apiosporina collinsii: vi, 714

Apocynum androsaemifolium: v, 699

Arabia canadensis: vi, 707

Aralia nudicaulis: iv, 689

Arenaria lateriflora: iv, 689

Artemisia absinthium: vi, 709

Artemisia ludoviciana: v, 693

Asclepias syriaca: v, 692, 701; vi,

713

Asclepias verticellata: vi, 713

Aster: v, 692; vi, 705

Aster azureus: v, 694

Aster drummondii: v, 700

Aster macrophyllus: iv, 680

Aster puniceus: iv, 675

Astragalus canadensis: iv, 686

Baptisia leucantha: v, 702

Betula alba:v, 698

Bidens cernua: iv, 677

Bidens vulgata: iv, 679

Boehmeria cylindrica: iv, 681, 682;

vi, 711

Bromus altissimus: v, 694; vi, 708

Bromus secalinus: v, 695

Calamagrostis canadensis: v, 697,

698; vi, 708

Capsicum: iv, 686

Carex cephalophora: vi, 708

Carex gracillima: iv, 689

Carex grisea: iv, 687

Carex paupercula irrigua: iv, 689

Carex pennsylvanica: iv, 685

Carex siccata: v, 695

Carex trichocarpa: iv, 680

Carya alba: v, 694

Carya cordiformis: v, 694

Carya ovata: iv, 672

Chenopodium capitatum: iv, 683; vi,

708

Chrysanthemum: iv, 685

Cichorium intybus: vi, 715

Cicuta maculata: v, 700

Cinna arundinacea: v, 695

Cirsium altissimum: v, 699

Claytonia virginica: vi, 706

Clematis: v, 698

Clintonia borealis: iv, 677

Cornus paniculata: v, 701

Corylus americana: iv, 679; v, 697

Corylus rostrata: v, 694

Crataegus: v, 692

Cucumis sativus: v, 694, 699

Cucurbita melo: v, 694

Datura metel: iv, 689

Datura stramonium: iv, 689

Delphinium penardi: vi, 712

Dentaria diphylla: iv, 677

Desmpdium paniculatum: v, 694

Diervilla lonicera: iv, 689; vi, 714

Echinocystis lobata: v, 697

Eleocharis acicularis: vi, 715

Elymus: iv, 677; v, 696

Elymus virginicus: v, 701

Epilobium adenocaulon: iv, 678

Davis — Index to Hosts.

717

Erigeron: vi, 705

Erigeron canadense: iv, 677, 679

Eriophorum virginicum: v, 703

Eupatorium purpureum: v, 702

Eupatorium urticaefolium: iv, 675

v, 700

Euphorbia dentata; v, 694

Fagopyrum: vi, 714

Fragaria virginiana: v, 691

Galeopsis tetrahit: vi, 707

Galium claytoni: vi, 707

Gaylussacia baccata: vi, 713

Glyceria nervata: iv, 678

Halenia deflexa: iv, 677, 688

Helianthemum canadense: iv, 687

Helianthus: iv, 689; vi, 712

Helianthus strumosus: v, 700

Hepatica acutiloba: v, 692

Hepatica triloba: v, 692

Heuchera hispida: vi, 707

Hordeuxn vulgare: iv, 678; vi, 713

Houstonia longifolia: v, 703

Humulue lupulus: iv, 671; vi, 707

Hystrix patula: v, 696

Iris: iv, 687

Iva xanthifolia: iv, 683

Juglans cinerea: iv, 677

Juniperus communis depressa: vi,

711

Koeleria cristata: v, 695

Krigia amplexicaulis: v, 693, 695

701

Kuehneola uredinis: vi, 707

Lactuca scariola: vi, 713

Lactuca scariola integrata: vi, 713

Lactuca spicata: iv, 680

Lechea intermedia: vi, 712

Lepidium apetalum: v, 694

Liatris cylindracea: v, 695

Liatris scariosa: v, 695

Linaria canadensis :vi, 710

Liinnaea borealis: iv, 681

Lonicera hirsuta: iv, 677

Lupinus perennis: iv, 677; v, 702;

vi, 707, 712

Luzula saltuensis: iv, 680

Lycopus uniflorus: v, 700; vi, 707

Mitella: v, 701

Mitella diphylla: iv, 689; vi, 711

Monarda fistulosa: iv, 688

Muhlenbergia: v, 697

Napaea dioica: iv, 678

Nepeta cataria: vi, 712

Oakesia sessilifolia: v, 703

Oryzopsis asperifolia: v, 697

Ostrya virginiana: iv, 677

Panax trifolia: vi, 712

Panicum huachucae: v, 697

Panicum latifolium: v, 697, vi, 714

Panicum virgatum: iv, 685

Physalis pubescens: v, 694

Physostegia parviflora: vi, 709, 710

Pinus austriaca: vi, 709

Pinus banksiana: v, 693, 695, 696

Pinus resinosa: vi, 707

Pinus strobus: v, 696, 703

Platanus occidentalis: iv, 679

Poa triflora: iv, 678

Polygonatum biflorum: iv, 678

Polygonatum commutatum: vi, 707

Polygonum erectum: v, 702

Polygonum pennsylvanicum: v, 694

Polygonatum biflorum: iv, 678

Polytaeiiia nuttallii: v, 702

Populus balsamifera: iv, 679

Populus deltoides: iv, 679

Populus grandidentata: iv, 676

Populus tremuloides: iv, 676, 686

Potentilla arguta vi, 712

Potentilla canadensis: iv, 678

Prunus americana: iv, 683; vi, 706

Prunus cuneata: iv, 680

Prunus domestica: iv, 678

Prunus pennsylvanica: v, 694

Prunus nigra: vi, 706

Prunus pumila: vi, 707

Prunus serotina: v, 694; vi, 705

Prunus virginiana: vi, 705

Pteris aquilina: iv, 689; v, 701

Puccinia curtipes: vi, 707

Quercus bicolor: vi, 709

Quercus ellipsoidalis: iv, 678; vi,

708, 709

Quercus macrocarpa: v, 693; vi, 709

Quercus rubra: vi, 709

Quercus velutina: iv, 672

Medicago sativa: iv, 683; v, 698, 703 Radicula nasturtium-aquaticum: iv,

Melampsora: iv, 679 687

Melica striata: iv, 676 Ranunculus abortivus: vi, 706

Mentha arvensis: vi, 712 Ranunculus septentrionalis : vi, 706

Mentha canadensis: iv, 688 Ribes arnericanum: iv, 68 3

718 Wisconsin Academy of Sciences , Arts , and Letters ,

Ribes cynosbati: v, 703

Rubus hispidus: iv, 677; v, 693, 696;

vi, 707, 709

Rubus triflorus: iv, 677

Rudbeckia hirta: iv, 680

Rumex britannica: vi, 705

Rumex mexicanus: iv, 673

Rumex verticillatus: vi, 705

Sagittaria arifolia: v, 704; vi, 708,

709

Sagittaria heterophylla: v, 704, vi,

708

Sagittaria latifolia: v, 704

Sagittaria sagittifolia: v, 704

Salix: v, 701

Salix cordata: iv, 680; v, 690

Salix discolor: iv, 680, 686; vi, 708

Salix fendleriana: v, 690

Salix longifolia: iv, 686

Salix lucida: iv, 687; v, 690

Salix pedicellaris: iv, 680

Salix rostrata: vi, 708

Sambucus canadensis: iv, 688

Sambucus racemosa: v, 693

Sanicula gregaria: iv, 687

Sanicula marilandica: v, 700

Saponaria officinalis: iv, 689

Secale cereale: vi, 708

Sedum purpureum: vi, 712

Senecio aureus: v, 703

Silene antirhina: vi, 710

Silphium: iv, 689; v, 700

Silphium perfoliatum: iv, 686

Silphium terebinthinaceum: iv, 689

Sisyrinchium: v, 703

Sium cicutaefolium: vi, 709

Smilax: iv, 672

Smilax ecirhata: vi, 708

Smilax rotundifolia: iv, 673

Solidago: iv, 675; vi, 705

Solidago altissima: iv, 680, 681

Solidago canadensis: iv, 689

Solidago serotina: vi, 705

Sonchus asper: v, 703

Spartina: v, 692

Sphenopholis obtusata: iv, 680

Spirogyra: iv, 681

Stachys tenuifolia: v, 701

Steironema ciliatum: iv, 689

Steironema lanceolatum: v, 694

Strelitzia angusta: iv, 672

Symphoricarpos orbiculatus: iv, 678

Thalictrum: v, 698

Tiarella: v, 701

Tilia americana: iv, 683

Trifolium hybridum: iv, 684; v, 692

Trifolium pratense: v, 692

Trifolium repens: iv, 674, 684

Triticum vulgare: iv, 685; vi, 708

Tsuga canadensis: vi, 711

Typha latifolia: iv, 684

Ulmus americana: vi, 711

Ulmus fulva: iv, 685

Ulmus racemosa: v, 693; vi, 711

Urtica gracilis: vi, 710

Uvularia grandiflora: v, 693

Vaccinium oxycoccus: iv, 679

Vernonia: v, 700

Viola: vi, 714

Viola canadensis: iv, 674

Viola conspersa: iv, 677

Zizia aurea: v, 700

Davis—Index to Fungi.

719

INDEX TO FUNGI

Referred to in “Notes” I-VI

Actinonema actaeae: (Allesch.)

Died.: v, 698

Actinonema rosae (Lib.) Fr.: i, 80

Aecidium compositarum: ii, 96

Aecidium falcatae Arth: ii, 96

Aecidium houstoniatum Schw. : v,

703

Aecidium liatridis Ell. & And.: iii,

269

Aecidium lupini Pk.: iii, 269

Aecidium maianthae Schum.: iii,

262; v, 703

Aecidium nesaeae Ger. : iv, 676

Aecidium proserpinacae B. & C.: ii,

107

Aecidium ranunculacearum D C; iii,

262; iv, 676

Aecidium uvulariae Schw.: v, 703

Aecidium xanthoxyli Pk.: ii, 107

Albugo Candida (Pers.) Kuntze; iv,

677; vi, 707

Alternaria crassa (Sacc.) Rands: iv,

689

Alternaria sonchi Davis: v, 703

Aphanomyces phycophila DBy.: iv,

681

Apiosporina collinsii (Schw.)

Hoehn.: iv, 671

Ascochyta aceris Lib.: i, 80, 81

Ascochyta actaeae (Bres.) n. comb.:

v, 698

Ascochyta alismatis E. & E.: i," 84

Ascochyta alismatis (Oud.) Trail: i,

84

Ascochyta asclepiadis E. & E.: v, 701

Ascochyta caulicola Laubert: ii, 102;

iv, 673

Ascochyta chenopodii (Karst.)

Rostr.: iv, 683

Ascochyta clematidina Thuem.: v,

698

Ascochyta clematidina thalictri

Davis: v, 698

Ascochyta compositarum n. sp.: v,

700

Ascochyta compositarum parva n.

var.: v, 700

Ascochyta confusa E. & E.: iv, 673

Ascochyta confusa Bubak: iv, 685

Ascochyta cucumis Fautr. & Roum.:

v, 699

Ascochyta graminicola Sacc.: v, 698

Ascochyta imperfecta Pk.: v, 698

Ascochyta lethalis Ell., & Barth.: ii,

102; iv, 673

Ascochyta lophanthi Davis: v, 699

Ascochyta lophanthi osmophila n.

var.: v, 700

Ascochyta marginata n. sp.: iii, 263

Ascochyta meliloti (Trel.): iv, 673

Ascochyta nepetae n. sp.: vi, 711

Ascochyta pisi Lib.: i, 80

Ascochyta salicifoliae (Trel.): iv, 673

Ascochyta saniculae n. sp.: ii, 105;

v, 700

Ascochyta thaspii E. & E.: v, 700

Ascochyta thaspii lycopina n. var.:

v, 700; vi, 707

Ascochyta treleasei Sacc & Vogl.: v,

700

Ascochyta trifolii Boud. & Triouss.;

iv, 684

Ascochyta trifolii S'iemaschko: iv,

684

Ascochyta wisconsina n. sp.: ii, 101;

v, 693

Asterina cupressina Cke.: ii, 101

Asterina plantaginis Ellis: i, 78

Asterina rubicola E. & E.: i, 78; iii,

258

Asteroma ribicolum E. & E.: iv, 683

Asteroma umbonatum Desm.: iv, 683

Asteroma tiliae Rud.: iv, 683

Basidiophora entospora Roze &

Cornu: iv, 677

Bremia lactucae Regel: v, 693

Caeoma abietis-canadensis Farl.: ii,

96; iv, 676

Caeoma nitens Schw.: iii, 257; vi, 715

Calyptospora goeppertiana Kuehn:

ii, 96

Cercospora absinthii (Pk.) Sacc.:

iii, 269; vi, 709

Cercospora ageratoides E. & E.: iii,

269; iv 675

Cercospora althaeina Sacc.: iii, 260

720 Wisconsin Academy of Sciences, Arts, and Letters .

Ceroospora aquilegiae Kell. & Sw.:

i, 92

Cercospora arctostaphyli n. sp.: iii,

268

Cercospora camptosori n. sp.: iii, 267

Cercospora caricina Ell. & Dearn.:

i, 86; ii, 100

Cercospora ceanothi Kell. & Sw.: i,

86

Cercospora chenopodii Fres.: vi, 708

Cercospora cichorii n. sp.: vi, 715

Cercospora circumscissa Sacc : iii

259; v, 694

Cercospora comandrae E. & Dearn.:

iii, 267

Cercospora condensata E. & K.: iii,

267

Cercospora corni n. sp.: iii, 268; iv,

675

Cercospora crassa Sacc.: iv, 689

Cercospora datura© Pk.: iv, 689

Cercospora depazeoides Sacc.: iv,

688

Cercospora dubia (Riess) Wint.: vi,

708

Cercospora echinochloae n. sp.: ii,

106;

Cercospora echinocystis E. & M.: iii,

268

Cercospora effusa (B. & C.) E. & E.:

iii, 268

Cercospora erysimi n. sp.: iii, 267

Cercospora fingens n. sp.: i, 92

Cercospora fuliginosa E. & E.: i, 86

Cercospora gentianae Pk.: iv, 688

Cercospora gentianicola E. & E.: iv,

688

Cercospora geranii Kell. & Sw.: i, 83

Cercospora grindeliae Ell. & Evht.:

iii, 269

Cercospora helvola zebrina (Pass.)

Ferraris: iv, 675

Cercospora leptosperma Pk.: iii, 255;

vi, 706

Cercospora longispora Pk.; v, 702

Cercospora macclatchieana Sacc. &

Syd.: i, 86

Cercospora megalopotamica Speg.:

iii, 256

Cercospora muhlenbergiae Atk.: iii,

267

Cercospora nasturtii Pass.: iv, 687

Cercospora negundinis E. & E.: iii,

267

Cercospora panici n. sp.: vi, 714

Cercospora passaloroides Wint.: ii,

106

Cercospora pentstemonis Ell. &

Kell.: iii, 260

Cercospora polytaeniae Ell. & Kell.:

v, 702

Cercospora rhoina Cke. & Ell.: ii,

100

Cercospora sanguinariae Pk.: iii, 267

Cercospora saniculae n. sp.: iv, 687

Cercospora sequoiae juniperi E. &

E.: ii, 95

Cercospora subsanguinea E. & E..: i,

83

Cercospora varia Pk.: iii, 260

Cercospora velutina Ell. & Kell.:' v,

702

Cercospora vexans C. Massal.: v, 691

Cercospora violae Sacc.: vi, 714

Cercospora zebrina Pass.: iv, 675

Cercosporella cana Sacc.: iv, 675

Cercosporella cana gracilis n. var.:

iv, 675

Cercosporella dearnessii Bubak &

Sacc.: iv, 675

Cercosporella exilis n. sp.: i, 91

Cercosporella filiformis n. sp.: iii,

266; vi, 706

Cercosporella leptosperma (Pk.): vi,

706

Cercosporella nivea Ell. & Barth.: ii,

105; iv, 675

Cercosporella ontariensis Sacc.: iv,

675

Cercosporella reticulata Pk.: iv, 675

Cercosporella scirpina n. sp.: iii, 266

Cercosporella trichophila n. sp. iii,

266

Cladosporium gloeosporioides Atk.:

i, 91

Cladosporium humile n. sp.: v, 702

Cladosporium letiferum Pk.: iii, 256

Cladosporium paeoniae Pass.: i, 91

Cladosporium subsessile Ell. &

Barth.: iv, 675

Coccochora rubi n. sp.: v, 696

Coccomyces hiemalis Higgins: iii,

255

Coccomyces lutescens Higgins, iii,

255

Coccomyces prunophorae Higgins:

iii, 255

Coleosporium sonchi-arvensis

(Pers.) Lev.: i, 92

Colletotrichum circinans (Berk.)

Vogl.: v, 701

Colletotrichum graminicolum (Oes.)

Wilson: iii, 265; vi, 708

Colletotrichum helianthi n. sp.: i, 89

Colletotrichum lagenarium (Pass.)

E. & Hals.: v, 694

Colletotrichum nigrum Ell. & Hals.:

iv, 686

Colletotrichum salmonicolor O’Gara:

vi, 713

Colletotrichum silphii n. sp.: iv, 686

Davis — Index to Fungi .

721

Colletotrichum solitarium Ell. &

Barth.: i, 89

Colletotrichum sordidum n. sp.: iii,

265

Cronartium comandrae Arth.: iii, 261

Cronartium comptoniae Arth.: vi,

709

Cronartium quercus (Brondeau)

Schroet.: vi, 709

Cronartium ribicola Fisch de

Waldh. : v, 708

Cylindrosporium betulae Davis: ii,

99

Cylindrosporium eminens n. sp.: iv,

687

Cylindrosporium glyceriae E. & E.:

ii, 99

Cylindrosporium hiemale Higgins:

iii, 255

Cylindrosporium leptospermum Pk.:

iii, 255; vi, 706

Cylindrosporium lutescens Higgins:

iii, 255

Cylindrosporium oculatum E & F

i. 82

Cylindrosporium padi Karst.: iii, 255

Cylindrosporium prunophorae Hig¬

gins: iii, 255

Cylindrosporium ribis Davis: iv, 673

Cylindrosporium saccharinum E. &

E.: i, 81; iv, 679

Cylindrosporium salicifoliae (Trel.)

Davis: iv, 673

Cylindrosporium sheph-erdiae Sacc.:

ii, 105

Cylindrosporium vermiforme n. sp.:

ii, 104; iv, 679; v, 694

Cytodiplospora elymina n. sp.: v, 701

Darluca filum (Biv.) Cast.: iv, 679;

vi, 707

Depazea carpinea (Schw.) Fr.: i, 88

Dibotryon morbosum (Schw.) Theiss.

& Syd.: iv, 671

Didymaria astragali (E. & H.) Sacc.:

iii, 265

Dimerosporium collinsii (Schw.)

Thuem.: ii, 97; iv, 671

Diplocarpon rosae Wolf: i, 80

Diplodia uvulariae n. sp.: i, 87; v,

693

Doassansia deformans Setch.: v, 704

Doassansia furva n. sp.: v, 704

Doassansia martianoffiana (Thuem.)

Schroet.: v, 704

Doassansia ranunculina Davis: iv,

681

Doassansia sagittariae (West.) Fisch:

v, 703; vi, 709

Doassansia zizaniae Davis: v, 704

Dothidella ulmea (Schw.) E. & E.:

iii, 258; iv. 671

46— S. A. L.

Endodothella junci (Fr.) Theiss. &

Syd.: iv, 672

Endodothella strelitziae (Cke.)

Theiss. & Syd.: iv, 672

Entomosporium maculatum cydon-

iae Sacc.: ii, 98

Entyloma australe Speg. : v, 694

Entyloma compositarum Farl.: iv,

680

Entyloma floerkeae Holw.: i, 85

Entyloma linariae veronicae Wint.:

i, 85

Entyloma lineatum (Cke.) Davis: ii,

96; vi, 715

Entyloma nymphaeae (Cunn.)

Setch.: ii, 97

Entyloma parvum n. sp.: vi, 715

Entyloma polysporum (Pk.) Farl.:

iv, 680; v, 694

Epichloe typhina (Pers.) Tul.: iv,

678

Erysiphe cichoracearum DC.: iii,

252; iv, 678

Erysiph© graminis D C.: iv, 678

Erysiphe polygoni DC.: iii, 257

Euryachora ulmi (Fr.) Schroet: iii,

{258 ; iv, 672

Exoascus betulinus (Rostr.) Sadeb.:

iii, 262

Exoascus cerasi (Fckl.) Sacc.: iv,

672

Exoascus coerulescens (M. & D.):

Tul, ii, 98; iv, 678; v, 693

Exoascus communis Sadeb.: iii, 262;

iv, 678; vi, 707

Exoascus confusus Atk.: ii, 97

Exoascus insititiae Sadeb.: ii, 97

Exoascus mirabilis Atk.: iv, 683

Exoascus pruni Fckl.: iv, 678

i i

Fusarium carpineum n. sp.: ii, 106

Fusarium graminum Cda.: vi, 706

Fusarium heterosporum Nees: vi,

706

Fusarium sphaeria-e robustum n.

var.: vi, 714

Fusarium uredinum E. & E.: i, 84

Fusicladium radiosum (Lib.) Lind:

ii, 99; iii, 256

Fusicladium radiosum mierosporum

(Sacc.) Allesch.: iii, 256; iv, 675

Fusidium asteris Phil. & Plowr. : v,

692

Gloeosporium apocryptum E. & E.:

v, 691

Gloeosporium boreale E. & E.: v, 690

Gloeosporium canadense E. & E.: ii,

99

Gloeosporium caryae Ell. & Dearn.:

iii, 259; iv, 672; v, 694

Gloeosporium cinctum B. & C.: 1, 89

722 Wisconsin Academy of Sciences, Arts, and Letters.

Gloeosporium cladosporioides E. &

Hals.: i, 91

Gloeosporium confluens Ell. &

Dearn. : vi, 708

Gloeosporium cylind rospermum

(Bon.) Sacc.: ii, 103; v, 691

Gloeosporium davisii E. & E.: iv, 686

Gloeosporium fragariae (Lib=)

Mont.: i, 83

Gloeosporium leptospermum Pk.:

v, 701

Gloeosporium meliloti Trel. : iv, 673

Gloeosporium mollerianum folliculo-

sum: vi, 713

Gloeosporium nervisequum (Fckl.)

Sacc. : ii, 99; iv, 679

Gloeosporium pallidum Karst. &

Har. : i, 89

Gloeosporium populinum Pk.: iv,

673 •

Gloeosporium ribis (Lib.) M. & D.:

i, 84; ii, 99; iii, 259

Gloeosporium robergei Desm.: ii, 98

Gloeosporium saccharinum E. & E.:

i, 86; ii, 94

Gloeosporium septorioides Sacc. : ii,

98; iii, 254, 259

Gloeosporium thalictri Davis: iii, 255

Gloeosporium tremuloides E. & E.:

i, 84

Gloeosporium trifolii Pk.: ii, 265;

iv, 674, 684

Glomerella cingulata (Stonem.) S. &

V. S.: i, 89

Gnomonia caryae Wolf: iv, 672

Gnomonia ulmea (Schw.) Tbuem.:

iv, 672

Gnomoniella fimbriata (Pers.) Sch-

roet. : i, 79

Gnomoniella tubiformis (Tode)

Sacc. : v, 691

Graphiothecium vinosum n. sp: i,

90

Gymnoconia peckiana (Howe) Trot¬

ter: iii, 257; vi, 709

Gymnosporangium clavariaeforme

(Jacq.) DC.: ii, 95

Gymnosporangium cor niculans

Kern: ii, 107

Gymnosporangium globosum Farl.:

v, 692

Hendersonia typhae Oud.: iv, 684; v,

690

Heterosporium gracile (Wallr.)

Sacc.: iv, 687

Hormodendron farinosum Bon.: 1,

90

Hyaloceras kriegerianum (Bres.)

Died.: v, 691

Hyalopsora aspidiotus Pk.: ii, 107

Hypo derma desmazieri Duby: v, 696

Keithia tsugae Farl. : vi, 711

Kunkelia: vi, 715

Laestadia aesculi Pk.: iii, 252

Leptosphaeria caricicola Fautr. : i,

87

Leptosphaeria caricina Schroet.: i,

87

Leptosphaeria foliiculata oxyspora

n. var.: i, 87

Leptothyrium alneum (Lev.) Sacc.:

v, 691

Leptothyrium betulae Fckl.: i, 89

Leptothyrium dryinum Sacc.: iii,

254; vi, 708

Lophodermium amplum n. sp.: iii,

' 252; v, 695-6

Lophodermium juniperinum (Fr.)

De Not.: vi, 711

Lophodermium lineare Pk.: v, 696

Lophodermium pinastri ( Schroet. )

Chev. : v, 696; vi. 707

Macrophoma cruenta (Fr.) Ferrar-

is: i, 80

Macrosporium saponariae Pk.: iv,

689

Marsonia secalis Oud.: vi, 713

Marssonina actaeae (Bres.) Magn. :

v, 698

Marssonina baptisiae (E. & E.)

Magn. : ii, 103

Marssonina brunnea (E. & E.)

Magn. : i, 84

Marssonina castagnei (D. & M.)

Magn. : i, 84; iv, 679, 686; vi, 705

Marssonina coronaria (E. & Davis)

Davis: ii, 103

Marssonina martini (S. & E.) Magn.:

ii, 99

Marssonina neilliae (Hark.) Magn.:

ii, 103

Marssonina populi (Lib.) Magn.: vi,

705

Marssonina potentillae tormentillae

Trail : iii, 259

Marssonina rhabdospora (E. & E.)

Magn.: i, 82; ii, 103; iv, 674

Marssonina rosae (Lib.) Trail : i, 80

Marssonina rubiginosa E. & E. : v,

701

Melampsora abietis-c anadensis

(Farl.) Ludwig: iv, 676

Melampsora arctica Rostr. : ii, 107;

iv, 680

Melampsora farlowii (Arth.) Davis:

ii, 107

Melampsora populi-tsugae nom.

nov. : iv, 676

Davis — Index to Fungi.

723

Melampsoropsis cassandrae (P. &

C.) Arth.: ii, 101; iii, 257

Melampsoropsis chiogenis (Diet.)

Arth.: ii, 95

Melampsoropsis ledi (Lk.) Arth.; ii,

95

Melampsoropsis ledicola (Pk.)

Arth.: ii, 95

Metasphaeria chaetostoma urticae

Hehm: vi, 711

Microsphaera alni (Wallr.) Wint.:

ii, 97; iv, 677

Microsphaera diffusa: iv, 678

Microstroma juglandis (Bereng.)

Sacc.: ii, 99; iii, 2 59

Monilia angustior (Sacc.) Reade: vi,

706

Monilia cinerea Bon.: vi, 706

Monilia corni Reade: v, 701

Monilia fructigena Pers.: iii, 259; vi,

706

Monilia peckiana Sacc. & Vogl.: vi,

713

Monilia: iv, 683; vi, 705, 708

Montagnella heliopsidis (Schw.)

Sacc.: iv, 672

Mycosphaerella aurea Stone: v, 690

Mycosphaerella grossulariae (Fr.)

Auersw. : iv, 673

Mycosphaerella lethalis Stone: iv,

673

Mycosphaerella pinodes (Berk. &

Blox.) Niessl: i, 80

Mycosphaerella plantaginis (Ell.)

Theiss. : i, 78

Mycosyrinx osmundae Pk.: i, 84

Myrioconium comitatum n. sp.: v,

686

Neeium farlowii Arth.: ii, 107

Nigredo pustula (Schroet.) Arth.:

iii, 269

Ovularia asperifolii Sacc. var. lap-

pulae n. var.: i. 89; iv, 674

Ovularia asperifolii Sacc., var. sym-

phyti-tuberosi Allesch: i, 90; iv,

674

Ovularia avicularis Pk.: v, 702

Ovularia pulchella agropyri n. var.:

vi, 714

Ovularia rigidula Delacr.: v, 702

Passalora fasciculata (C. & E.)

Earle: iii, 1259

Periderimum balsameum Pk. : ii, 96

Peridermium cerebrum Pk.: iii, 261

Peridermium comptoniae Orton &

Adams: iii, 261, 262; v, 692; vi,

709

Peridermium consimile Arth. &

Kern: ii, 101

Peridermium decolorans Pk.: ii, 95

Peridermium flscheri Kleb.: iii, 261

Peridermium pyriforme Pk.: iii,

261; v, 693

Peronospora chamaesycis Wilson: iii,

257

Peronospora effusa (Grev.) Ces.: iii,

251

Peronospora euphorbiae Fckl.: ii,

94; iii, 257

Peronospora grisea Ung.: ii, 97

Peronospora linariae Fckl.: vi, 710

Peronospora parasitica (Pers.) Tul.:

ii, 97, iii, 251, 257

Peronospora potentillae DBy. : iv,

677; v, 693

Peronospora rubi Rabh.: v, 693

Peronospora silenes Wilson: vi, 710

Peronospora trifoliorum DBy.: iii,

251, 257; iv, 677; vi, 707

Peronospora viciae (Berk.) DBy.:

ii, 93

Pestalozzia kriegeriana Bres.: v, 691

Phleospora aceris (Lib.) Sacc.: i, 81;

iv, 679; vi, 708, 711, 712

Phleospora celtidis E. & M.: iii, 265

Phleospora oxyacanthae (Kze. &

Schm.) Wallr.: iii, 254

Phleospora trifolii Cav.: iv, 684

Phleospora trifolii recedens C. Mas-

sal.: iv, 684

Phleospora ulmi (Fr.) Wallr.: iii,

-258; iv, 672

Phoma minutissima Cke.: i, 87

Phoma virginiana Ell. & Hals.: i, 79

Phomopsis vexans (Sacc. & Syd.)

Harter: iii, 253

Phragmidium disciflorum (Tode)

James: ii, 101; iii, 260

Phragmidium occidentale Arth.: ii,

96

Phragmidium rosae-acicularis Liro:

ii, 101

Phyllachora ambrosiae (B. & C.)

Sacc.: iv, 672

Phyllachora graminis (Pers.) Fckl.:

v, 696-7

Phyllachora graminis panici Shear:

v, 697

Phyllachora junci (Fr.) Fckl.: iv,

672

Phyllachora oryzopsidis Theiss. &

Syd.: v, 697

Phyllachora panici (Rehm) Theiss.

& Syd.: v, 697

Phyllachora vulgata Theiss. & Syd.:

v, 697

Phyllachora wittrockii (Erikss.)

Sacc.: iv, 681

724 Wisconsin Academy of Sciences , Arts , and Letters.

Phyllactinia corylea (Pers.) Karst.:

iv, 672

Phyllosticta atriplicis Desm.: iv, 683

Phyllosticta boehmeriicola n. sp.: vi,

711

Phyllosticta caricis (Fckl.) Sacc.: iii,

264

Phyllosticta caryae Pk.: v, 694

Phyllosticta crataegi (Cke.) Sacc.:

iii, 263

Phyllosticta cruenta (Pr.) Kx.: i,

80, 87; iv, 678; vi, 707

Phyllosticta decidua E. & K. : iii,

258; iv, 678; v, 693; vi, 707

Phyllosticta desmodii E. & E.: i, 79

Phyllosticta destruens Desm.: i, 79;

iii, 263

Phyllosticta discincta Davis: i, 80

Phyllosticta grossulariae Sacc.: iii,

263

Phyllosticta hamamelidis Pk.: vi,

705

Phyllosticta hortorum Speg.: iii, 253

Phyllosticta innumerabilis Pk.: i, 79

Phyllosticta ivaecola E. & E.: iv, 683

Phyllosticta liatridis n. sp.: i, 87

Phyllosticta livida E. & E.: i, 87

Phyllosticta medicaginis (Fckl.)

Sacc.: iv, 683

Phyllosticta minima (B. & C.) E. &

E.: iii, 258; iv, 678

Phyllosticta minutissima E. & E.: vi,

711

Phyllosticta mitellae Pk.: vi, 711

Phyllosticta mulgedii Davis: i. 79

Phyllosticta orbicularis E. & E.: v,

697

Phyllosticta pallidior Pk.: i, 80

Phyllosticta paviae Desm.: iii, 252

Phyllosticta phomiformis Sacc.: iii,

254, 258

Phyllosticta populina Sacc.: i, 83;

iii, 263

Phyllosticta smilacis E. & M.; iv,

672

Phyllosticta trifolii Rich.: iv, 684

Phyllosticta trifoliorum Barbarine:

iv, 684

Phyllosticta ulmicola Sacc.: vi, 711

Phyllosticta uvulariae Galloway: i,

87

Physalospora ambrosiae E. & E.: iv,

672

Physoderma vagans Schroet.: vi, 709

Phytophthora thalictri Wils. & Dav¬

is: i, 92

Piricularia grisea (Cke.) Sacc.: iii,

259

Piricularia parasitica E. & E.: iii,

256

Placosphaeria punctiformis (Fckl.)

Sacc., iii, 263

Plasmopara acalyphae Wilson: v,

695

Plasmopara australis (Speg.) Swin¬

gle: iii, 257

Plasmopara cephalophora n. sp.: vi,

709-710

Plasmopara halstedii (Farl.) Berl.

& De T.: v, 693; vi, 707

Plasmopara humuli M. & T.: i, 78;

iv, 671; v, 690

Plasmopara pygmaea (Ung.)

Schroet.: ii, 97

Plasmopara pygmaea fusca (Pk.)

ii, 94

Plasmopara ribicola Schroet.: ii, 94;

iii, 251

Plasmopara viburni Pk.: ii, 101

Plowrightia morbosa (Schw.) Sacc.:

iii, 258; iv, 671

Protomyces andinus Lagh.: i, 79; ii,

94

Protomyces fuscus Pk.: ii, 94

Pseudopeziza autumnalis (Fckl.)

Sacc.: vi, 707

Pseudopeziza repanda (Fr.) Karst.:

iii, 263; vi, 707

Puccinia agropyri E. & E.: iv, 676

Puccinia albiperidia Arth.: iv, 677

Puccinia andropogonis Schw.: ii,

100; iii, 260

Puccinia apocrypta Ell. & Tracy:

iii, 257

Puccinia bartholomaei Diet.: v, 692

Puccinia bolleyana Sacc.: iii, 260

Puccinia caricis-asteris Arth.: iv,

676

Puccinia caricis-erigerontis Arth.:

iv, 676

Puccinia caricis-solidaginis Arth.:

iv, 676

Puccinia cichorii (DC.) Bell.: ii, 106

Puccinia cirsii-lanceolati Schroet.:

ii, 9 5

Puccinia claytoniata (Schw.) Syd.:

vi, 706

Puccinia coronata Cda.: ii, 100, v,

695

Puccinia curtipes Howe: ii, 101

Puccinia cyperi Arth.: ii, 100

Puccinia dulichii Syd.: iv, 676

Puccinia eatoniae Arth.: iv, 680

Puccinia elymi-impatientis n o m.

nov.: iv, 677

Puccinia erikssonii Bubak: iv, 676

Puccinia eriophori Thuem.: v, 703

Puccinia extensicola Plowr. : iv, 676

Puccinia gigantispora Bubak: ii,

106

Davis — Index to Fungi.

725

Puccinia graminis Pers.: iii, 260; v,

695

Puccinia impatientis (Schw.) Arth.;

iii, 257, 260; iv, 677

Puccinia karelica Tranz.: iv, 689

Puccinia koeleriae Arth.: v, 695

Puccinia mariae-wilsoni Clint.: vi,

706

Puccinia melicae (Erikss.) Syd.: ii,

106; iv, 676

Puccinia microsora Koern.: i, 92

Puccinia minuta Diet.: iv, 680

Puccinia minutissima Arth.: iv, 676

Puccinia obscura Schroet. : iv, 680 i

Puccinia patruelis Arth.: ii, 100; iv,

680; v, 695

Puccinia perminuta Arth.: iii, 260

Puccinia polygoni-amphibii Pers.:

iii, 260

Puccinia pringsheimiana Kleb.: iv,

677

Puccinia pruni-spinosae Pers.: iv,

680

Puccinia rubigo-vera (DC.) Wint. :

ii, 95; iv, 676

Puccinia sessilis Schneid.: iii, 2 62;

v, 703

Puccinia seymouriana Arth.: v, 692

Puccinia tomipara Trel.: iv, 676

Puccinia uniporula Orton: iv, 689

Pucciniastrum agrimoniae (Schw.)

Tranz.: iii, 260

Pucciniastrum myrtilli (Schum.)

Arth.: ii, 96

Pyrenopeziza medicaginis Fckl.: iv,

683

Ramularia acris Lindr.: vi, 706

Ramularia aequivoca (Ces.) Sacc. :

iii, 259; vi, 706

Ramularia alismatis Fautrey: i, 84;

vi, 708

Ramularia anomala Pk.: vi, 714

Ramularia aromatica (Sacc.)

Hoehn.: iv, 687

Ramularia asteris (Sacc.) Barth.:

ii, 99; v, 692

Ramularia asteris (Phil. & Plowr.)

Bubak. : v, 692

Ramularia astragali Ell. & Hoi.: iii,

265

Ramularia calthae Lindr.: i, 90

Ramularia desmodii Cke.: ii, 99, v,

694

Ramularia dioscoreae E. & E.: iii,

255

Ramularia dispar n. sp.: v, 702

Ramularia effusa Pk.: ii, 99

Ramularia fraxinea n. sp.: ii, 105

Ramularia ionophila n. sp.: iii, 266;

iv, 674

Ramularia lamiicola C. Massal.: v,

688

Ramularia lucidae n. sp.: iv, 687

Ramularia lycopi Hollos: iv, 688

Ramularia lysimachiae Thuem.: v,

694

Ramularia menthicola Sacc.: iv, 688

Ramularia modesta Sacc.: v, 691

Ramularia multiplex Pk.: iv, 679

Ramularia nemopanthis Pk.: iv, 674

Ramularia occidentalis Ell. & Kell.:

ii, 99

Ramularia plantaginis E. & M.: i, 84

Ramularia pratensis Sacc.: ii, 99, iii,

259

Ramularia rosea (Fckl.) Sacc.: iii,

259

Ramularia rufomaculans Pk.: iii,

259; vi, 714

Ramularia scelerata Cke.: vi, 706

Ramularia spiraeae Pk.: iii, 266

Ramularia serotina E. & E.: iii, 256

Ramularia subrufa Ell. & Hoi.: iii,

255

Ramularia symphyti-tuberosi (Al-

lesch.) Jaap.: iv, 674

Ramularia umbrina n. sp.: vi, 714

Ramularia uredinis (Voss) Sacc.: i,

84; iv, 679

Ramularia variata n. sp.: iv, 688

Ramularia veronicae Fckl.: ii, 99

Ramularia virgaureae Thuem.: iii,

256; iv, 680

Rhynchosporium graminicola Hein-

sen: vi, 713

Rhynchosporium secalis (Oud.): vi,

713

Rosenscheldia heliopsidis (Schw.)

Theiss. & S<yd.: iv, 672

Sacidium microspermum (Pk). i, 88

Sacidium ulmi-gallae Kell. & Sw.:

iv, 685

Sclerospora graminicola (Sacc.)

Schroet.: iii, 257

Sclerotium deciduum n. sp.: iv, 689

Sclerotium zizaniae Davis: v, 704

Scolecosporium typhae (Oud.)

Hoehn.: v, 690

Septocylindrium acutum n. sp.: vi,

713

Septocylindrium aromaticum Sacc.:

iv, 687

Septocylindrium caricinum Sacc.: iv,

687

Septocylindrium concomitans (Ell.

& Hals.) Hals.: iv, 679

Septocylindrium ranunculi Pk.: ii,

99; vi, 706

726 Wisconsin Academy of Sciences, Arts, and Letters .

Septogloeum apocyni Pk.: v, 699

Septogloeum atriplicis Desm. : iv,

683

Septogloeum salicinum (Pk.) Sacc.:

v, 690, 691, 692; vi, 708

Septogloeum ulmi (Pr.) Died.: iv,

672

Septoria acerella Sacc.: iii, 264

Septoria acerina Pk.: vi, 712

Septoria adenocauli E. & E.: ii, 103

Septoria agrimoniae-eupatorii

Bomm. & Rouss.: ii, 98; iii, 253

Septoria agropyri Ell. & Evht.: vi,

708

Septoria albaniensis Thuem.: v, 690

Septoria alismatis Oud.. i, 84

Septoria alni Sacc.: ii, 103

Septoria alnifolia Ell. & Evht.: ii,

94; iii, 258

Septoria andropogonis n. sp.: i, 88

Septoria anemones Desm.: iv, 685

Septoria aquilegiae E. & K.: vi, 712

Septoria araliae Ell. & Evht.; vi,

712

Septoria argyraeae Sacc.: ii, 105

Septoria astericola E. & E. : i, 86;

iii, 258

Septoria atropurpurea Pk.: iii, 258

Septoria aurea E. & E. : v, 690

Septoria bacilligera Wint.: vi, 705

Septoria betulae (Lib.) West.: ii, 102

Septoria betulicola Pk.: ii, 102

Septoria betulina Pass.: ii, 102

Septoria brencklei Sacc.: iii, 253

Septoria cacaliae Ell. & Kell.: ii, 98

Septoria cannabina West.: iv, 673

Septoria cannabis (Lasch) Sacc.:

iv, 673

Septoria caricinella Sacc. & Roum.:

vi, 708

Septoria carpinea (Schw.?) i, 88

Septoria cassiaecola Kell. & Sw.: ii,

103

Septoria chamaecisti Vestergr.: vi,

712

Septoria chenopodii West.: iv, 683

Septoria chrysanthemella Cav.: iv,

685

Septoria compta Sacc.: iv, 685

Septoria cylindrospora n. sp.: iii,

265

Septoria davisii Sacc.: vi, 705

Septoria delphinella Sacc.: vi, 712

Septoria dentariae Pk.: ii, 94; iii,

258

Septoria echinocystis E. & E.: iii,

253

Septoria epilobii West.: iv, 678

Septoria erigerontis Pk.: iv, 679

Septoria galeopsidis West.: vi, 707

Septoria glumarum Pass.: iv, 686 -

Septoria graminum Desm.: v, 694

Septoria grossulariae (Lib.) West.:

i, 80

Septoria helenii E. & E.: i, 80

Septoria hepaticae Desm.: ii, 103

vi, 712

Septoria intermedia E. & E.: iii, 253

Septoria krigiae Dearn. & House:

v, 701

Septoria lepidiicola E. & M.: v, 694

Septoria lophanthi Wint.: iii, 264

Septoria lupincola Dearn.: vi, 712

Septoria menthicola Sacc. & Let.:

vi, 712

Septoria microsperma Pk.: i, 88

Septoria mitellae E. &. E.: v, 701

Septoria musiva Pk. : i, 81, 82, 83

Septoria nematospora n. sp.: iv, 685

Septoria nubilosa E. & E.: i, 80

Septoria passerinii Sacc.: vi, 708

Septoria paupera Ellis: vi, 712

Septoria phlogis Sacc. & Speg.: iii,

264

Septoria polita n. sp.: i, 88

Septoria polygonorum Desm.: v, 694

Septoria polymniae E. &. E.: i, 88

Septoria populi Desm.: i, 82

Septoria potentillica Thuem.: vi, 712

Septoria purpurascens E. & M.: vi,

712

Septoria ribis Desm.: i, 80; iii, 258;

iv, 673

Septoria rostrupii Sacc & Syd.: iv,

685

Septoria saccharina E. &. E.: i, 80;

Septoria salicifoliae (Trel.) Berl. &

Vogl.: iv, 673

Septoria salicina Pk.: i, 82; v, 690

Septoria sambucina Pk.: iii, 258

Septoria sedi West.: vi, 712

Septora sedicola Pk.: vi, 712

Septoria senecionis-aurei n. sp.: ii,

103

Septoria senecionis-sylvatici Syd.: ii,

103

Septoria sibirica Thuem.: iv, 673

Septoria sicyi Pk.: iii, 253

Septoria sigmoidea E. & E. : iv, 685

Septoria silphii E. & E.: ii, 98

Septoria sisymbrii Ellis: ii, 94

Septora sisymbrii Hennings &

Ranojevic: ii, 94

Septoria solidaginicola Pk.: iii, 254;

v, 694

Septoria stachydis Rob. & Desm.: v,

701

Septoria unicolor Wint.: vi, 713

Septoria xanthiifolia E. & K.: iii, 265

Sphacelotheca cruenta (Kuehn)

Potter: iv, 676

Davis — Index to Fungi.

727

Sphacelotheca sorghi (Lk.) Clinton:

iv, 676

Sphaeria solidaginis Schw.: iv, 681

Sphaeropsis betulae foliicola n. var.:

v, 697

Sphaerotheca humuli (D C.) Burr.:

iii, 257

Sphaerotheca humuli fuliginea

(Schl.) Salm. : iv, 677

Sphaerotheca mors-uvae (Schw.)

B. & C.: ii, 97

Sporonema phacidioides Desm.: iv,

674, 684

Stagonospora apocyni (Pk.) Davis:

v, 699

Stagonospora atriplicis (West.)

Lind: iv, 683, 684

Stagonospora caricinella Brun.: iii,

264

Stagonospora cirsii n. sp.: v, 699

Stagonospora compta (Sacc.) Died.:

iv, 685

Stagonospora dearnessii Sacc.: iv,

674, 684

Stagonospora intermixta (Cke.)

Sacc.: i, 87; ii, 98

Stagonospora paludosa (Sacc. &

Speg.), Sacc.: ii, 102; iii, 264

Stagonospora smilacis (E. & M.)

Sacc.: iv, 672; vi, 708

Stagonospora trifolii Ell. & Dearn.:

iv, 684, 685

Stagonospora typhoidearum (Desm.)

Sacc.: iv, 684

Stagonospora zonata n. sp.: v, 701

Stagonosporopsis actaeae (Allesch.)

Died.: v, 698

Synchytrium aureum Schroet.: i,

85; iv, 677

Synchytrium cellulare n. sp.: iv, 681,

682

Synchytrium decipiens Farl.: iii,

251

Taphrina coerulescens (Desm. &

Mont.) Tul.: iv, 678; v, 693

Taphrina coryli Nishida: v, 697

Taphrina flava Pari.: iii, 2 62

Taphrina potentillae (Pari.) Jo¬

hans.: iv, 678

Taphrina virginica Seym. & Sadeb.:

ii, 98

Uncinula macrospora Pk.: v, 693

Uncinula parvula Cke. & Pk.: iii,

262

Uredinopsis atkinsonii Magn.: ii,

101; iii, 261

Uredo aecidioides, Pk.: iii, 251

Uredo oxytropidis (Pk.) De Toni: iii,

269

Urocystis anemones (Pers.) Schroet.

v, 692

Urocystis waldsteiniae Pk. : iv, 675

Uromyces acuminatus Arth.: iii, 260

Uromyces albus (Clint.) Diet. &

Hoi.: iii, 257

Uromyces astragali (Opiz) Sacc.:

iii, 269

Uromyces euphorbiae C. & P.: ii, 100

Uromyces graminicola Burr.: ii, 106

Uromyces' halstedii De Toni: ii, 100

Uromyces houstoniatus (Schw.) J. L.

Sheldon: v, 703

Uromyces hyperici-frondosi (Schw.)

Arth.: ii, 100: iii, 260

Uromyces junci-tenuis Syd.: ii, 100

Uromyces murrillii Ricker: v, 703

Uromyces poinsettiae Tranz. : iii, 260

v, 694

Uromyces proeminens (D C.) Lev.:

ii, 100; iii, 260; v, 694

Uromyces pustulatus Schroet.: iii,

269

Uromyces scirpi Burr.: ii, 100

Uromyces striatus Schroet.: v, 703

Urophlyctis major Schroet.: vi, 705

Ustilago lorentziana Thuem.: i, 85

Ustilago osmundae Pk.: i, 84

Ustilago utriculosa (Nees) Tul.: ii,

100

Ustilago violacea (Pers.) Fckl.: iv,

689

Venturia tremulae Aderh.: iii, 256

Vermicularia liliacearum West.: iii,

263

Woroninella aecidioides (Pk.) Syd.:

iii, 251

Xyloma carpinea Schw.: i, 88

728 Wisconsin Academy of Sciences , Arts 9 and Letters.

CONTRIBUTION TO THE CHEMISTRY OF AMERICAN

CONIFERS.

BY A. W. SCHORGER.

The chemistry of conifers is deserving of particular study both

on account of its scientific interest and economic importance.

Pinene, the chief terpene occurring in the volatile oils of the

Coniferae, derived its name from the genus Pinus in which it is

found so abundantly. Through the study of pinene and its

derivatives was laid the foundation of the chemistry of the

terpenes which forms one of the most interesting chapters devel¬

oped in organic chemistry during the past twenty«-five years;

and yet in spite of a vast amount of research, pinene is still one

of the few terpenes whose constitution is not known with abso¬

lute certainty.

From the economic standpoint the* conifers are the most im¬

portant of the forest trees. The annual cut of timber from this

class in the United States exceeds that of all other woods by

fourfold, while the value of the various oils and resins obtained

as by-products amounts to approximately $40,000,000. The coni¬

fers also supply the bulk of the raw material used in the pulp

and paper industry. In addition, the development of terpene

chemistry has pointed out the way for new uses of forest pro¬

ducts. Camphor can be successfully synthesized from pinene,

and turpentine can be broken down into isoprene which can

in turn be readily polymerized into rubber. Success in the latter

direction depends upon improvement in the yields of isoprene.

The present survey of the composition of the conifers has been

made for the purpose of determining their constituents per se

with a view to their utilization in the arts, and as a preliminary

step in obtaining more fundamental knowledge of the constit¬

uents themselves. The naval stores industry of the South is de-

Schorger — : Chemistry of American Conifers. 729

pendent upon the longleaf pine and Cuban pine and the ex¬

haustion of these species is in sight. It has been found, how¬

ever, that the western yellow pine will be capable of furnishing

naval stpres satisfactory both as to quality and quantity after

the species in present use are exhausted.

There are approximately 92 species of conifers in the United

States. From each species there is a possibility of obtaining

four distinct oils from as many different portions of the tree,

namely, the needles, bark, oleoresin, and wood, making in all

368 separate oils. This large field for investigation has been

practically untouched. The author has examined 25 different

volatile oils and oleoresins while approximately 26 others have

received close investigation by various chemists.

Previous Work

The literature has been carefully examined in order to obtain

references to the composition of the oils and oleoresins of Amer¬

ican species. In some cases the information is very meager be¬

ing limited to the yield of oil, saponification number or other

constants. Certain species have been excluded from the follow¬

ing table since the articles relating to them gave no definite in¬

formation in regard to the constituents present.

Needle Oils

Red spruce ( Picea rubens Sarg.)1

Black spruce ( Picea mariana Mill.)2

White spruce ( Picea canadensis Mill.)1

Hemlock (Tsuga canadensis Linn.)3

Balsam fir (Abies balsamea Linn.)4

Tamarack ( Larix americana Mich.)2

White cedar (Thuja Occident aUs Linn.)5

1 Hanson and Babcock, Jour. Am. Chem. Soc. 28 (1906) 1198.

2 Kremers, Pharm. Rund. 13 (1895) 135; Hanson and Babcock, Jour. Am.

Chem. Soc. 28 (1906) 1198; Schimmel & Co., Ber. Oct. (1897) 25.

8 Hunkel, Pharm. Rev. 14 (1896) 34; Bertram and Walbaum, Arch. d.

Pharm. 231 (1893) 290; Power, “Descriptive Catalogue of Essential Oils,”

p. 74; Hanson and Babcock, loc. cit. ; Pancoast and Graham. Proc. Pa.

Pharm. Ass. (1905) 184; Schimmel and Co. Ber. Oct. (1894) 21, Oct. (1897)

25.

4 Hunkel, Am. Jour. Pharm. 67 (1895) 9.

6 Wallach, Annalen 272 (1892) 99; Jahns, Arch. d. Pharm. 221 (1883)

748; Ayer, Oil, Paint and Drug Rep. June 25, 1906, p. 17.

730 Wisconsin Academy of Sciences , Arts, and Letters.

Western red cedar ( Thuja plicata Don.)6

Red juniper ( Juniperus Virginia Linn.)7

Douglas fir ( Pseudotsuga taxifolia Britt.)8

Oloresins

Amabilis fir (Abies amaUlis Forb.)9

Balsam fir ( Abies balsamea Mill.)10

Douglas fir (Pseudotsuga taxifolia Britt.) 11

Norway pine (Pinus resinosa Ait.)12

Cuban pine (Pinus heterophylla Sud.)13

Longleaf pine (Pinus palustris Mill.)14

Pond pine (Pinus serotina Mich.)15

Shortleaf pine (Pinus echinata Mill.)16

Loblolly pine (Pinus taeda Linn.)16

Digger pine (Pinus sabiniana Dougl.)17

Jeffrey pine (Pinus Jeffreyi ).18

6 Rose and Livingston, Jour. Am. Chem. Soc. 34 (1912) 201; Blasdale,

Jour. Am. Chem. Soc. 29 (1907) 539; Brandel and Dewey, Pharm. Rev. 26

(1908) 248; Schimmel & Co. Report, April (1909) 89.

7 Schimmel & Co., Ber. April (1894) 56; April (1898) 13; Hanson & Bab¬

cock, loc. cit.

8 Brandel and Sweet, Pharm. Rev. 26 (1908) 326.

9Rabak, Pharm. Rev. 46 (1905) 23.

10 Tschirch and Briining, ( Abies canadansis). Arch. d. Pharm. 238 (1900)

487 ; Emmerich, Am. Jour. Pharm. 67 (1895) 135.

n Blasdale, Jour. Am. Chem. Soc. 23 (1901) 162; Frankforter, Jour. Am.

Chem. Soc. 28 (1906) 1467; Rabak, Pharm. Rev. 22 (1904) 293.

12 Frankforter, Jour. Am. Chem, Soc. 28 (1906) 1467; Ibid. 31 (1909) 561.

13Herty, Jour. Am. Chem. Soc. 30 (1908) 863; Kremers, Pharm. Rundsch,

13 (1895) i35 ; Long, J. Anal, and Appl. Chem. 6 (1891) 1; 7 (1893) 99.

14 Kremers, Pharm. Rund. 13 (1895) 135; Pharm. Rev. 15 (1897) 7; Long,

Jour. Am. Chem. Soc. 16 (1894) 844; 21 (1899) 637 ; Jour. Anal, and Appl.

Chem. 6 (1891) 1; Semmler, Ber. 33 (1900) 1455; Ahlstrom and Aschan,

Ber. 39 (1906) 1441; Barbier and Hilt, Compt. Rend. 108 (1889) 519; Herty,

Jour. Am. Chem. Soc. 30 (1908) 863; Herty and Dickson, Jour. Ind. Eng.

Chem. 4 (1912) 495; Tschirch and Koritschoner, Arch. d. Pharm., 240

(1902) 568.

15 Herty and Dickson, Jour. Am. Chem. Soc. (1908) 872.

16 Herty and Stern, Science, 27 (1908) 327.

17 Wenzell, Am. Jour. Pharm. 44 (1872) 97; Pharm. Rev. 22 (1904) 408;

Thorpe, Jour. Chem. So:c. 35 (1879) 296; Samuels, Pharm. Rec. 8 (1888)

39; Blasdale, Jour. Am. Chem. Soc. 23 (1901) 162; Kremers Pharm. Rev.

18 (1900) 165; Rabak, Pharm. Rev. 25 (1907) 212; for additional references

see Bull. 119, U. S. Forest Service, p. 21.

18 Wenzell, Pharm. Rev. 22 (1904) 408; Blasdale, Jour. Am. Chem. Soc.

23 (1901) 162; Leuchtenberger, Arch. d. Pharm. 245 (1907) 701.

Schorger — Chemistry of American Conifers. 731

Wood Oils

Red juniper ( Juniperus virginiana L.)1

Longleaf pine (Finns palustris Mill.)2

Western yellow pine ( Finns ponderosa Laws.)3

Singleleaf pine (Finns monophylla Torr.)3

Jeffrey pine (Finns Jeffreyi ).3

Examination of Woods

The literature on the analysis of American woods is very

meager. Usually only one or two determinations were made on

each species. De Chalmot4 determined the yields of furfural

from a large number of woods, and Dean and Tower5 give the

cellulose content of a few species.

Scope of Present Work

The present investigation covers the examination of 25 oils

and oleoresins, and seven species of wood. Only three of these

oils had been previously examined by other investigators, the

remaining 22 being new to chemical literature. The following

tables give the products analyzed :

Needle Oils

Longleaf pine (Finns palustris Mill.)

Cuban pine (Finns heterophylla Sud.)

Western yellow pine (Finns ponderosa Laws.)

Sugar pine (Finns lambertiana Dougl.)

Digger pine (Finns sabiniana Dougl.)

Lodgepole pine (Finns contort a Loud.)

Red fir (Abies magnifica Murr.)

White fir (Abies concolor Parry.)

Douglas fir (Pseudotsuga taxifolia Britton.)

Incense cedar (Libocedrns decurrens Torr.) ‘

1 Waiter, Ann. Chim. Fhys. 1 (1841) 501; 8 (1843) 354; Chapmann and

Burgess, Proc, Chem. Soc. 168 (1896) 140; Semmler and Hoffmann, Ber. 40

(1907) 3521.

2 Teeple, Jour. Am. Chem. Soc. 30 (1908) 412; Kremers, Pharm. Rev. 22

(1904) 150; Schimmel and Co., Ber. April (1910) 109; Toch, Jour. Ind.

Eng. Chem. 6 (1914) 720.

8 Adams, Jour. Ind. Eng. Chem. 7 (1915) 957.

4 Am. Chem. J. 16 (1894) 224, 589.

5 Jour. Am. Chem. Soc. 29 (1907) 1119.

732 Wisconsin Academy of Sciences , Arts , and Letters.

Cone Oils

Western yellow pine ( Pinus ponder osa Laws.)

Sugar pine ( Pinus lambertiana Dougl.)

Longleaf pine ( Pinus palustris Mill.)

Oleoresins

Western yellow pine ( Pinus ponder osa Laws.)

Western yellow pine ( Pinus ponderosa scopulorum Engelm.)

Sugar pine ( Pinus lambertiana Dougl.)

Lodgepole pine ( Pinus contorta Loud.)

Digger pine ( Pinus sabiniana Dougl.)

Pinon pine ( Pinus edulis Engelm).

Sand pine ( Pinus clausa Sarg.)

Singleleaf pine ( Pinus monophylla Torr. and Frem.)

Jeffrey pine ( Pinus Jejfreyi).

Bark Oils

Incense cedar ( Libocedrus decurrens Torr.)

White fir ( Abies concolor Parry.)

Wood Oils

Port Orford cedar (Chamaecy paris lawsoniana Parlatore.)

Examination of Woods

Woods from four conifers and three hardwoods were analyzed

the species being:

White spruce (Picea canadensis B. S. P.)

Douglas fir ( Pseudotsuga taxifolia Britton.)

Longleaf pine ( Pinus palustris Mill.)

Western larch ( Larix Occident alis Nutt.)

Sugar maple ( Acer saccharum Marsh.)

Yellow birch (Betula lutea Michx.)

Basswood ( Tilia americana Linn.)

The three hardwoods are added for comparison with the coni¬

fers.

The analysis of each wood covered the following determina¬

tions: (1) moisture; (2) ash; (3) ether extract ; (4) cold water

extract; (5) hot water extract ; (6) solubility in alkali ; (7) pen-

Schorger — Chemistry of American Conifers. 733

tosan and methylpentosan ; (8) cellulose; (9) acids formed by

hydrolysis; (10) methoxy groups; and (11) the ash, pentosan,

and methylpentosan content of the cellulose. A great amount

of experimentation was necessary in order to work out methods

giving accurate results.

Resume of Results

The composition of some of the volatile oils is particularly in¬

teresting. From the oil of Port Orford cedar wood was obtained

a very pure d-a-pinene having a higher specific rotation than

had been previously reported for this terpene. The leaf oil of

incense cedar contained a new sesquiterpene that was named

“labocedrene”. Previous to the present work /?-pinene had

been detected in quantity in only one oil while in 12 of the oils

from American conifers /?-pinene was found to be the major

constituent. It was possible to obtain apparently pure fractions

of /3-pmene from some of the conifers, and the constants for

the natural terpene were found to be considerably higher than

those recorded by Wallach for his synthetic ^-pinene.

Turpentine oils usually consist only of terpenes, a-pinene,

/8-pinene, and camphene being the usual constituents. Phellan-

drene had not been previously recorded as occurring in oils of

this class but it was found that the turpentine oil of P. contorta

consisted almost entirely of this terpene. The same holds true

with respect to sesquiterpenes. Cadinene was identified in the

turpentine oils of P. edulis and P. monophylla, and an uniden¬

tified sesquiterpene occurs in P. ponderosa. So far as known

the only turpentine previously mentioned as containing a ses¬

quiterpene is P. longifolia of India.1

The composition of the oils has brought out several points of

phytochemical and botanical interest. The oil obtained from the

oleoresin of P. sabimana consists almost entirely of n-heptane

while that from the needles consists of terpenes. The source of

the small amount of heptane, 3 per cent, present in the needle

oil may be safely attributed to the small twigs, since they were

not removed from the needles before distillation. The phyto¬

chemical processes occurring in the wood and in the needles are

accordingly entirely different.

1 Schimmel and Company.

734 Wisconsin Academy of Sciences , Arts , and Letters.

Recently the composition of certain oils has been applied to

determining species.1 On the Pacific coast there occur two spe¬

cies of pines, P. ponderosa and P. J effreyi , that appear to grad¬

ually merge into each other, the intermediate forms being known

as ‘ ‘ cross variety’ ’ or “bastard” pine. Identification in the

field and in the laboratory even by the trained botanist was very

uncertain. Analyses of the oleoresins from five typical trees of

each type showed clearly that there was no intergradation be¬

tween P. ponderosa and P. J effreyi and that the “cross variety”

pines should be referred to P. ponderosa. Heptane was found

only in typical P. J effreyi.

The eastern form of P. ponderosa occurring in the Rocky

Mountain region is known as P. ponderosa scopulorum. Some

botanists maintain a distinction between the two while others

class them under a single species. It was found, however, that

the turpentine oils were distinctly different. The oils from the

P. ponderosa were laevo-rotatory and consisted very largely of

/?-pinene, while those from P. ponderosa scopulorum were d-ro-

tatory and contained about 65 per cent a-pinene. The well-

defined differences between the volatile oils shows that a dis¬

tinction between the species and its variety should be main¬

tained.

The cellulose content of the woods was found to be nearly con¬

stant both for the conifers and hardwoods especially if the per¬

centage content is based on the wood free from water soluble

and ether soluble constituents. The quantity of pentosans pres¬

ent in the hardwoods is considerably greater than in the coni¬

fers. This distinction is also maintained in the celluloses. It

is a striking fact that the pentosan content of the isolated cellu¬

loses is practically the same as that of the original wood, point¬

ing to distinctly different kinds of cellulose. The quantities of

methoxy groups and hydrolytic acid obtained from the conifers

are also smaller than from the hardwoods.

The wood of the western larch ( Larix occidentalis ) was found

to contain, about 10 per cent of a galaetan2 that had not been

previously described in the literature. This galaetan yielded

only galactose on hydrolysis. Further investigation showed that

1 Schorger — “Chemistry as an Aid in the Identification of Species”, Proc.

Soc. Am. Foresters, 11 (1916) 33-39.

2 Schorger and Smith, “The Galacton of Larix Occidentalis ”, Jour. Ind.

Eng. Chem. 8 (1916).

Schoryer — -Chemistry of American Conifers. 735

galactans were characteristic of the conifers as they were de¬

tected in five additional species. The significance, if any, of

their occurrence remains to be determined.

Examination of Oils and Oleoresins

Oil of Port Orford Cedar [Chamaecy pans lawsoniana (Murr.)

Parlatore] . 1

This species is limited in its distribution to southwestern Ore¬

gon and northern California. Selected pieces of resinous wood

when distilled with steam gave 10 per cent of oil having the

constants: d15° 891; nDl5° 1.477. After standing in a tightly

stoppered amber-colored bottle for four years, the oil had the

constants: d15° 0.9061; nDl5° 1.4806. On rectification by shak¬

ing with sodium carbonate solution and distillation with steam

the, oil lost 16.4 per cent by volume. The rectified oil had nearly

the same properties as the original oil as shown by the following ;

d16° 0.8905; nDi5° 1.4758; aD25° +39.60; acid No. 0.30; ester

No. 32.8; ester No. after acetylation 71.57.

A very pure d-a-pinene was obtained by repeated fractiona¬

tion, the constants of which were as follows: b. p. 156.0 - 156.1°

(760 mm.) ; d15° 0.8631 ; nDl5° 1.4684; specific rotation [a] D +

51.52° ; molecular refraction, M — 43.88 ; calculated for C10H16

f, 43.54. This is the highest previously recorded rotation for

a-pinene. Vezes2 had found for d-a-pinene from Grecian tur¬

pentine oil the rotation [a]D+48.4°, and for 1-a-pinene from

eucalyptus oil (E. laevopinea) Smith3 had found [a]Di90-48.630.

In conformity with its high rotation it was found impossible to

obtain a nitrosochloride from the purified pinene ; oxidation with

alkaline K2Mn208 gave d-pinonic acid ( [a]D+92.69°) m. p.

68-69°, the semicarbazone of which melted at 203-205°.

Dipentene was detected by means of the tetrabromide m. p.

124°. Saponification of the ester fractions gave an oil containing

d-borneol as shown by formation of d-camphor on oxidation;

the semicarbazone melted at 236-237°. Cadinene, m. p. of dihy¬

drochloride 117-8°, occurred in the high boiling fractions.

Analysis of the silver salts of the combined acids showed them

to consist of silver acetate and silver caprinate : Ag in silver

1 Jour. Ind. Eng. Chem.,- 6, 631 (1914).

2 Bull. Soc. Chim. (4) 5, 932 (1909).

3 Jour, and Froc. Roy. Soc. N. S. W. 32, 195 (1898).

736 Wisconsin Academy of Sciences , Arts , and Letters.

caprinate, C9H19COO Ag, calculated 38.66%— found 38.45% ;

Ag in silver acetate, CHsCOO Ag — calculated 64.64% — found

64.42%. Acetic, caproic and formic acids were also found free,

in the old oil.

The rectified oil had approximately the following composi¬

tion: d-a-pinene 60-61%; dipentene 6-7%; free d-borneol

11% ; bornyl acetate 11.5% ; cadinene 6-7% ; losses 5%.

Leaf Oil of Douglas Fir ( Pseudotsuga taxifolia Britt)1

The oil of this species was examined by Brandel and Sweet2

who claimed to have found free borneol, bornyl acetate and con¬

siderable camphene; pinene and limonene were thought to be

present but were not identified. The results obtaind by the

author were very different. Camphene could not be detected

and /2-pinene was found to be the principal constituent.

A series of six samples were examined with the following re¬

sults: d15° 0.8727-0.8759; nDl5° 1.4758-1.4780; aD20o-17.02o to

-22.17 ; acid No. 0.65-1.10; ester No. 11.13-24.25; ester No. after

acetylation 27.50-51.78.

Furfural was detected in the first fraction of the oil by the

deep rose-color obtained on treating the aqueous extract with

aniline-hydrochloric acid solution. From a fraction b.p. 156-

157°, d15° 0.8682, aD220-ll-940, a-pinene, m. p. of nitrosochloride

103°, was obtained; its nitrolpiperidine melted at 118°. Examin¬

ation of the fraction b. p. 160-162° for camphene gave negative

results.

A fraction b. p. 170-172°, d15o 0.8628, aD25o-28.120 gave a

dihydrochloride m. p. 50°. The next fraction b. p. 172-178.2°,

d15° 0.8616, aD25-26.240, gave with difficulty a tetrabromide m.

p. 117-119° after two crystallizations from ethyl acetate, and

after a third crystallization, at 121-2°. The high rotation of the

fractions combined with the melting point of the tetrabromide

indicate the presence of liminene in addition to dipentene.

Borneol was isolated from a fraction b. p. 208-213, aD260-

19.42°, as the pthalic ester. The liberated alcohol on oxidation

gave camphor melting at 174°. The borneol was in part com¬

bined with acetic acid since the silver content of the salt isolated

1 Jour. Am. Chem. Soc. 35, 1895 (1913).

2 Pharm. Rev. 26, 326 (1908).

Schorger — Chemistry of American Conifers.

737

contained 64.26 per cent Ag; Ag calculated for CH3COOAg

is 64.64 per cent.

The highest boiling fractions contained “ green oil” of which

no definite derivatives were obtainable.

The major portion of the oil boiled between 164-167° and

consisted of /Fpinene. A fraction, b. p. 164-166°, d15° 0.8720,

aD220”17.190 gave a large yield of sodium nopinate on oxidation

with alkaline K2Mn208. The free nopinic acid melted at 126°.

The approximate composition of the oil was the following:

l-a~pinene 25% ; l-/3-pinene 48% ; i-(and 1-) limonene 6% ; bomyl-

acetate 6%; free alcohol as borneol 6.5%; “ green oil” 3%;

furfural, trace.

Oleoresin of Sand Pine ( Finns clausa Sarg.)1

The sand pine is a small tree practically confined in its range

to the state of Florida. The oleoresin contained 18.93% volatile

oil, 72.30% rosin, the remainder consisting of water and foreign

matter. Two samples of the volatile oil had the following prop¬

erties: d15° 0.8725-0.8723; nDl5° 1.4768-1.4767; aD20°-22.49 to

-22.80°.

The first fraction of the oil b. p. 157-160°, d15° 0.8656, aD2o°-

20.17°, cantained a-pinene the nitrolpiperidine of which melted

at 119°. Camphene was found in the fraction b. p. 160-162°,

d15° 0.8671, aD2o°-29. 31°, by conversion into isoborneol melting

at 207-9°.

/Fpinene was found to constitute about 75% of the oil. The

sodium nopinate obtained was oxidized to nopinene whose semi-

carbazone melted at 189°. Since the oil consisted so largely of

/8-pinene an attempt was made to isolate it in a pure state.

After ten fractionations over metallic sodium, two fractions of

fairly constant boiling point were obtained. The properties of

these fractions and of a synthetic /Fpinene prepared by Wallach

were the following.

Fraction B. P. nD20° d20^ [a]D

20°

1 164-165° 1.4772 0.8700 -25.00°

2 165-166° 1.4784 0.8709 -23.73°

1 Jour. Ind. Eng. Chem. 7, 321 (1915).

M Calculated

found for C10H16/=

44.19 43.54

44.23 43.54

47— S. A. L.

738 Wisconsin Academy of Sciences, Arts, and Letters.

Wallach ’s1 synthetic /3-pinene:

B. P.

163-164°

M

found

1.4724 0.8660 -22°201 44.13

Calculated

for

c10H16r

43.54

Fraction 2 was about four times as large as fraction 1 and

the differences in the constants suggests the presence of a second

terpene. All the constants have higher values than those given

by Wallach but this has been the author’s general experience

in the examination of those volatile oils of which /?-pinene was

the chief constituent. On the possibility that the increased val¬

ues might be due to the presence of camphene, fraction 1 was

examined for this terpene but with negative results.

/?-pinene is widely distributed in nature, but it may be of in¬

terest to mention that previous to the examination of the present

series of volatile oils, this terpene had not been deteced in quan¬

tity except in hyssop oil.2 The author has found /?-pihene to be

the principal constituent of the following oils: the needle oils

of longleaf pine, Cuban pine, Douglas fir, white fir, western yel¬

low pine, sugar pine and lodgepole pine ; the cone oils of western

yellow pine and sugar pine; the bark oil of white fir; and the

turpentine oils of western yellow pine and sand pine.

The rosin from the sand pine crystallized readily from ace¬

tone. The abietic acid crystals began to melt at 150-151° and

were completely liquid at 157°. When the rosin was crystallized

from alcohol containing 10% of concentrated hydrochloric acid

the crystals began to melt at 157-158° and were not com¬

pletely liquid until 167°. The resin acids occurring in the oleo-

resin evidently undergo rearrangement with heat, and in pres¬

ence of acids and other reagents. The abietic acid had the ro¬

tation [a]D-85.46°. Analysis of the silver salt follows :

0.4885 g. silver salt gave 0.1234 g. Ag. =26.34% Ag.

Calculated for silver abietate Ag. (C20H29O2), 26.37% Ag.

The turpentine oil of the sand pine has the following com¬

position : 1-a-pinene, 10% ; 1-camphene, 10% ; l-/?-pinene, 75%.

The rosin consists mainly of abietic acid.

1 Ann. 363, 1 (1908).

2 Schimmel & Company, April Report, 1908, p. 58.

Schorger — Chemistry of American Conifers. 739

The Oleoresin of Jeffrey Pine (Pinus Jeffreyi.)1

Five samples of oleoresin were examined in all. The yield of

oil varied from 8.81-11.25%, the average being 9.96%. The oils

had the following properties: d15° 0.6951-0.7110 ; nDl5° 1.3927-

1.4060. On fractionation 92.45% of this oil distilled between

98.2-113.0° principally between 99 and 102°. Redistillation

using a Hempel column gave an oil whose properties (b. p. 98.4°

and d15° 0.6881) showed it to consist of n-heptane.

The residue left above the temperature 113° distilled prin¬

cipally between 200-215°. A portion of the oil formed a floc-

culent precipitate with sodium bisulphite and showed other prop¬

erties characteristic of an aldehyde. A semicarbazone melting

at 91-92° was prepared. Owing to lack of material no further

derivatives could be prepared. Judging from the lemon-like

odor and the m. p. of the semi-carbazone it was thought that

citronellal2 was probably present, the racemic form of citron-

allal semicarbazone melting at 96°.

The colophony had an acid No. of 147.6, a saponification No.

178.1, and contained 12.5 per cent of resene. Using acetone

as the solvent, resin acid crystals melting at 137-8° were ob¬

tained, while when crystallized from acetone containing hydro¬

chloric acid they melted at 145-6°. The colophony of this spe¬

cies crystallizes readily differing in this respect from the colo¬

phony of P. sabiniana which also yields heptane.

The resin crystals obtained from the crude oleoresin melted at

170-171°. The silver salt was analyzed as follows: 0.3926 g. of

silver salt gave 0.1027 g. Ag — 26.16% Ag. Silver abietate,

Ag (C20H29O2), requires 26.37% Ag.

Leuchtenberger3 extracted the colophony of Jeffery pine with

ammonium carbonate and sodium carbonate solutions obtaining

the following acids: a-jeffropinic acid C10H14 02, m. p. 160-161° ;

/bjeffropinic acid, C12H1802, m. p. 81-82° ; a-jeffropinolic acid,

C14H2002 or C14H2202, m. p. 117-118° and /3-jeffropinolic acid

having the latter formula, m. p. 77-78°. None of these acids

agree in melting point with those obtained by the author. The

1 Jour. Ind. Eng. Chem. 5 (1913) 971.

2 Schimmel & Co. (Report, Oct. 1914-April 1915, p. 45) working with a

considerable quantity of material showed that the non-heptane constituents

consisted of n-decylic aldehyde, linalool, and methylchavicol.

3 Arch. d. Pharm. 245 (1907) 701.

740 Wisconsin Academy of Sciences, Arts, and Letters.

acid obtained from the oleoresin melted at 170-171°, and its sil¬

ver salt contained 26.16% of Ag agreeing with the formula of

abietic acid, C2OH30O2. a-jeffropinic acid requires 39.51% Ag

and a-jeffropinolic acid requires 32.98% Ag. To obtain acids

of these formulae it would be necessary for the original resin

acids to undergo profound alteration in heating to 145° C. which

is contrary to experience with resin acids.

The Oleoresin of Singleleaf Pine ( Pinus monophylla Torr.)1

The oleoresin contained 19.00% of volatile oil having the fol¬

lowing properties; d15° 0.8721-0.8733; nDi5° 1.4732-1.4733;

aDl5° + 14.41° to + 17.26°.

The oil distilled mainly between 156-160° and consisted largely

of d-a-pinene; m. p. of nitrolpiperidine 118°. /3-pinene was not

detected. The fraction b. p. 170-180°, aDis°-l-18°, gave readily

dipentene dihydrochloride, m. p. 49°. The highest boiling frac¬

tions contained cadinene. The fraction, b. p. 250-280°, aD25°

-f-10.58, gave 1-rotatory cadinene dihydrochloride, whose crys¬

tals melted at 117-118°.

The acid No. and saponification No. of the colophony were

155.9 and 163.3, respectively. The resin crystals from the colo¬

phony melted at 119-120° and were completely liquid at 129°.

The oleoresin contained large resin acid crystals that melted at

129-130° after six crystallizations from acetone. The resid acid

evidently has the formula, C20H30O2, since the silver salt con¬

tained 26.65% Ag; Ag (C20H29O2) requires 26.37% Ag.

The composition of the volatile oil is approximately as follows :

85% d-a-pinene; 4-5% i- or 1-limonene ; and 4-6% cadinene.

The Leaf and Twig Oil of Cuban Pine (Pinus heterophylla

Ell.)2

Four samples of leaf and twig oil had the following range of

properties: d15° 0.8877-0.8894; nDl5° 1.4845-1.4869; aD28°-32.09

to -35.67°; acid No. 0.65-0.75; ester No. 9.73-10.54; ester No.

after acetylation 46.26-53.81; average yield of oil 0.271%.

A sample of oil distilled from needles free from twigs had the

constants: d15° 0.8895; nDl5° 1.4880; aD28°-36.54; acid No. 0.78;

ester No. 8.75; ester No. after acetylation 43.46; yield of oil

0.193%.

1Jour. Ind. Eng-. Chem. 5 (1913) 971.

2 Journ. Ind. Eng. Chem. 6 (1914) 723.

1

Schorger — Chemistry of American Conifers. 741

Furfural was qualitatively determined in the pinene fractions

by the colorimetric method with aniline salts. The presence of

1-a-pinene was shown by means of the nitrolpiperidine, m. p.

117-8°. The 1-rotatory fractions b. p. 160-162° contained cam-

phene which was converted into isoborneol, m. p. 209-210°, and

then into camphor; m. p. of semicarbazone, 235-236°.

The principal terpene present in the oil was /Lpinene a frac¬

tion having the constants, b. p. 164-166°, d15° 0.8704, aD250-24.12°

gave one third of its weight of sodium nopinate. The nopinic

acid, m. p. 125°, was further oxidized to nopinone ; m. p. of semi¬

carbazone 185-6°. Dipentene was detected by means of the di¬

hydrochloride m. p. 49°, and tetrabromide, m. p. 115-7°. Phel-

landrene was absent.

The ester fraction contained 1-rotatory borneol, m. p. 201-202°,

isolated by means of the pthalic ester. The combined acids appear¬

ed to be caprylic and caproic acids from analysis of their silver

salts. The fraction b. p. 270-280°, d21° 0.9190, aD2i0-14.76°, gave

crystals of cadinene dihydrochloride, m. p. 118°. An 11.13%.

solution of the crystals had the rotation aD2i0-3.510.

The leaf and twig oil of Cuban pine has the following compo¬

sition: furfural trace; 1-pinene 4%; 1-camphene 10%;

l-/3-pinene 35-36% ; dipentene 8%; bornyl ester (as acetate)

3.5%; free borneol 11.4%; d-cadinene 18-19%. The combined

acids were apaprently caproic and caprylic acids.

Leap and Twig Oil of Longleaf Pine (Pinus palustris Mill.)1

A series of four oils had the following constants: d15° 0.8829-

0.8849; nDl5° 1.4818-1.4825; aD28°-26.78 to -30.49° ; acid No.

0.55-0.73 ; ester No. 6.05-7.22 ; ester No. after acetylation 36.53-

46.37 ; average yield of oil 0.401%.

It was thought that the yield of oil from the various species

might be correlated with the number and size of the oil ducts.

Microphotographs of cross sections of the needles brought out

this relation in a striking manner. The leaf of the long-leaf pine

containing five large ducts gave 0.401% of oil, the Cuban

pine needles containing ten small oil ducts gave 0.271% of oil

while the lodgepole pine needles containing only two oil ducts

gave but 0.112% of oil.

JJour. Ind. Eng. Chem. 6 (1914) 723.

742 Wisconsin Academy of Sciences , Arts f and Letters.

In harmony with most of the needle oils, small amounts of

furfural were present. The first fraction of the oil contained

1-a-pinene, m. p. of nitrolpiperidine 119°. Camphene was also

present in the fractions boiling between 160-162° as shown by

obtaining isobornoel, m. p. 207-210°, by hydration with acetic

acid-sulphuric acid mixture. /3- pinene was present in large

amounts; m. p. of nopinic acid 126-7° ; m. p. of nopinone semi-

carbazone 187°. Dipentene was detected through its tetrabro-

mide, m. p. 124°. Phellandrene and sylvestrene were apparently

absent.

The ester fraction after saponification yielded an 1-rotatory

oil, aD28°-37.170, having the boiling point of borneol. By means

of the pthalic ester method borneol, m. p. 201-202°, was obtained

which was further identified by oxidation to camphor ; m. p. of

semicarbazone 231-3°. The highest boiling fractions contained

cadinene whose dihydrochloride melted at 117-118°.

The approximate composition of the oil is the following : fur¬

fural trace ; 1-a-pinene 8-9% ; 1-eamphene 13-14% ; 1-/Lpinene

44% ; dipentene 5% ; bornyl ester (as acetate) 2.4% ; free alcohol

10.0% ; d-cadinene 10-11%.

Leaf Oil of Longleaif Pine (Pinus palustris Mill.)

An oil obtained by distilling needles from which all the woody

twigs had been removed by hand had the following properties :

d15° 0.8841 ; nDl5° 1.4834 ; aD28-32.50 ; acid No. 0.67 ; ester No.

5.91 ; ester No. after acetylation 40.46 ; yield of oil 0.417%.

Analysis allowed the same constituents to be present as in the

leaf and twig oil. The oil in the wood of this species consists

mainly of a-pinene. It was anticipated that the leaf oil would

accordingly contain less a-pinene and have a higher alcohol and

ester content than the leaf and twig oil. Less a-pinene was actu¬

ally found but the ester content was slightly lowered rather than

increased. The same result was obtained in the oils of the Cuban

pine.

The turpentine oils of the Cuban and longleaf pines are very

similar. It is interesting to note that the leaf and twig oils of the

two species contain the same constituents in practically the same

proportion.

The composition of the leaf oil is the following : furfural trace :

1-a-pinene 2% ; 1-camphene 12-13% ; l-/?-pinene 50% ; dipentene

8 'chorger — Chemistry of American Conifers.

743

5% ; bornyl ester 2% ; free borneol 9.8% ; d-cadinene 11% ; the

combined acids consist of caprylic acid, with probably heptoic

and eaproic acids.

The Cone Oil of Longleaf Pine (Pinus palustris Mill.)1

The green cones distilled in June gave 0.363% of oil having

the following constants; d15° 0.8756; nDl5° 1.4760; aD28°~9.22° ;

acid No. 0.42 ; ester No. 3.95 ; ester No. after acetylation 31.07.

The fraction, b. p. 156-158°, d15° 0.8637, aD240+6.820, gave

pinene nitrolpiperidine melting at 118-9°. In the cone oil ac¬

cordingly d-a-pinene is present while in the leaf and twig oil of

this species the a-pinene is decidedly 1-rotatory. Camphene was

present in the weakly 1-rotatory fractions b. p. 160-162° as shown

by conversion into isoborneol m. p. 208-210°. /1-pinene was iden¬

tified by oxidation to nopinic acid; m. p. 125-126°. Dipentene

was present, m. p. of tetrabromide 123-4°, but phellandrene was

not found.

The higher boiling fractions contained borneol, m. p. 202-

203°, and cadinene, m. p. of dihydrochloride 116-7°.

The cone oil has the following composition : furfural ; d-a-pin¬

ene 39-40% ; 1-camphene 12% ; l-/3-pinene 25% ; dipentene

6-7% ; bornyl ester 1.4% ; free borneol 7.6% ; d-cadinene 1-2%.

The Leaf and Twig of White Fir ( Abies concolor Parry.)2

A series of seven oils had the following range of constants:

d15° 0.8720-0.8777; nDl5° 1.4781-1.4796; aD25o-20.11o to -27.94° ;

acid No. 1.01-1.81 ; ester No. 14.48-27.34 ; ester No. after acety¬

lation 47.84-55.51; average yield of oil 0.128%. The oil dis¬

tilled from leaves taken from the top showed a slightly higher

total alcohol content than the oil from leaves at the base of the

same tree.

Furfural was detected in the first fraction. L-a-pinene was

present in small quantity; m. p. of nitrolpiperidine 118.5°.

From the fraction b. p. 160-162°, d15° 0.8695, aD230-27.39°,

isoborneol, m. p. 209-210°, was obtained showing the pres¬

ence of camphene. ^-pinene was the chief constituent of

the oil. The fraction b. p. 164-166.5° d15° 0.8715, aD230

-23.66°, gave on oxidation large quantities of sodium nopinate.

1 Jour. Ind. Eng. Chem. 6 (1914) 723.

2 Jour. Ind. Eng. Chem. 6 (1914) 809.

744 Wisconsin Academy of Sciences, Arts, and Letters.

The free nopinic acid melted at 126.6-127°. The oil boiling be¬

tween 170-180° gave a mass of crystals of phellandrene nitrite

melting at 102°. Limonene was not detected as ether the dihy¬

drochloride or tetrabromide.

Borneol was shown to be present by oxidation to camphor the

semicarbazone of which melted at 236-7°. The bornyl ester is

mainly the acetate since the silver salt of the acid obtained by

saponification contained 64.56% Ag. The fraction b. p. 265-

285° was emerald green in color and had the constants: d19.5o

0.925; nDl5° 1.4936; aD2o0-0.490 for a 37.83% solution in ether.

No solid derivatives of this oil was obtained.

The leaf and twig oil had the following composition : furfural

trace; a-pinene 12%; 1-camphene 8%; l-/3-pinene 42%; 1-phel-

landrene 15% ; bornyl acetate 6.5% ; free borneol 9.5% ; “ green

oil” 3%.

The Bark Oil of White Fir (Abies concolor Parry.)1

Two oils, distilled from the bark from small" trees peeled for

poles had the following constants: d15° 0.8767-0.8702; nDl5°

1.4833-1.4809 ; aD2O°-20.95° to 20.15° ; acid No. 1.22-0.87 ; ester

No. 6.88-6.43; ester No. after acetylation 23.34-20.45; average

yield of oil 0.095%.

About 80% of the oil distilled between 162.5° and 180°. Fur¬

fural was present as usual. About 9.0% of the oil consisted of

1-a-pinene, the nitrolpiperidene of which melted at 118°. The

fractions boiling between 163-170° gave an oxidation nopinic

acid, m. p. 126-127° ; further oxidation gave the ketone nopinone

whose semicarbazone melted at 188°. The presence of /3-pinene

is accordingly assured. The 1-rotatory fraction boiling between

170-180° gave dipentene dihydrochloride but no solid deriva¬

tive was obtained on bromination.

The fraction, b. p. 192-250°, containing the esters amounted

to only 4.5 g. and was not further examined. The ester and

free alcohol are calculated as bornyl acetate and borneol. The

highest boiling fraction consisted of “ green oil”.

The bark oil has the following composition : furfural ; 1-a-pin-

ene 9.0%; l-/?-pinene 60%; dipentene 12-13%.; ester as bornyl

acetate 2.5% ; free broneol 4.5% ; “ green oil” 5%.

1Jour. Ind. Eng. Chem. 6 (1914) 809.

S chorger — Chemistry of American Conifers » 745

The Leaf and Twig Oil of Western Yellow Pine {Pinus pon-

derosa Laws.)1

A series of 10 oils distilled from the leaves only had the fol¬

lowing range of properties: d15° 0.8718-0.8849 ; nDi5° 1.4789-

1.4815; aD22o°~15.73 to -19.59° ; acid No. 0.85-2.36 ; ester No.

3.88- 7.83 ; ester No. after acetylation 24.11-35.10 ; average yield

of oil 0.071%. A series of four oils distilled from the needles

and twigs had the constants ; d15° 0.8755-0.8844; nDl5° 1.4805-

l. 4838 ; aDo0°-15.94 to -17.26 ; acid No. 0.67-0.87 ; ester No.

5.89- 8.10 ; ester No. after acetylation 25.14-35.68 ; average yield

of oil 0.114%.

The oils contained very little a-pinene. After repeated frac¬

tionation only 1.5% was obtained distilling between 157 and

160°, having the constants, d15° 0.8660 and aD23-27.0°.

The pinene nitrosochloride obtained melted at 102.5°. Cam-

phene was not found. /J-pinene was present in large amounts ;

it was oxidized to nopinic acid, m. p. 126°, and to nopinone,

m. p. of semicarbazone 188°. Dipentene was present as shown

by the tetrabromide m. p. 124°.

Borneol was detected with difficulty. After saponification of

the ester fraction, the liberated alcohols were heated with

phthalic anhydride and the ester purified in the usual way. On

subsequent saponification an oil was obtained ; on oxidizing this

oil a few crystals having the appearance and odor of camphor

were formed. After sublimation the crystals melted at about

160°. Formic and acetic acids were present in the oil both in

the free and combined state. The fraction b. p. 255-285° con¬

tained the ‘ ‘ green oil” found in so many of the needle oils.

The composition of the oil is approximately as follows :

1-a-pinene 2%; 1-^-pinene 75% ; dipentene 6% ; bornyl acetate

2% ; free alcohol as borneol 7% ; “ green oil” 3%.

The Cone Oil of Western Yellow Pine (Pinus ponderosa

Laws.)1

The pale green oil had the following properties : d15° 0.8757 ;

nDl5° 1.4789 ; aD2o0-ll-48 ; acid No. 1.27 ; ester No. 7.20 ; ester

No. after acetylation 22.41 ; yield of oil 0.063%.

Furfural was detected colorimetrically. The fraction b. p.

1 Jour. Ind. Eng. Chem. 6 (1914) 893.

746 Wisconsin Academy of Sciences , Arts, and Letters.

159-164°, aD250-25.33° contained a-pinene; m. p. of nitroso-

chloride 103°. (3- pinene was shown to be present by obtaining

nopinic acid melting at 126-7°. The fraction b. p. 170-173° was

examined for phellandrene with negative results, while the frac¬

tion b. p. 173-176° gave a good yield of dipentene dihydm-

chloride, m. p. 50°.

The ester fraction was too small for further examination.

“Green oil” was present in the higher fraction.

The composition of the oil is the following: furfural, trace;

1-a-pinene 6.0% ; l-/?-pinene 60% ; dipentene 12-13% ; ester as

bornyl acetate 2.5%; free alcohol as borneol 4%; “green oil”

3-4%.

The Leaf and Twig Oil of Sugar Pine (Pinus Lambertiana

Dough)1

The seven oils examined had the following range of prop¬

erties: d15° 0.8676-0.8738; nDl5° 1.4777-1.4795; aD2O°-11.07 to

-16.50° ; acid No. 0.68-2.38 ; ester No. 2.22-5.91 ; ester No. after

acetylation 23.25-32.04; average yield of oil 0.090%.

The fraction b. p. 156-160° contained furfural and 1-a-pinene,

the pinene nitrolpiperidine melting at 119°. The greater por¬

tion of the oil distilled between 164-167° and contained 1-/1 -pi¬

nene. The oil when oxidized in the customary manner gave

nopinic acid, m. p. 126°, and nopinone, the semicarbazone melt¬

ing at 188.5°. Dipentene was present in the fractions b. p.

170-178°, the tetrabromide melting at 124°. The dihydrochlo¬

ride was also prepared. Since this compound melted at 50°,

sylvestrene was evidently absent.

Borneol was present as shown by oxidation to 1-camphor melt¬

ing at 167-170°. The silver salts prepared from the acids ob¬

tained from the ester fraction contained 64.86%, 40.80%, and

35.27% Ag respectively. Acetic acid was accordingly present

along with higher acids. “Green oil” was again present in the

higher fractions.

The composition of the oil is the following: furfural, trace;

1-a-pinene 21% ; l-/3-pinene 51% ; dipentene 12% ; bornyl acetate

1.5% ; free 1-borneol 8% ; “green oil” 1%.

JJour. Ind. Eng. Chem. 6 (1914) 893.

S charger — Chemistry of American Conifers .

747

The Cone Oil of Sugar Pine (Finns lambertiana Dougal.).1

The light green oil had the following constants : d15o 0.8692 ;

nDl5° 1.4771; aD2o0-23.180'; acid No. 0.63; ester No. 3.75; ester

No. after acetylation 17.04; yield of oil 0.318%.

Furfural was present in the first fraction along with 1-a-pi-

nene. The pinene nitrosochloride melted at 98-99°, and the

nitrolpiperidine at 116°. The 1-rotary fraction b. p. 160-163°

contained camphene. This terpene was identified by conversion

into isoborneol melting at 211-212° in a sealed tube. /Lpinene

was present as usual. For identification the nopinene semicar-

bazone melting at 188-188.5° was prepared. The small fraction

b. p. 170-180° gave dipentene dihydrochloride, m. p. 49-50°,

when treated with hydrochloric acid gas.

The ester fraction was too small for examination. A yellow oil

was obtained boiling between 255-290° that may be a sesqui¬

terpene. When dissolved in ether and saturated with HC1 gas

the solution became deep purple. A solid hydrochloride could

not be obtained.

The composition of the cone oil is approximately the following :

furfural, trace; 1-a-pinene 22%; 1-camphene 21%; l-/?-pinene

39-40% ; dipentene 4-5% ; ester as bornyl acetate 1.5% ; free

alcohol as 1-bomeol 3.5% ; sesquiterpene (?) 1%.

The Leaf and Twig Oil of Digger Pine (Finns sabiniana

Dough)2

Three samples of the oil had the following constants: d15°

0.8517-0.8566; nDl5° 1.4670-1.4708; aD2O-20.93° to -38.36° ; acid

No. 1.47-2.05 ; ester No. 6.77-11.98 ; ester No. after acetylation

25.86-37.16; average yield of oil 0.09%.

The oil began to distill at 100° and 6% was collected up to

152°. This fraction was repeatedly treated with concentrated

sulphuric to remove terpenes. The residual oil amounting to 3%

consisted of heptane as shown by the following properties: b. p.

98.5-101°, d15° 0.7013. The twigs present in the distillation ma¬

terial without doubt were the source of this small amount of

heptane, since the oil from the oleoresin obtained from the wood

of this species consists almost entirely of n-heptane.

The fraction b. p. 156-157°, d15° 0.8618, and aD20-26.24°

1 Jour. Ind. Eng. Chem. 6 (1914) 893.

2 Jour. Ind. Eng. Chem. 7 (1915) 24.

748 Wisconsin Academy of Sciences , Arts , and Letters.

contained a-pinene ; m. p. of nitrasoehloride 104-105° ; m. p. of

nitrolpiperidine 117°. The small amount of oil distilling between

160-170° was examined for /Fpinene with negative results,

Limonene was present, m. p. of tetrabromide 124°, while phel-

landrene and sylvestrene were absent.

The oil obtained by saponification of the ester fractions was

oxidized with a saturated solution of potassium permanganate.

Steam distillation yielded a small amount of oil having a strong

odor of camphor. From the oxidation liquors an acid was ob¬

tained that sublimed readily and crystallized from water in thin

needles. By titration of a known weight with standard alkali

and by determination of its melting point, 183-184°, this acid

was found to be anisic acid, indicating the presence of methyl-

chavicol in the oil. A small amount of green oil was present in

the higher fractions.

The fact that the oil from the needles of this species consists of

terpenes while the oil from the wood is mainly n-heptane has a

particular significance. It proves that in the digger pine at

least, if not in all conifers, that the phytochemical processes tak¬

ing place in the leaves and in the wood are entirely different.

The composition of the leaf and twig oil is the following :

n-heptane 3% ; 1-a-pinene 58-59% ; 1-limonene 18% ; ester as

bornyl acetate 3.5% ; free alcohol as borneol 6% ; methylchav-

icol (?) ; ‘ ‘ green oil” 2-3%.

The Leaf and Twig Oil of Lodgepole Pine (Finns contorta

Loud.)1

The sample examined had the following constants : d15° 0.8690 ;

nDl5° 1.4831 ; aD2o0-17.840 ; acid No. 0.90 ; ester No. 6.02 ; ester

No, after acetylation 32.30 ; yield of oil 0.234%.

An aqueous extract of the first fraction contained furfural.

This fraction b. p. 156-160°, d15° 0.8662, aD25°-24.85°, consisted

chiefly of a-pinene ; m. p. of nitrosochloride 103.0-103.5° ; m. p.

of nitrolpiperidine 118°. Camphene was shown to be present by

conversion into isoborneol m. p. 205-207° after one crystalli¬

zation. The principal terpene in the oil was /3-pinene, the

nopinic acid melting at 127°. The fraction b. p. 170-180° con¬

sisted largely of 1-phellandrene, the nitrite of which melted at

102°. Phellandrene is the chief terpene present in the turpen-

1 Jour. Ind. Eng. Chem. 7 (1915) 24.

Schorger — Chemistry of American Conifers. 749

tine oil of this species. Bromination of portions of the oil col¬

lected between 170-180° did not yield a solid dipentene tetra-

bromide, owing possibly to the large amount of phellandrene

present; however, dipentene dihydrochloride melting at 49° was

obtained.

Oxidation of the alcohols obtained by saponification of the

ester fractions gave a small amount of an oil having a strong

odor of camphor. The oxidation liquors contained anisic acid,

m. p. 183-184°. As in the case of the leaf and twig oil of digger

pine anisic acid indicates the probable presence of methyl chav-

icol. The fraction boiling between 265 and 284° and having the

rotation aD2i° +14.69 was rich in cadinene. The cadinene dihy¬

drochloride obtained melted at 117-118° and had the specific

rotation [a] d -45.66° It may be mentioned that all the cadinene

fractions from the various oils examined were d-rotatory while the

cadinene dihydrochlorides obtained were always 1-rotatory.

The oil has the following composition : furfural, trace ; 1-a-pi-

nene 3% ; 1-/Lpinene 49-50% ; 1-phellandrene and dipentene

19% ; ester as bornyl acetate 2.0% ; free alcohol as 1-borneol

7.5%; methyl chavicol (?) ; cadinene 7%.

The Leaf and Twig Oil of Bed Fir ( Abies magnified Murr. ) 1

The properties of the oil were the following : d15° 0.8665 ;

nDi5° 1.4861; aD2o°-16.700 acid No. 0.75; ester No. 9.93; ester

No. after acetylation 36.22; yield of oil 0.154%.

The oil did not begin to distill until a temperature of 167°

was reached. By repeated fractionation 3.6 grams of oil were

obtained distilling between 160-164°. On treatment with ethyl

nitrite and hydrochloric acid, the intense green coloration char¬

acteristic of the formation of pinene nitrosochloride was obtained

but none of the solid derivative separated out. Oxidation of the

oil distilling between 164-168° gave nopinic acid melting at

126-127° ; this proves the presence of /Lpinene. Phellandrene

was the only additional terpene that could be detected. Large

amounts of phellandrene nitrite melting at 102-103° were ob¬

tained. Dipentene could not be detected as either the tetra-

bromide or dihydrochloride.

The oil obtained by saponifying the ester fractions gave on

oxidation so small an amount of solid camphor that it could not

1 J our. Ind. Eng\ Chem. 7 (1915) 24.

750 Wisconsin Academy of Sciences , Arts , a/nd Letters.

be further characterized. About 13% of “ green oil” was pres¬

ent in the higher fractions. It had the following properties:

b. p. 255-260°; d15° 0.8963; nDl5° 1.4952; specific rotation [a]D

-6.05°. A drop of the oil when dissolved in glacial acetic acid

and then treated with bromine vapors, gave a purple solution,

becoming deep blue. . Attempts to prepare solid derivatives

such as the bromide, hydrochloride, nitrite, nitrosochloride,

etc., were unsuccessful. A careful study of this “green oil”,

characteristic of so many of the conifer leaf oils, should prove to

be highly interesting. The material, however, has been difficult

to obtain.

The ‘ ‘ green oil ’ ’ will probably prove to be related to the ‘ ‘ blue

oil” (azulene) found in numerous volatile oils.

The composition of the oil is approximately the following : fur¬

fural, trace; a-pinene (?); l-/?-pinene 16-18%; 1-phellandrene

52% ; ester as bornylacetate 3.5% ; free alcohol as borneol 75% ;

“green oil” 13%.

The Leaf and Twig Oil of Incense (Libocedrus decurrens

Torrey) d

Nine samples of oil distilled from normal material in the regu¬

lar manner had the following range of properties: d15° 0.8655-

0.8733; nDl5° 1.4754-1.4775; aD20° -3.20 to +38.68°; acid No.

0.48-0.74 ; ester No. 19.19-24.27 ; ester No. after acetylation

28.64-39.83 ; average yield of oil 0.225%. The variation in the

optical rotation is very pronounced.

A quantity of leaves and twigs that had been thoroughly mixed

was divided into three portions; the first portion was distilled

while fresh, and the second and third portions were distilled after

having been stored two and four weeks respectively in the open

air. Analysis of the three oils obtained showed a remarkably

close agreement in all of their constants, showing that the storage

had been without perceptible influence. It is interesting to note

that there was a slight increase in the yield of oil from the stored

material even when the calculation was based on the original

green weight.

In one case the distillate from a charge of leaves and twigs

was caught in four fractions and these fractions were examined

separately. The properties of the first fraction differed slightly

JJour. Ind. Eng. Chem. 8 (1916) 22.

Schorger — Chemistry of American Conifers. 751

from the remainder, but even in this case the difference was less

than anticipated.

The distillation experiments lasted from May to November.

The yield of oil was greatest during May and November but the

total borneol content of the oils was greatest in August and

September.

The first fraction consisted of 1-a-pinene and contained a small

amount of furfural. Eegardless of the rotation of the original

oil the pinene fractions were decidedly 1-rotatory. For example,

an oil having the rotation aD20o + 38.68° gave a fraction having

the boiling point of pinene and the rotation aD24o -19.88°

Pinene nitrolpiperidine melting at 117-118° was prepared from

it. /?-pinene and camphene were not found.

The oil distilling between 170-180° contained dipentene, limo-

nene and sylvestrene. The first two terpenes were shown to be

present by obtaining two tetrabromides by fractional crystalli¬

zation melting at about 113° and 123.5°. Sylvestrene was identi¬

fied by preparation of the dihydrochloride melting at 72-72.5°

and by the deep blue color which the sylvestrene, regenerated

from the dihydrochloride, gave with acetic anhydride and con¬

centrated sulphuric acid. Sylvestrene is one of the rarer ter¬

penes and this appears to be the first record of its occurrence in

any American oil.

Borneol was identified by oxidation to camphor melting at

173-174°. The combined acids consisted of acetic and caproic

acids. After removal of the esters a sesquiterpene was obtained

in the fraction b. p. 250-280° and a deep green oil between 280

and 310°. The sesquiterpene had the following properties: b. p.

260-280° ; d20° 0.9292; nD2.6° 1.4994; aD26° +6.4°. The hydro¬

chloride prepared from this fraction crystallized from ethyl ace¬

tate in thin plates and melted at 132-133°. This sesquiterpene,

“libocedrene”, could not be identified with any of the sesqui¬

terpenes recorded in the literature. Lack of material prevented

a more detailed study.

The composition of the oil is the following: furfural, trace;

1-a-pinene 12—16% ; d-sylvestrene, d-limonene and dipentene

54-58% ; bomyl acetate 8% ; free borneol 4% ; libocedrene 6-

7% ; “green oil” 2%.

752 Wisconsin Academy of Sciences , Arts, and Letters.

The Bark Oil of Incense Cedar ( Libocedrus decurrens Torrey.)1

The oil has the following constants; d15° 0.8621 ; nDl6° 1.4716;

aD2o° +1-10 ; acid No. 0.60 ; ester No. 3.22 ; ester No. after acety¬

lation 9.53 ; yield of oil 0.14%.

Furfural was detected colorimetrically. The oil consisted

largely of a-pinene, the nitrolpiperidine melting at 117-118°.

The small amount of oil distilling between 160-168° was exam¬

ined for /3-pinene with, negative results. The oil distilling be¬

tween 168 -173° gave dipentene dihydrochloride melting at 48-

49°. The melting point of the dihydrochloride indicates the ab¬

sence of sylvestrene.

The ester fraction was too small for identification of the con¬

stituents. “ Green oil” was again present in the high boiling

fractions.

The oil has the following composition : furfural, trace ; a-pinene

75-85% ; dipentene 5-6% ; ester as bornyl acetate 1% ; free alco¬

hol as borneol 2% ; “green oil” 3%.

The Oleoresin of Digger Pine (Pinus sabiniana Dougl.)2

The oleoresin contained 11.4% of oil having the constants:

d15° 0.6971; nDl5° 1.3903.

About 95% of the oil distilled between 96.1 and 98.8°. This

oil consisted of n-heptane as shown by determination of the phy¬

sical properties.

Rabak3 states that both the oleoresin and rosin are optically

inactive but this was not found to be true of either substance.

A 5.58% alcoholic solution of the rosin had the rotation aD2o0

+0.38°.

All attempts to obtain a crystalline resin acid from the orig¬

inal rosin were unsuccessful. At 10 mm. pressure, the rosin

distilled between 240 and 250° with only slight decomposition.

The distillate cooled to a hard transparent mass that crystallized

readily from acetone. The crystals melted at 151-152°. The

silver salt contained 26.15% of silver showing that the resin

acid had the formula of abietic acid, C20H30O2, the silver salt

of which requires 26.37 % silver.

Resin crystals removed from the original oleoresin by suction

1 Jour. Ind. Eng. Chem. 8 (1916) 22.

2 Forest Service — Bulletin 119, p. 18.

3 Pharm. Bev. 25 (1907) 212.

Schorger — Chemistry of American Conifers.

753

and then repeatedly crystallized from acetone and methyl alco¬

hol melted at 131° and had the specific rotation [a] D-95.82°.

When a portion of the same crystals were crystallized from

methyl alcohol containing hydrochloric acid triangular crystals

melting at 158-159° resulted. The molecular rearrangement

produced by hydrochloric acid in the case of resin acids is very

marked. The silver salt contained 26.44% Ag showing that the

resin acid had the formula C20H30O2.

It is shown that in accordance with the observations of pre¬

vious investigators the volatile consists largely of n-heptane.

Resin acids having the formula C20H30O2 were isolated from the

crude oleoresin and from the colophony distilled under reduced

pressure. The colophony could not be made to crystallize in

its original state.

The Oleoresin of Sugar Pine ( Pinus lamhertiana Dougl.)1 2

The oleoresin contained 16.4% volatile oil, 75.3% rosin, and

8.3% water and foreign matter.

The oil had the following constants: d15° 1.4727-1.4728;

[a]D+10.42°. The oil consisted largely of d-a-pinene, the nitro-

sochloride of which melted at 103°. The small fraction distill¬

ing between^ 160-168° contained some /3- pinene since a small

amount of nopinic acid melting at 125° was obtained on oxida¬

tion. By repeated fractionation about 10 cc. of oil having the

specific gravity 0.8550 was collected between 169-174.5°. Bro¬

mine did not give a solid derivative but a copious precipitate

was obtained with nitrous acid. The crystals when filtered off

with a force pump suddenly decomposed into an amorphous mass

that could not be obtained again in a srystalline state. It is

probable that a small amount of phellandrene or terpinene is

present.

A fraction boiling between 110 and 130° at 25 mm. contained

an aliphatic hydrocarbon. After repeated treatment with con¬

centrated sulphuric acid, it had the constants: b. p. 194 to 201°

at 742.7 mm. ; d15° 0.7549 ; nDl5° 1.4249. It is possible that the

container in which the oleoresin had been shipped contained a

small amount of a petroleum hydrocarbon.

1 Forest Service Bulletin 119, p. 22.

2 Jour, and Proc. Roy. Soc. 1ST. S. W. 25 (1901) 124.

48— S. A. L.

754 Wisconsin Academy of Sciences , Arts , and Letters.

The hydrocarbon in the highest boiling fractions resembled

the sesquiterpene, aromadendrene, described by Smith.2 It had

the following properties: b. p. 144-148° at 30 mm. (250-255°

at 739.9mm.) ; d15° 0.9238; nDl5° 1.5006; [a]D +37.88°. No solid

derivatiyes were obtained.

Attempt to crystallize the original colophony as well as the

product obtained by distilling it under reduced pressure were

unsuccessful.

The volatile oil had approximately the following composition :

70-75% d-a-pinene; 5% /3- pinene; 2 to 3% of a terpene possibly

phellandrene ; 2 to 3% of an aliphatic hydrocarbon probably an

impurity; and 10 to 12% of a sesquiterpene.

The Oleoresin of Western Pine ( Pinus ponder osa Laws.)1

The six samples of oleoresin examined from California con¬

tained an average of 17.8% of oil, having the following proper¬

ties: d15o 0.8625 - 0.8688; nD15l 1.4772 - 1.4793: aD21o - 12.41

to - 26.52°.

a-pinene was identified by conversion into the nitrosochloride,

m. p. 103°, and the nitrolpiperidine, m. p. 118°. The oil con¬

sisted largely of (3- pinene. After repeated fractionation 40%

of the oil distilled between 166.6° and 167.6° ; it had the con¬

stants; d15o 0.8670; nDl5o 1.4762; [a]D -15.33°. On oxidation

about 22% of sodium nopinate was obtained. The nopinic acid

melted at 126°. It is a curious fact that in spite of the wide

distribution of /Lpinene in the conifer oils the 1-rotatory form

has so far been met with. Limonene was found in the oil boil¬

ing at about 175°. The tetrabromide melted at 104° and the

dihydrochloride at 50°.

The first sample examined contained about 7% of oil boil¬

ing above 180° that appeared to be mainly polymerization pro¬

ducts; it had a rotation of -0.86°. Later an oil was found

containing about 13% distilling above 200°. This residue dis¬

tilled mainly between 250-280°, and had the constants: d15o

0.9276; aD20o+17.68°. When the etheal solution was saturated

with HC1 gas a crystalline dihydrochloride could not be ob¬

tained from the residue left after evaporation of the solvent.

The behavior when inoculated with crystalline hydrochlorides

was interesting. When a crystal of dipentene dihydrochloride,

m. p. 49-50°, was added, a small amount of crystals was ob-

1 Forest ServJ. £ Bulletin 119, p. 11; Proc. Soc. Am. For. 11 (1916) 36.

Schorger — Chemistry of American Conifers.

755

tainted that melted at 102-106° after two crystallizations from

alcohol; after a third crystallization the m. p. was 101-103°.

When inoculated with cadinene dihydrochloride, m. p. 118°, a

crop of crystals were obtained that melted at 118°. It is prob¬

able that a small amount of cadinene is present, although the

dihydroehloride of this sesquiterpene usually crystallizes with

ease.

According to patents held by Schering and Company,1 /3-pin-

ene is stated to give much larger yields of isoprene than a-pin-

ene. Since the oil of western yellow pine could be rendered

available in large quantities and since it contained so large a

proportion of /3-pinene it was desirable to investigate the above

statement. An improved form of the Harries isoprene lamp

was constructed. With this apparatus, however, it was found

that both a-pinene and /?-pinene gave practically the same yield

of isoprene, namely 10%. 2

The colophony had the specific rotation [a] d- 12.88°. The

crystals obtained by digesting the powdered colophony with

alcohol containing hydrochloride acid followed by recrystalliza¬

tion from acetone melted at 159-160° and had the specific rota¬

tion [a]D-78.44°. The crystals obtained from dilute acetone

had the characteristic shape of abietic acid. The identifica¬

tion was checked by analysis of the silver salt; found 26.25%

Ag; calculated 26.37%Ag. The resin crystals obtained from

the rosin distilled under reduced pressure melted at 150-151°

and had the specific rotation [a]D-54.28°.

The volatile oil3 contains about 5% 1-a-pinene; 60% l-/?-pin-

ene; 20% 1-limonene; and about 10% of a sesquisterpene which

appears to be cadinene. The rosin contains about 90% abietic

acid.

The Oleoresin of Western Yellow Pine, Variety Scopulorum

(Pinus ponder osa scopulorum Englem)4

The oils contained from oleoresins collected in Arizona had

the following properties: d15° 0.8639-0.8672; nDl5° 1.4723-

1.4729 ; [a] d+ 12.86 to + 13.03°.

1 German Patent 260,934; K. Stephan, U. S. Patent 1,057,680 (1913)

(Assignor to Schoring and Company).

2 Jour. Ind. Eng. Chem. 7 (1915) 924; with R. Sayre.

3 Adams [Jour. Ind. Eng. Chem. 7 (1915) 957] working in Wallach’s

laboratory reached the conclusion that the oils distilled from the wood of

western yellow pine, digger pine, singleleaf pine, have about the same com¬

position as the author had found for the oils from the oleoresins of the same

species.

4 Forest Service Bulletin 119, p. 15.

756 Wisconsin Academy of Sciences, Arts , and Letters.

The oil consisted largely of a-pinene, the nitrosochloride melt¬

ing at 103°. /3-pinene was present in very small amounts in

contrast with the oil of P. ponderosa. The nopinic acid ob¬

tained melted at 125°. Limonene was identified by means of

the tetrabromide, m. p. 104.5, and dihydrochloride, m. p. 50°.

It will be noted that the turpentine oils from Pinus ponderosa

and its variety P. p. scopulorum are distinctly different ; the oil

from the former is 1-rotatory and consists mainly of /?-pinene,

while the oil from the latter is d-rotatory and consists largely of

a-pinene. The decided difference between these oils is good

evidence that the distinction between the species and subspecies

should be maintained.1

The resin had the specific rotation [aJD -30.95°. After pre¬

liminary digestion with alcohol containing hydrochloric acid,

crystals of abietic acid were obtained melting at 159°. Three

silver salts prepared from the abietic acid had an average silver

content of 26.25%; silver abietate, Ag (C20H29O2), requires

26.37% silver.

The turpentine oil of P. p. scopulorum has the following com¬

position: 60-70% d-a-pinene; 5% /?-pinene; and 20-25% lim¬

onene. The rosin consists of abietic acid.

The Oleoresin of Lodgepole (Pinus contorta Loud.)2

The oleoresin gave on steam distillation 14.7% of oil having

the following constants : d15° 0.8518-0.8549 ; nDi5° 1.4860-1.4862 ;

[a]D-20.12°.

About 82% of the oil distilled between 170-180° at atmos¬

pheric pressure. The residue remaining in the flask and

amounting to 15% solidified on cooling to a hard amber-colored

mass. The high degree of polymerization pointed to phellan-

drene. This was confirmed by preparation of the nitrite melt¬

ing at 103°. A carefully purified sample of the phellandrene

had the following properties: b. p. 60° at 11 mm.; d2P 0.8460;

15°

nDi5° 1.4861; [a]D -12.36°. No additional terpenes could be

detected. This occurrence of phellandrene is very interesting

since it is the first recorded occurrence of phellandrene in the

turpentine oils of any of the Pinus family.

1 Schorg-er, Froc. Soc. Am. Foresters 11 (1916) 33.

a Forest Service Bulletin 119, p. 25.

fichorger — Chemistry of American Conifers. 757

The colophony contained some of the polymerized phel-

landrene. About 80% of abietic acid crystals were obtained

from the colophony by crystallization from alcohol containing

hydrochloric acid. The triangular plates melted at 159-160°,

The silver salt contained 26.15% Ag in agreement with the

formula Ag (C20H29O2).

The turpentine oil of lodgepole pine accordingly consists

mainly of l-/?-phellandrene and the colophony of abietic acid.

The Oleoresin of Pinon Pine (Pinus edulis Engelm)1

The oleoresins of pinon pine and singleleaf pine are very sim¬

ilar in odor, appearance and composition. The oleoresin of

pinon pine contained 76.5% colophony and 20% of a volatile

oil having the following properties: d15° 0.8680; nDl5° 1.4707;

[a]D+19.26°.

The oil consisted largely of d-a-pinene the nitrosochloride

melting at 103°. /?- pinene was detected with difficulty, the

few crystals of nopinic acid obtained melting at 123°. The

high boiling fractions contained the sesquiterpene cadinene : b. p.

135-140° at 20 mm.; d15° 0.9173; nDl5° 1.4926; [a]D +15.41°.

The dihydrochloride melted at 118 ° and was 1-rotatory. So far

as known this was the first case in which cadinene had been

found in a turpentine oil.

All attempts to obtain crystalline a resin acid from the colo¬

phony were unsuccessful. The crystals obtained from the crude

oleoresin melted at 129-130° after four crystallizations from

acetone. When these were dissolved in methyl alcohol and

hydrochloric acid was added, triangular plates melting at 137°

were obtained. The latter crystals had the specific rotation

[a] D -52.77° and the silver salt contained 26.46% Ag. The acid

accordingly has the empirical formula of abietic acid.

The volatile oil of this species contains 70-75% d-a-pinene,

about 5% +pinene, and 15-20% d-eadinene. The resin acid

in the oleoresin is isomeric with abietic acid.

1 Forest Service Bulletin, 119, p. 28.

758 Wisconsin Academy of Sciences, Arts, and Letters.

PART II

Analysis of Woods

The methods for the analysis of woods are largely empirical.

The only determination that may be considered as accurately

showing the amount of a definite group present is the methoxy

determination according to Zeisel. The acetic acid obtained on

digestion with dilute sulphuric acid may be considered as derived

from acetyl groups (CH3CO-) and acetic acid residues

(-CH2CO-) . The decomposition of the wood is evidently con¬

siderable since birch sawdust loses about 30% by the above di¬

gestion.

The estimation of pentosans and methylpentosans by deter¬

mining the amounts of furfural and methyl furfural formed

on distillation with 12% hydrochloric acid gives closely agreeing

results when the procedure worked out by Tollens and his pupils

is followed. In the case of woods the difficulty lies in determin¬

ing the proper source of the furfural. According to Cross and

Bevan, in addition to the pentosans, wood also contains “fur-

furoids,” while to the cellulose is assigned the structure of an

oxycellulose which in turn gives furfural. All the furfural

obtained is usually calculated as pentosan though it is evident

that this procedure is not strictly correct. It is a striking fact

that the pentosan content of the isolated cellulose as calculated

from the yield of furfural is practically the same as that of the

original wood. Whether the furfural originates from the cellu¬

lose proper or from pentosan residues in the cellulose has not

been definitely decided.

The cellulose was determined by the chlorine method. As

originally described by Cross and Bevan1 it calls for a pre¬

liminary boiling of the ligneous material with lOOcc. of 1%

NaOH. Also following chlorination and the addition of sodium

sulphite solution, the latter is brought to boiling, 0.2% of NaOH

are added and the solution is boiled for five minutes. Accord¬

ing to the investigations of Renker2 the preliminary treatment

1 “Cellulose”, p. 95.

2 “Bestimmungsmethoden der Cellulose”, (1910) p. 44.

Schorger — Chemistry of American Conifers.

759

with NaOH as well as the subsequent addition of NaOH to the

sulphite solution causes an attack of the cellulose resulting in

a lower yield. Both these observations have been confirmed.

Since solutions of sodium sulphite have a decidedly alkaline

reaction as a result of hydrolysis, there was a possibility that

even the sodium sulphite attacked the cellulose. This was

found to be the case since when the solution was kept saturated

with sulphur dioxide during heating the yield of cellulose was

increased 1-2% in some cases.

The chlorination was limited to 30 minute periods since in

many cases a first chlorination lasting one hour as usually recom¬

mended is too long. The length of time and manner of heat¬

ing the sulphite solutions was also fixed to 30 minutes heating

in a water bath. Renker recommends heating the sulphite

solution on the steam bath for 4 ‘ 1 to 2 hours. ’ ’ On account

of the alkaline reaction of the sodium sulphite, the period of

heating should be as short as possible.

The conifers are much more resistant to the action of chlorine

than the broad-leaved trees, showing that there is a difference

in the lignin. The lignin of the conifers contains fewer meth-

oxy groups' and gives less acetic acid on hydrolysis. There is

also a wide difference in the pentosan content of the two classes

of woods. Yellow birch, for example, contains four times the

amount of pentosan found in Douglas fir. As previously men¬

tioned the cellulose from the various species give about the

same amount of furfural as the original woods.

When the percentage of cellulose is based on the wood free

from materials soluble in hot water and ether the following is

obtained.

The conifers accordingly contain a slightly greater amount of

cellulose.

760 Wisconsin Academy of Sciences , Arts , and Letters.

The methods of analysis being largely empirical, they are

given in considerable detail. In order to obtain closely agree¬

ing results, it is necessary, especially in the case of woods, to

follow the methods exactly as described.

Method of Analysis

Sampling - — A cross-sectional disc about two inches thick is

taken from the tree about 20 feet from the ground and from

this disc two diagonally opposite sectors are split out, the size

of the sectors depending upon the diameter of the trees. The

material employed for analysis consists of two forms — thin

shavings and sawdust. The shavings are obtained by plan¬

ing off a radical face from each of the sectors previously de¬

scribed. The damp shavings are then passed through a grinder

having a shredding effect, the resulting fragments being 3-5mm.

long and l-2mm. wide. The material after air drying is

then screened and all that passes through a 40-mesh sieve is

rejected. The residual material is then thoroughly mixed

to insure a uniform sample. The remaining portions of the sectors

are then cut into sawdust and the sawdust thoroughly mixed. A

portion of the sawdust from coniferous woods will be kept in a

sealed container (Mason jars are very convenient) for the

determination of moisture by the xylol method and the deter¬

mination of volatile oil, while the remainder after air drying

is so ground in a mill as to pass through a 40-mesh sieve. All

the moisture content being determined in a separate sample,

the material used for analysis should be in the air-dry form,

the moisture content being determined in a separate sample.

All results are calculated on the oven-dry basis.

The 40-mest sawdust should be kept in a rubber-stoppered

flask so that the moisture having once been determined the

samples taken out for analysis can be easily reduced to the dry

weight by calculation.

Moisture — Three grams of 40-mesh sawdust are weighed out

in a glass-stoppered weighing bottle and dried to constant weight

in an air oven at 105° C. Dry wood is very hygroscopic

and should always be weighed in a closed vessel In the case

of coniferous woods the moisture figure must be corrected for

volatile oil.

Volatile Oil — Twenty-five grams of sawdust from the sealed

container are quickly weighed, placed in a 250 c.c. Erlenmeyer

Schorger— Chemistry of American Conifers. 761

flask, and 75 c.c. of water saturated xylol added. On distilla¬

tion the xylol and water distill over together, the distillate be¬

ing collected in a graduated funnel. The amount of water

present can then be read off directly. (For details of this method

see Forest Service Circular 134) .

Ten grams of sawdust are weighed into a tared wide-mouthed,

stoppered Erlenmeyer flask. The flask is then provided with a

rubber stopper containing a tube extending nearly to the bot¬

tom of the flask for the introduction of steam and an outlet tube

for connection with a condenser. The flask is heated in an oil

bath maintained at 110° C. and steam is passed in gently until

oil ceases to pass over. This point can be readily ascertained

by catching a few cc of the distillate in a test tube in which

case even traces of oil are distinguishable on the surface. When

all the oil has been driven over the stopper is withdrawn and

any adhering sawdust is washed down into the flask. Continue

heating the flask in the oil bath until practically all the water

is expelled. This operation is greatly facilitated by inserting

a tube into the mouth of the flask and applying suction with

a water pump. The exterior of the flask is then carefully

cleaned and the drying completed in the air oven. The

stoppered flask is then weighed after cooling.

In this way the weight of wood substance is obtained, the

water and volatile oil having been removed. Since the mois¬

ture content of the original sample has been determined by the

xylol method, subtracting the combined weight of residual wood

substance and moisture from the original weight of the sample

gives the amount of volatile oil.

The determination of volatile oil by heating a sample in the

oven and subtracting from the total loss in weight the water

found by the xylol method usually does not give the true oil

content. The x ‘ pine oil ’ ’ of longleaf pine can be quite readily

expelled with steam but only partially by heating for a brief

period in the oven.

The volatile oil determination may be neglected in the case of

only slightly resinous conifers.

Waxes , Fats , Resins — 3-4 grams of 40-mesh sawdust are ex¬

tracted with ether in a Soxhlet extractor, the amount of material

extracted being determined by weighing the residue remaining

after evaporation of the solvent. Calculations should be based

on dry wood.

762 Wisconsin Academy of Sciences, Arts, cmd Letters.

Ash — Five grams of sawdust are incinerated in a shallow

platinum dish in the electric muflle at a dull red heat. The

contents of the dish should be stirred occasionally, if necessary,

to insure complete combusion of the carbon. If the combustion

is incomplete the carbon will appear as a black suspended ma¬

terial on treatment with dilute hydrochloric acid.

Alkali Soluble — Two grams of 40-mesh sawdust are placed in

a 250 cc beaker, 100 cc of 1 per cent NaOH added, covered with

a watch glass, and placed in a pan of boiling distilled water for

exactly one hour, the height of the water in the pan being main¬

tained level with the solution in the beaker by addition of boil¬

ing distilled water. The contents of the beaker are occasionally

stirred. The material is then collected in a tared alundun

crucible, washed consecutively with hot distilled water, one per

cent acetic acid, and hot water ; it is then dried. The difference

is the portion soluble in alkali and consists of pentosans, lignin,

resin acids, etc.

Hot Water Soluble — Two grams of 40-mesh sawdust are di¬

gested with 100 cc of H20 in a 300 cc Erlenmeyer flask provided

with a reflux condenser. After the water has been boiled gently

for three hours, the contents are transferred to a tared alundum,

crucible, washed with hot water, dried and weighed.

Cold Water Soluble — Two grams of 40-mesh sawdust are

placed in a 400 cc beaker, 300 cc of water added, and allowed to

digest with frequent stirring for 48 hours. The sawdust is

then transferred to a tared alundrum crucible, washed with cold

distilled water, dried and weighed in a weighing bottle.

Pentosan and Methyl Pentosan — Two grams of 40-mesh saw¬

dust from coniferous woods (1 g. from hardwoods) are placed

in a 250 cc flask provided with a separatory funnel and attached

to a condenser. Add 100 cc of 12 per cent hydrochloric acid

(sp. gr. 1.06) 1 and distill at the rate of 30 cc of distillate in ten

minutes. The distillate should pass through a small filter be¬

fore entering the receiver. As soon as 30 cc of distillate are

collected, 30 cc of HC1 are added to the distillation flask and

the distillation is continued in this manner until 360 cc of dis-

1 The solution of hydrochloric acid is conveniently prepared as follows :

300 cc of the ordinary concentrated HC1 are diluted to 1000 cc and cooled

to room temperature with tap water. A hydrometer reading 1.06 is sus¬

pended in the acid and by adding a small amount of either con. HC1 or

water, as necessary, the desired specific gravity 1.06 is easily obtained.

Schorger — Chemistry of American Conifers. 763

tillate are collected. To the total distillate, add 40cc of filtered

phloroglucine solution that has been prepared at least a week

previously by heating 11 grams of phloroglucine in a beaker

with 300 cc of 12 per cent HC1, and after solution has taken

place make up to 1500 cc with 12 per cent HC1. After addi¬

tion of the phloroglucine, the solution soon turns greenish black.

Let stand 16 hours, when the furfural phloroglucide will have

settled to the bottom of the beaker. If a drop of the super¬

natant liquid gives a pink color with aniline acetate paper2 the

precipitation of the furfural is incomplete. A further amount

of phloroglucine solution is then added and the beaker allowed

to stand over night as formerly.

The furfural phloroglucide is filtered through a tared asbestos

crucible and washed with exactly 150 cc of water. The crucible

is then dried for four hours in a water oven and weighed in

a weighing bottle.

The crucible is then placed in a small beaker and 20 cc of 95%

alcohol are added to the crucible. The beaker is then placed

in a water bath, maintained at 60°, for ten minutes. The alco¬

hol is then removed with a suction pump and the process re¬

peated (usually four or five times) until the alcohol that runs

through is practically colorless.* 1 The crucible is then dried

for two hours in the water oven and again weighed^ The weight

of the residual phloroglucide subtracted from the weight of

mixed phloroglucides gives the weight of methyl furfural-

phloroglucide. From the weights of furfural-phloroglucide

and methyl-furfural-phloroglucide obtained the amounts of pen¬

tosan and methyl-pentosan present in the wood are calculated

from the tables of Kroeber and Tollens on pages 137 and 154

of Vol. II of Aberhalden’s “Handbuch der Biochemischen Ar-

beitsmethoden. ’ ’

Cellulose—' Two grams of shavings in a tared alundum crucible

are extracted in a Soxhlet extractor for 3 or 4 hours with a mix¬

ture of equal parts of alcohol and benzol. After removal of

2 The aniline acetate paper is conveniently prepared by dipping strips of

filter paper into aniline acetate. The latter is prepared by adding acetic

acid drop by drop to a mixture of equal parts of aniline and water until

a clear solution is obtained.

1 Extraction of the methyl-furfural-phloroglucide in a modified Soxhlet

extractor as described by Ishida and Tollens (J. f. Landw. (1911) 59) in

the author’s experience does not give accurate results owing to the difficulty

in determining when the extraction is completed.

764 Wisconsin Academy of Sciences , Arts , and Letters.

the solvent the shavings are thoroughly washed with hot water

using the suction pump. The moist shavings are then transferred

to a 250 cc beaker with a pointed glass rod, evenly distributed

over the bottom, and subjected to a slow stream of washed

chlorine gas for half an hour. The end of the tube delivering

the chlorine gas should be about one-half inch above the shav¬

ings. After the chlorine treatment the shavings are treated

with a solution of S02 until the chlorine odor disappears, trans¬

ferred to the alundum crucible, and washed with water. The

shavings are again returned to the beaker with the glass rod,

and 100 cc of a 2 per cent sodium sulphite solution are added.

The covered beaker is then placed in a boiling water bath for

30 minutes, the water in the bath being maintained on a level

with the solution in the beaker by the addition of hot distilled

water. The fibers are then transferred to the crucible and

washed with hot water. The above treatment is seldom suffi¬

cient to remove all the lignin, so that the treatment with chlor¬

ine and subsequent procedure as outlined above is repeated until

the fibers are practically a uniform white. The second and

following treatments with chlorine should not be longer than 15

to 30 minutes. After all the lignin has been removed the fibers

are given a final bleaching with 10 cc of a 0.1 per cent solution

of potassium permanganate, and rendered colorless with S02

solution. The fibers are then thoroughly washed with hot

water, acetic acid, and alcohol, and finally with ether and dried

at 105° in the air oven, the crucible being weighed in a weigh¬

ing bottle.

Acid Hydrolysis — Approximately 2g. of 40-mesh sawdust are

placed in a 250 c.c. Erlenmeyer flask and 100 c.c. of 2.5 per cent

H2S04 added. The flask is connected with a reflux condenser and

the contents are boiled quietly for 3 hours and then allowed to

cool. Wash down the interior of the condenser with a little distill¬

ed water and transfer the contents of the flask to a 250° c.c. grad¬

uated flask. Make up to the mark with distilled water free

from carbon dioxide. Let the solution stand several hours with

frequent shaking, and then filter.

A wide-mouthed, round-bottomed, 750 c.c. flask is provided

with a rubber stopper containing (1) a dropping funnel; (2)

a glass tube drawn out to a capillary, closed with a rubber tube

and pinch cock, and extending to the bottom of the flask ; and (3)

a Soxhlet connecting bulb-tube. Use an ordinary condenser, to

Schorger — Chemistry of American Conifers.

765

the end of which is attached for a receiver a 500 c.c. distilling

flask cooled with a stream of water and connected with a mano¬

meter and suction pump.

Place a few pieces of pumice in the boiling flask and then add

200 c.c. of the filtrate obtained above (in the case of hardwoods

use 100 c.c.). The flask is heated in an oil bath maintained

at 85° C. while the pressure is reduced to 40-50 mm. When

the contents of the flask are reduced to about 20 c.c., add dis¬

tilled water through the dropping funnel, drop by drop, at the

same rate that distillation takes place. When 100 c.c. of wash

water have been distilled over, titrate the distillate with N/10

NaOH using phenolpthalein as the indicator. If (a) 200 c.c.

or (b) 100 c.c. of solution were taken for distilla¬

tion, multiply the number of c.c. of NoOH used by (a) 5/4

or (b) 5/2 respectively, and calculate as acetic acid.

This method gives accurate results. - Duplicate determinations

should agree within 0.10 of 1 per cent. It is necessary to use

low temperatures and pressures to prevent decomposition of the

carbohydrates, etc., by the sulphuric acid before all the acetic

acid is removed.

All the distilled water used in this determination should have

been recently boiled to expel carbon dioxide.

Determination of Methoxy Group (CHsO)- — The principle of

the methoxy determination depends upon heating the sub¬

stance to be examined with hydriodic acid, whereby methyl iodide

is formed. The methyl iodide is swept from the reaction flask

into vessels containing a known volume of an alcoholc solution

of N /IQ silver nitrate, the methyl iodide being decomposed with

the formation of silver iodine. The undecomposed silver ni¬

trate is estimated volumetrically or the silver iodide formed is

precipitated by diluting the solution, filtering, and weighing.

Since 1 part of silver iodide is equivalent to 0.132 part of CH30

or 1 part of Ag N03 is equivalent to 0.1823 part of CH30 the

percentage of methoxy groups in the sample can be easily cal¬

culated. The details of the Zeisel method may be found in most

works on organic chemistry or organic analysis.

TABLE I. — Analysis of Woods.

766

Wisconsin Academy of Sciences , Arts , and Letters.

0* 3

a s

o.§

e

J

b§

£ e

tag

§1

o-§

§

*3

Si

0> O

1 » «

•S

a> »

© g

ae

CO £

Sg

gg

K o

" -ri

.1

If

cc §•

c« ^

c$ ^

PQ.§

°s

©£

kH^5

II

si

00 o

Wakeman — Pigments of Flowering Plants.

767

PIGMENTS OF FLOWERING PLANTS.

By Nellie A. Wakeman.

INTRODUCTORY CHAPTER.

Theories of Color in Organic Compounds.

While the study of pigmentation in plants early attracted the

attention of chemists as well as botanists, it was not until the in¬

troduction of synthetic dye stuffs in the latter part of the 19th

century that any considerable amount of attention was directed

to the determination of the cause of color in the pigment itself.

Until this time indeed, the constitution of most of the na¬

tural dye stuffs was unknown, consequently any consideration

of the relationship between color and molecular structure was

impossible. With the introduction of dye stuffs of known

constitution, however, the question not only presented itself

but well nigh forced itself upon the attention of chemists. The

earlier endeavors were, for the most part, directed toward de¬

termining a direct relationship between color and molecular

constitution. This led to a study of so-called chromophorous

groups and chromogens, a study which, while it has been fruit¬

ful of results in the manufacture of dye stuffs, has been of

much less value in the study of plant pigments. Recently,

however, these studies have assumed a more basal character

and the subject has been approached through the general ques¬

tion of absorption spectra, the invisible as well as the visible

portion of the spectrum being taken into consideration.

It is obvious that color does not inhere in the colored sub¬

stance itself, but is the response of sensation to the stimulus of

light which proceeds from the colored substance either by trans¬

mission or reflection. The different dyes and pigments pos¬

sess their many varying hues because, by a process known as

768 Wisconsin Academy of Sciences , Arts, and Letters.

selective absorption, each pigment absorbs certain definite colors

from white light and transmits or reflects only those which it does

not absorb. A transparent object takes on the color of the

light which it transmits, while an opaque object takes on that

of the light which it reflects.* If an object absorbs all of the

radiations of white light and transmits none, it is black; if it

absorbs all but the red radiations, for example, it is red; but

if it absorbs none and transmits all of the radiations of white

light, it appears to be colorless. Again, if light of only one color

be absorbed, violet for example, its complementary color, yel¬

low in this instance, will alone be visible. If on the other hand

two complementary colors alone are absorbed, the object will

appear relatively colorless. Many substances are quite trans¬

parent and colorless within the limits of the visible spectrum

which show selective absorption in the infra-red or ultra-violet

regions. Such substances only appear colorless. In a phy¬

sical sense they are similar to colored substances, for, physi¬

cally, there is little difference whether absorption is of radiant

energy of short wave length in the ultra violet, of medium

wave length in the visible portion of the spectrum, or of long

wave length in the infra-red.

That a substance shows selective absorption is probably due

to the fact that the oscillation frequencies of its molecules cor-

spond to certain definite wave lengths of radiant energy,

the energy corresponding to such wave lengths being absorbed

by the molecules. In accordance with this theory of color

in material objects, much attention has been paid in recent years

to the question of what molecular structures are likely to cor¬

respond to more or less definite periods of molecular vibra¬

tions, thus producing selective absorption. Narrowed down

to the study of pigments, the question has taken the form of

what particular configurations, as well as the introduction of

what group or groups of elements, will throw this selective ab¬

sorption into the region of the visible spectrum where color

will be produced. This brings the whole subject of chromo-

phorous groups into a new light and explains how the intro¬

duction of a given group, supposed to aid in the production

* Comparatively few substances, e. g. the metals, some solid organic dyes, feathers,

etc., which have a metallic lustre, owe their color to reflection. Most substances gen¬

erally considered opaque transmit light for some distance below the surface. Color in

such substances -is a transmission rather than reflection phenomenon.

Wakeman — Pigments of Flowering Plants.

769

of color, might result in one case in the change of a colorless

substance to a colored one, while in another case it might have

the opposite result of taking away the color from a colored

substance. It shows, in fact, that color in a substance is not a

function of a particular group of elements but of the struc¬

ture of the entire molecule.

The first attempt to show the relationship between constitu¬

tion and color in organic compounds appears to have been that

of Graebe and Liebermann1 in 1868. These investigators laid

down the rule as of general application that, if the colored

metallic salts of colorless organic acids are excepted, all col¬

ored organic compounds are rendered colorless by reducing

agents, and that in this reduction the compound adds on hy¬

drogen without the elimination of any other elements from the

molecule.

As illustrations they quote quinone, C6H4

°\

o/

1 011

reduced to hydroquinone, C6H6 l ; azobenzene, C6H5 N=N —

JOH

etc.

C6H5; reduced to hydrazobenzene, C6H5 N

-N — C6Hj

l

i

H

From these reactions they infer that colored compounds either

contain elements with incompletely saturated affinities, or that

some of the atoms. are more intimately bound than is neces¬

sary for their retention in the molecule; furthermore, that the

physical property of color depends upon the manner in which

the oxygen or nitrogen atom is combined, in the colored com¬

pounds these elements being in more intimate combination

than in the colorless compounds. In the case of colored nitro

and nitroso compounds, which are rendered colorless by re¬

duction to amido compounds, it is the intimate association of

the oxygen and nitrogen to form a group which renders the

substance colored.

Graobe and Liebermann ’s theory was formulated before the

present diketone formula for quinones was accepted, their con¬

ception of a quinone being that of a benzene nucleus with two

oxygen atoms linked together, hence the idea of “more inti¬

mate, or internal, combination. ’ ’

In 1876 Witt2 advanced an entirely different explanation.

1 Ber., 1, p. 106.

a Ber., 9, p. 522.

49— S. A. L.

770 Wisconsin Academy of Sciences , Arts, and Letters.

Color in a substance, according to Witt, is due to the presence

of a chromophore group in the molecule. Such a substance,

though generally colored, is not a dyestuff and is called by

Witt a chromogen. It becomes a dye by the introduction of a

salt forming auxochrome group. According to Witt the

principal chromophore groups are. the nitro _ > the ni-

Wo

troso, — N = O, the carbonyl — C = 0, and the allied group

the thio carbonyl, = C = S ; and also the azo menthin group

— C = N — , the azo group — N — N — . The principal auxo¬

chrome groups are the hydroxyl, the amino, and the mono-

and di- alkyl amino groups. Witt’s theory, while it proved

of great value in the synthesis of artificial dyes, as stated be¬

fore, ha^ been of comparatively little use in the study of plant

pigments, since only the corbonyl group among the so called

chromophore groups and the hydroxy among the auxochrome

groups are of at all frequent occurrence in the plant pigments

of known constitution. Moreover the mere presence of these

two groups, or of multiples of one or both, is not sufficient to

explain the phenomenon of color in the plant pigment mole¬

cule.

From time to time other chromophore groups have been

added to those named by Witt. Principal among these are the

— N— N— — N=N —

ethylene3 group =C=C— , the azoxy4 group ^ / or ||

o o

— N = N—

or \^/ , and combinations of some of the above named groups.

In 1888 Armstrong0 introduced his quinone theory of color.

Since dyestuffs in general can, by the addition of hydrogen, be

reduced to the corresponding leuco bases, Armstrong consid¬

ered all colored compounds to be quinones and the correspond¬

ing colorless compounds to be hydroquinones. Using the

Fittig diketone formula for quinones, Armstrong attempted to

show that the structure of colored compounds in general may

be represented by a quinoidal formula. Under the term quin-

oidal formula Armstrong included all structures containing

3 Ber., 33, p. 666.

«Ber., 31, p. 1361; 33, p. 123; 29, p. 2413.

6 Proc. Chem. Soc., 4, p. 27; 8, pp. 101, 143, 189, 194.

Wakeman — Pigments of Flowering Plants. 771

either the para quinone or the ortho quinone grouping, the

double bonds being satisfied by oxygen or any other divalent

element or group or by combinations of any of them.

Armstrong’s theory has received a great deal of attention,

much evidence both for and against it having been produced.

Though our present knowledge of the structure of colored com¬

pounds would indicate that by no means all colored substances

are of quinoidal character, yet a surprisingly large number, if

not all, of the substances of a quinoidal configuration are col¬

ored. The quinoidal configuration is in fact one of the best

known and most reliable chromogens.

In the study of plant pigments the quinone theory has proved

of much more value than Witt’s theory of chromophorous

groups. The constitution and the properties of a very large

number of vegetable dyestuffs, and of other colored substances

derived from plants, have been accounted for by assuming a

quinoidal structure. Moreover the closely related quinhydrone6

hypothesis of pigmentation in some plants promises to explain

biochemically the existence of many colors and shades of color,

as well as many changes of color, which have hitherto been un¬

accounted for.

In considering quinone and quinhydrone hypotheses of pig¬

mentation mention should be made of Richter’s7 oxonium

theory of quinones. According to Richter the characteristics

of oxonium salts, namely simple addition of the components

in their formation, ready decomposition in solution, and upon

sublimation, and marked increase in intensity of color, are also

those of the quinhydrones. For these and other reasons

hydroquinones, phenoquinones, etc., are regarded by Richter as

oxonium compounds formed by the addition of pnenols, etc., to

the tetravalent oxygen of quinones.

Assuming that the doubly bound oxygen of quinones acts

as a tetravalent oxygen does not impair the validity of the

quinhydrone hypothesis as suggested by Kremers and Brandel.

It brings the quinone pigments into line with the anthocyanin

pigments, as interpreted by Willstaetter, and explains how

many quinones, as well as many flavone and xanthone deriva¬

tives, also haematin and brazilin, dissolve in acids with an in-

6Ph. Rev., 19, p. 200.

7 Ber., 43, p. 3603.

772 Wisconsin Academy of Sciences, Arts, and Letters.

tense color, but are precipitated unchanged from this solution

by the addition of water. It is easy to understand how the

tetravalent oxygen in quinones, being basic, might add on the

elements of phenols as well as acids or how it might add on

the elements of a molecule of water. While it would not be

wise, however, without very careful investigation, to say it

were impossible, it is not easy, without altering our present

conception of the tetravalent oxygen, to see how the same oxy¬

gen could be able to form addition products with organic

nitrogen bases, such as phenylendiamine, and even with po¬

tassium hydroxide, which Richter represents it as doing.

In 1879 Nietzki* 8 formulated a rule, supposed to be of general

application, that the pigments of most simple construction are

yellow and by increase of molecular weight they gradually

change from yellow to red, then to violet, then to blue.

Schuetze9 in 1892 found that Nietzki ’s rule holds only in

certain cases; but that changes in color in general are the re¬

sults of changes in selective absorption in the regions of the

visible spectrum. The results of Schuetze ’s investigations are

summed up as follows :

1. A change of absorption from violet toward red usually

causes the following changes in color; greenish yellow, yellow,

orange, red, reddish violet, violet, bluish violet, blue, bluish

green, etc. Passing through the colors in this direction

Schuetze calls deepening or lowering the tint; in the opposite

direction, raising the tint.

2. Definite atoms and atomic groups by their entrance into

the molecule cause, for compounds of the same chromophore in

the same solvent, a characteristic deepening or raising of the

tint. Those which deepen the tint are called ‘ ‘ bathochrome ’ ’

groups or elements, those which raise the tint are called “hyp-

sochrome” groups or elements.

3. Hydrocarbon radicles are always bathoehromic. Conse¬

quently in homologous series the shade always deepens as the

molecular weight increases.

4. The same deepening of color is caused in the groups of

the periodic series as the atomic weights increase.

*Verhandl. des Vereins fur Befoerderung der Gewerbfleisses., 58, p. 231

(Quoted by Schuetze, Zeit. fur Phys, Chem., 9, p. 109).

9Zeit. fur Phys. Chem., 9, p. 109.

Wakeman — Pigments of Flowering Plants. 773

5. The addition of hydrogen always results in raising the tint.

6. The rise or fall of the tint (the passage of absorption

from violet to red) by substitution of hypsochrome or batho-

chrome groups, or by the addition or loss of hydrogen, is the

greater the nearer the atoms affected by the change are to the

chromophore group. From this it would appear that in the

bi-derivitives of benzene the substituents in para position are

nearer to each other than those in ortho position.

7. These rules hold only for monochromophoric compounds

and for symmetrical dichromophoric compounds. The color

of an unsymmetrical dichromophoric compound, Y, A, X, A, Z,

is approximately the same as that of a mixture of the two

symmetrical compounds, Y, A, X, A, Y, and Z, A, X, A, Z.

In general the term bathochrome group is interpreted to

mean a group which swings the absorption toward the red,

and a hypsochrome group, one which swings the absorption to¬

ward the violet. Among the former are the hydrocarbon

radicles, the halogens, and the salt forming groups with the ex¬

ception of the amino group. Among the latter are the acetyl

and the benzoyl groups, the alkyl-oxy groups, hydrogen, and

the amino group. The sulpho group is sometimes one and

sometimes the other.

The effect of the introduction of bathochrome and hypso¬

chrome groups upon the color of the original substance de¬

pends upon the original molecule, the position of the group,

and the number of groups introduced. It is easy to under¬

stand how the introduction of one bathochrome group might

deepen the color by throwing the absorption into the red,

while the introduction of two or three such groups would re¬

move it by throwing the absorption wholly outside the visible

spectrum. Again the same two or three groups might be re¬

quired to render another molecule colored. Here again we

find additional evidence that the color of a substance is not

conditioned by the presence of a definite group, or groups,

but by the entire structure of the molecule.

In 1904 Baly and Desch10 in the course of a study of the ultra¬

violet spectrum of certain enol-keto tautomerides brought forth

evidence to support the view that the absorption bands ex¬

hibited by these substances are due to the equilibrium existing

10 Proc. Chem. Soc., 85, p. 1029.

774 Wisconsin Academy of Sciences , Arts, and Letters.

between the two possible tautomeric forms. Neither of the

two substances in a pure state exhibits absorption but when the

two are present in mutual equilibrium, that is, when a number

of molecules are changing from one form to another, a very de¬

cided absorption band is formed. In 190511 they stated further :

1. No organic substance shows an absorption band unless a

possibility for tautomerism exists in the molecule.

2. This tautomerism may not be due to a labile atom, but may

be of the same order as that occurring in those aromatic com¬

pounds containing the true benzenoid structure.

3. In all cases of the simpler tautomeric molecule the vibra¬

tion frequencies of the absorption bands are very nearly the

same.

4. An increase in the mass of the molecule causes a decrease

in the oscillation frequencies of the absorption band, i. e. a

shifting toward the red.

Baly and Desch account for these facts and explain the for¬

mation of the absorption band by the same theory as that ad¬

vanced by physicists to explain the phenomena of radio acti¬

vity, emission spectra, etc., namely the electron theory.

In 1906 Baly and Stewart12 applied the principle involved

in the foregoing to many colored compouds. As a result of

their investigations they conclude :

The color of diketones and quinones is due to an oscillation

or isorropesis between the residual affinities of the oxygen atoms

which results in the absorption of light in the visible spectrum.

Also that in order to start the oscillation it is necessary that

some influence should be present to disturb the residual affini¬

ties of the oxygen atoms. When this disturbing influence is

present there is no doubt that the principle may be extended,

and that visible color is due to the oscillations between the resi¬

dual affinities on atoms or groups of atoms in juxtapposition.

They also call attention to the fact that the assumption that

two compounds must be fundamentally different in constitution

if one is colored and the other not is quite untrustworthy.

Many compounds can and do exist with all the conditions for

isorropesis and yet there is lacking the influence to disturb the

equilibrium between the residual affinities and so the com-

11 Proc. Chem. Soc., 8T7, p. 766.

12 Jr. Chem. Soc., 89, pp. 502, 514, 966, 982.

Wakeman — Pigments of Flowering Plants. 775

pounds are colorless. They consider this principle to be the

key to Armstrong’ theory of color and as an explanation of the

colors of many compounds which are difficult of interpretation

by Armstrong’s quinoid linking alone, for though Armstrong

was perfectly right in concluding that color is due to quinoid

linking, this formula gives no reasons why color is thus pro¬

duced.

In 190713 Hale drew practically the same conclusions as

those of Baly and his associates, namely that isorropesis is the

cause of color in both the aromatic and the aliphatic series. By

isorropesis is meant the making and breaking of contact between

atoms thus giving them marked activity. This change of

linkage which must accompany the transformation of one modi¬

fication of the compound to the other is the source of the oscilla¬

tions producing the absorption bands. If these oscillations are

synchronous with light waves of a high frequency they give

rise to absorption bands in the ultra violet and the compound is

colorless. If, however, they are less frequent, the absorption

band appears in the visible portion of the spectrum and this

absorption of colored rays results in the compound taking on

the complementary color.

In 1907 Hewett and Mitchell14 pointed out that in every

case of colored compounds the molecules contain not jnerely

double linkages but chains of alternate double and single link¬

ages. Generally speaking the longer this chain of conjugate

double linkages the slower the oscillation frequency of the mole¬

cule. This explains why a benzene nucleus gives absorption

bands in the ultra violet and is colorless while a quinone

nucleus gives absorption bands in the violet and is therefore

colored yellow. In estimating the number of such alternate

double and single linkages, when a benzene nucleus is encount¬

ered, one is justified in following the structure around one side

of the ring only until para position is reached. The chain in

the benzene nucleus, therefore, contains at best only two double

linkages, while that of the quinone contains three.

Hewett and Mitchell also conclude that a radical change in

the absorption spectrum of a compound when it undergoes salt

formation generally means the radical alteration of its const!

13 Pop. Sci. Mo., 72, p. 116.

14 Jr. Chem. Soc., 91, p. 1251.

776 Wisconsin Academy of Sciences , Arts , and Letters.

tntion. Other groups or elements when introduced in place

of hydrogen may diminish the oscillation frequency, but the

effect in such cases must be slight and the general character

of the absortion would remain unaltered. It is conceivable

that such groups introduced into the molecule of a substance

colorless in the ordinary sense, might, if its absorption occurs'

just outside the visible spectrum, render the substance colored

by a slight shifting of the absorption band; but when a radical

change in the color takes place on salt formation the salt is con¬

stituted differently from the parent substance.

In 1900 Hewett15 advanced the idea that symmetrical com¬

pounds capable of equal tautomeric displacements in either of

two directions should be fluorescent, for the molecule would

swing between the two extremes like a pendulum, the energy

absorbed in one wave length being degraded and given out with

slower frequency.

CH

O

CH

O

CH

COH

CH

In 1910 Porai-Koschitz16 summed up the more recent views

of the oscillation theory of the cause of color in organic com¬

pounds as follows: The change in color of a compound is due

to the retarding of the oscillations or the setting up of a new

16 Zeitschr. physikal. Chem., 34, p. 1. (See also Jr. Phys. Chem. 10, p. 375 :

Jr. Chem. Soc., 87, p. 7.68.)

18 Jr. Russ. Phys. Chem. Soc., 42, p. 1237. (Jr. Chem. Soc., A. II, p. 3.)

Wakeman — Pigments of Flowering Plants. 777

type of oscillations within the molecule by the entrance of a

new group, by the formation of a molecular compound, or by

the associations of the molecule of a solute with those of its

solvent. Three cases are possible:

1. The new oscillation may coincide with and increase the

original oscillation ; then the absorption band will move further

toward the ultra-violet and the compound will remain, or be¬

come visibly colorless.

2. The new oscillation may be an entirely different type from

the original, in which case new bands will appear, and since

the original oscillation will be retarded to some extent, there

will be a change but not a very considerable one in the visible

color of the substance.

3. The new oscillation may combine with the original and

retard it greatly, when there will be a considerable sharp

change in color.

PREFACE.

Work upon plant pigments was begun by the writer during

the summer of 1907 when, as an undergraduate student, her

attention was directed to pigmentation in the Monarda species.

Since that time, though the subject has been sometimes tem¬

porarily pushed aside by other interests, it has never been lost

sight of and it has usually been the subject of most absorbing

interest. At times the work has appeared to be of a purely

chemical nature, without any biochemical significance, as in the

study of thymoquinone, hydrothymoquinone, and the oxidation

products of thymoquinone. Its object at these times has been

to elucidate the behavior of certain plant pigments, i. e. those

of the Monarda species. Sometimes it has been of a character

usual in the study of plant pigments, the extraction of pigments

from the plants themselves and an examination of the pro¬

ducts obtained. At other times it has been of what is gener¬

ally considered of a more purely biochemical character, a study

of oxidases, water content, etc., and their relation to the for¬

mation of pigments in plants.

It has been found in the course of these investigations that no

adequate and satisfactory knowledge of plant pigments can be

778 Wisconsin Academy of Sciences, Arts, and Letters .

gained by a study of simply the pigments themselves; but that

each pigment should be considered not only in relation to the

other colored substances in the same and related plants, but

also to the non-colored substances as well. A close and pecu¬

liar relationship has often been found to exist between the col¬

ored and the non-colored constituents not only of the same

plant, but sometimes of the related species of a whole plant

family.

As the work progressed a complete revision of the literature

on plant pigments became necessary. Very little literature

of a general nature upon plant pigments was found to exist,

almost nothing in fact beyond Brandel’s excellent monograph.

Several treatises upon vegetable dye stuffs, it is true, are avail¬

able. Among these may be mentioned two by Thomas, Les

Matieres Colorantes Naturelles, and Les Planets Tinctoriales,

also Rupe’s more recent Chemie der natuerlichen Farbstoffe

(1909) and volume 6 of the Biochemisches Hand-Lexicon , Farb¬

stoffe der Pflanzen und der Tierwelt. (1911), as well as chap¬

ters on natural dye stuffs in various treatises on dye stuffs in

general. By far the larger literature on plant pigments, how¬

ever, is scattered through the chemical and botanical journals

of the past fifty years, some extending much further back.

Before attempting to proceed further with work upon plants

and plant products it seemed desirable to review this literature

in order,

1. To avoid useless repetition of work already done.

2. To interpret new work in the light of the old, and the old

in the light of recent experimentation.

3. To make comparisons, draw conclusions, and formulate

theories as a guide to future work.

In the course of this review of the literature upon plant pig¬

ments it was found that by arranging the pigments according

to the degree of saturation, as calculated from the underlying

hydrocarbons, certain relationships were brought out which

could not well be observed in any other way. Among the import¬

ant relationships emphasized by this classification are :

1. The influence of unsaturation upon the production of color

in a molecule.

2. The influence of so called chromophorous groups upon the

production of color in a molecule.

3. The existence of homologous series of pigments.

Wakeman — Pigments of Flowering Plants. 779

4. The existence of series of pigments related to similar sym¬

metrical, or almost symmetrical hydrocarbons of different de¬

grees of saturation.

1. The influence of unsaturation upon the production of color

in a molecule.

In this connection it should be pointed out that all organic

pigment molecules are unsaturated. The highest degree of sat¬

uration known in a pigment molecule is CnH2n_4, and visible

color exists in substances of this degree of saturation only

when the quinone grouping is present, the quinone grouping

being one of the best known and most reliable of the chromo-

phorous groups.

Among substances referable to hydrocarbons of the degree of

saturation CnH2n_6 no substances colored in the ordinary sense

are known to exist but several pigment producing substances

are known. All substances, however, having a benzenoid group¬

ing are colored in a physical sense, since they all exhibit selec¬

tive absorption, not, it is true in the visible portion of the

spectrum but just beyond it in the ultra violet.

The largest number by far of plant pigments are referable to

hydrocarbons of the degrees of saturation CnH2n— 14 and

CnH2n_16, through colored substances of known constitltion refer¬

able to hydrocarbons of higher unsaturation, up to CnH2n_34,

have been isolated from plants. Moreover, all colored hydro¬

carbons, in which the production of color cannot be attributed

to the usual chromophorous groups, are highly unsaturated,

caroten and lycopen being of the degree of saturation CnH2n_24,

while the blue hydrocarbon from oil of milfoil, having the for¬

mula C15H18, is apparently of the degree of saturation CnH2n_12.

2. Influence of co-called chromophorous groups upon the pro¬

duction of color.

As has been pointed out elsewhere in this paper, but little

has been contributed to our knowledge of pigmentation in plants

by a study of chromophorous groups, since only the corbonyl

of the so-called chromophorous groups and the hydroxyl of the

auxochrome groups are of at all frequent occurrence in plant

pigments. Neither is the mere presence of either or both of

these groups, or of multiples of one or both, sufficient to explain

the phenomenon of color in any known plant pigment. In

780 Wisconsin Academy of Sciences , Arts, and Letters.

many instances, however, the influence of both the presence and

the position of these groups, especially of the hydroxy group,

is evident. For example, the substitution of hydroxy groups

for hydrogen in the xanthone or flavone pigments usually in¬

tensifies both the color and the dyeing properties of these sub¬

stances, while the removal of such groups, either by replace¬

ment with hydrogen or by methylation, usually diminishes both.

In no instance does the presence of the chromophorous group

explain the color. In most cases it will be seen that it is not

the mere presence of these so-called chromophorous groups but

their relation to each other and to the rest of the molecule which

postulates color in a substance. Color, in other words, appears

to be a function, not of certain groups or elements but of the

entire molecule.

3. The existence of homologous series of plant pigments, or

more accurately, of pigments referable to homologous series of

hydrocarbons is worthy of note. This homology is manifest in

connection with every degree of saturation where a sufficiently

large number of pigments, or of pigment forming substances,

to admit of comparisons adequate to justify the drawing of con¬

clusions, has been isolated.

Under the degree of saturation CnH2n_4 we find evidence of

the existence of quinone, methyl quinone and of methyl

p-isopropyl quinone. Similarly, under the formula of satura¬

tion CnH2n_6 the pigment forming substances hydroquinone,

methyl hydroquinone, and methyl-p-isopropl hydroquinone

are found. A similar homology is found to exist in connection

with pigments referable to hydrocarbons of other degrees of

saturation, especially to CnH2n„16 where we find pigments

referable to homologuus of diphenyl ethene, diphenyl propane,

etc., as well as to homologous series of dihydroanthraeenes.

A condition quite similar in many respects to homology, and

sometimes confused with it, exists among the' pig¬

ments falling under the degrees of saturation CnH2n__14

and CnH2n_16. This is the existence of pigments referable to

closely related series of hydrocarbons, not truly homologous yet

differing from one another by CH2, such as diphenyl, diphenyl

methane, diphenyl ethane, diphenyl propane, among the former ;

and diphenyl ethene, diphenyl propene, and diphenyl butene

among the latter, as well as alkyl substitution products of these

Wakeman — Pigments of Flowering Plants. 781

hydrocarbons. This relationship is very similar to that exist¬

ing between pigments referable to hydrocarbons of different

degrees of saturation discussed in the following paragraph.

4. The existence of series of compounds referable to similar

symmetrical, or nearly symmetrical hydrocarbons of different

degrees of saturation.

A relationship quite similar to that expressed by homology

under the same degree of saturation is noted between the hydro¬

carbons of different degrees of saturation to which any of the

plant pigments are referable. This relationship is best ex¬

pressed by the accompanying chart of graphic formulae repre¬

senting the hydrocarbons to which a large majority of the plant

pigments falling under the degrees of saturation CnH2n_10

to 0nH2n _ 18 are referable.

In addition to the hydrocarbons listed in this table, attention

should here be called to pigments, or pigment forming substances,

referable to benzene and dihydrobenzene, naphthalene and dihy-

dronaphthalepe anthracene and dihydroanthracene series of hy¬

drocarbons. It is also interesting to note the symmetrical or

almost symmetrical character of all of the above hydrocarbons.

Whether this symmetry of arrangement of the underlying hy¬

drocarbon is only coincident with the conditions which produce

color in the molecule, or whether the symmetrical arrangement

is itself one of the conditions does not become manifest.

In order to bring out the relationships just discussed the

plant pigments of known constitution have here been classified

according to the underlying hydrocarbon. A second classification,

according to plant families, showing the relationship which exists

between the pigments and the noncolored constituents of the

same and related plants, was intended to be included. This

classification was, however, found to be too long for the purposes

of this paper, therefore will be published later as supplementary

to it. The experimental work of the writer1, where heretofore

published has been referred to in the same manner as that of

other investigators. Some work not previously published has

been briefly described, i. e. the study of the pigment of red ger¬

anium blossoms. In addition to the above a large amount of

1 Quantitative determinatino of oxidase in the leaves of Monarda fistulosa.

Ph. Rev., 26, p. 314.

Thymoquinone and Hydrothmoquinone.

Ph. Rev., 26, p.

Higher oxidation products of thymoquinone.

Proc. A. Ph. A., 58, p. 979.

The Monardas, a phytochemical study.

Bull, of Univ. of Wis., Sci. Ser., Vol. 4, No. 4, pp. 81-128.

SYMMETRICAL CONFIGURATIONS OF HYDROCARBONS UNDERLYING PIGMENT MOLECULE'S.

Wakeman — Pigments of Flowering Plants.

783

material has been collected and studied for the purpose of mak¬

ing comparisons and verifying conclusions.

PLANT PIGMENTS.

Pigments referable to hydrocarbons of the formula of

Saturation CnH2n--4.

All of the known plant pigments of this degree of saturation

are quinones or more particularly their quinhydrone or pheno-

quinone addition products, and metallic derivatives of the lat¬

ter, and are referable to dihydro benzene, dihydro toluene and

dihydro cymene.

Pigments referable to dihydrobenzene.

whose existence in plants we have any evidence, is the ordinary

quinone, or benzoquinone. However, its occurrence is purely

hypothetical. Though benzoquinone has never yet been iso¬

lated from a plant, its dihydro derivative, hydroquinone, is

known to occur in several species and under such conditions as

would suggest the formation of quinone and quinhydrone as a

possible explanation of the pigmentation which exists there.

For example, the glucosides arbutin and methyl arbutin occur in

the leaves of Gaultheria procumbens , Uva ursi , and several other

species of the Ericaceae. Arbutin upon hydrolysis yields hydro¬

quinone. Hydroquinone by the action of oxidases, known to occur

in Gaultheria and, no doubt, present in the other arbutin contain¬

ing plants, is readily converted into quinone with the forma¬

tion of quinhydrone as an intermediate product. The pres¬

ence of benzoquinhydrone, which is brownish-red in color, would

afford an explanation of the reddish tint commonly acquired

by the leaves and stems of these plants in the fall. It might

also account for the remarkable colorations of the Madrones

and Manzanitas so well known upon the Pacific coast, since both

are species of Arbutus and closely related to the above named

plants. Arbutin has been isolated from the leaves of at least

one of the manzanitas, Arctostaphlos glauca.

784 Wisconsin Academy of Sciences , Arts , and Letters.

Hydroquinone also exists as the mono methyl ether in the oil

of star anise. Illicium verumf a member of the family Mag-

noliaceae.1

Pigments referable to dihydrotoluene

Dihydrotoluene Methyl benzoquinone

As has been pointed out in connection with quinone, methyl

hydroquinone exists potentially in Gaultheria procumbens and

other species of the Ericaceae as the glucoside methyl arbutin.

The same possibilities for forming pigments by hydrolysis, oxi¬

dation, and addition exist in both quinone and methyl quinone.

Pigments referable to dihydrocymene

ch3

c

C Dihydroxythymoquinone

ch3 ch3

Monohydroxythymoquinones

1 For references see under Hydroquinone, formula of saturation Cn H2n-a

Wakeman — Pigments of Flowering Plants. 785

Of the oxidation products of dihydrocymene, three, and pos¬

sibly four, are believed to exist in plants. Of these thymo-

quinone and dihydroxy thymoquinone have actually been iso¬

lated, while there are strong reasons for believing that one or

both of the monohydroxy thymoquinones occur in Monarda

species either in the free state or as labile compounds.

Thymoquinone together with the corresponding hydroquinone

has been isolated from several species of Monarda , also from

the oil from the wood of Thuja articulata.2 Hydrothymo-

quinone also exists in the oil from the fruit of Foeniculum

vulgare ,3 also as dimethyl ether in the oil of Eupatorium trip-

linerve 4 (E. Ayapana) and in the oil from Eupatorium capil-

lifolium .5 Inasmuch as in the diethers the original phenol hy¬

drogens are replaced by alkyl radicals they are not prone to

oxidation in like manner as the phenols, hence, presumably do

not take part in pigment formation.

Monohydroxy thymoquinone6) is believed to occur in Monarda

fistulosa , Monarda citriodoraf and perhaps in other species of

Monarda.

Dihydroxy thymoquinone7) has been isolated from the vola¬

tile oils of Monarda fistulosa and Monarda citriodora. Its pres¬

ence has been indicated in Monarda didyma.

The chemical relationship of the thymoquinones to some of

the other constituents of the Monardas is very close and is

worthy of notice here. From the volatile oils of the several

species of Monarda so far examined, have been isolated both

of the monohydroxy phenols, thymol and carvacrol, and prob¬

ably eymene8) the hydrocarbon underlying not only these

phenols but hydrothymoquinone as well.

The relation of the pigment substances to each other and to

the volatile constituents of the Monardas, also the role which

some of the non-colored volatile and non-volatile substances

2C. r., 139, 927.

3 Schimmel, Gesch. Ber. 1906, Apr. p. 28.

4 Gildemeister — The Volatile Oils, p. 479.

3 Personal communication from Prof. E. R. Miller, Laboratory of Plant

Chemistry, University of Wisconsin.

8 Bulletin of the University of Wisconsin No. 448, p. 31-34.

7 Bulletin of the University of Wisconsin No. 448, p. 31-34.

8Ph. Rund., 13, p. 207; Ph. Rev., 14, p. 223. (The writer has not suc¬

ceeded in identifying^ eymene in her study of the hydrocarbons in the oil

of M. punctata.)

50— S. A. L.

786 Wisconsin Academy of Sciences, Arts, and Letters.

play in the formation of the pigments, can best be illustrated by

a series of graphical formulas given on the accompanying chart.

From this chart it becomes apparent that here we have to

deal with white (or colorless), yellow, orange, and red sub¬

stances, all of which are very closely related to each other. More¬

over, the thymoquinone, monohydroxythymoquinone and dihy¬

droxy thymoquinone, have the capacity of adding monatomic

phenols, thus yielding highly colored phenoquinones ; also diat¬

omic phenols thus yielding the equally highly colored quinhy-

drones.

Thymoquinhydrone has actually been isolated from the corol¬

las of Monarda fistulosa while the formation of phenoquinones

and quinhydrones of mono- and dihydroxythvmoquinone has

been considered as a probable explanation of the complexity of

the mixture of crystalline pigment originally referred to as

“ alizarin-like9 ).” The following table illustrates the pheno-

quinone and quinhydrone pigments that can result from the

addition of the phenols to the quinones thus far observed in the

Monardas.

9 Fh. Rev., 19, p. 244 ; Mid. Drug., Ph. Rev., 44, p. 342 ; Bulletin of the

Univ. of Wis., No. 448, p. 22.

Wakeman — Pigments of Flowering Plants. 787

yX

\

>3* Monohydroxythmo-

quinone

788 Wisconsin Academy of Sciences, Arts, and. Letters .

Quinones

Thymoquinone

Phenoquinones

1. ) With two mole¬

cules of thymol.

2. ) With two mole¬

cules of carva-

crol.

3. ) With one mole¬

cule each of thy¬

mol & carvacrol.

4. ) With two mole¬

cules of a-mono-

hydroxythymo-

quinone.

5. ) With two mole¬

cules of /3-mono-

h y droxythymo-

quinone

6. ) With one molecule

each of a- & /3-

m o n o hydroxy-

thymoquinone.

7. ) With one molecule

each of a-mono-

hydroxy thymo¬

quinone and thy¬

mol.

8. ) With one molecule

each of a-mono-

hydroxythymo-

quinone and car¬

vacrol.

9. ) With one molecule

each of j3-mono-

hydroxy thymo¬

quinone and thy¬

mol.

10.) With one mole¬

cule each of /?-

monohydroxythy-

moquinone and

carvacrol.

Quinhydrones

.) With hydrothymo-

quinone.

.) With dihydroxythy-

moquinone.

Wakeman — Pigments of Flowering Plants.

789

Quinones

a-Hydroxythymo-

quinone.

Phenoquinones

1. ) With two mole¬

cules of thymol.

2. ) With two mole¬

cules of earva-

crol.

3. ) With one molecule

each of thymol

and carvacrol.

4. ) With two mole¬

cules of a-mono-

hyd roxythymo-

quinone.

5. ) With two mole¬

cules of j9-mono-

h y droxythymo-

quinone

6. ) With one molecule

each of a- and /9-

m o n o h ydroxy-

thymoquinone.

7. ) With one molecule

each of ct-mono-

h y droxythymo-

quinone and thy¬

mol.

8. ) With one molecule

each of /3-mone-

h y d roxythymo-

q u i n o ne and

carvacrol.

9. ) With one molecule

each of 0-mono-

h y d roxythymo-

quinone and thy¬

mol.

10.) With one mole¬

cule each of j3-

mo no-hydroxy -

t h y m o quinone

and carvacrol.

Quinhydrones

L) With hydrothymo-

quinone.

I.) With dihydroxy thy -

moquinone.

790 Wisconsin Academy of Sciences, Arts, md Letters.

Quinones

j8 - Hydroxy thymo -

quin one.

Phenoquinones

1

2,

1.) With two mole¬

cules of thymol.

1.) With two mole¬

cules of carva-

crol.

3. ) With one molecule

each of thymol

and carvacrol.

4. ) With two mole¬

cules of a-mono-

h ydroxythymo-

quinone.

5. ) With two mole¬

cules of jS-mono-

h y d roxythymo-

quinone.

6. ) With one molecule

each of a- and j8-

m o n o hydroxy-

thymoquinone.

7. ) With one molecule

each of a-mono-

hy droxythymo-

quinone and thy¬

mol.

8. ) With one molecule

each of a-mono-

hy droxythymo-

quinone and ear-

vacrol.

9. ) With one molecule

each of j8-mono-

h y droxythymo-

quinone and thy¬

mol.

10.) With one mole¬

cule each of j8-

m o n o hydroxy-

t h y m oqumone

and carvacrol.

Quinhydrones

.) With hydrothymo-

quinone.

.) With dihydroxyth)'-

moquinone.

W akeman — Pigments of Flowering Plants.

791

Quinones

Dihydroxy thymo -

quinone.

Phenoquinones

1

2

1. ) With two mole¬

cules of thymol.

2. ) With two mole¬

cules of earva-

crol.

3. ) With one molecule

each of thymol

and carvacrol.

4. ) With two mole¬

cules of a-mono-

h y droxythymo-

quinone.

5. ) With two mole¬

cules of jS-mono-

h y droxythymo-

quinone.

6. ) With one molecule

each of a- and ]8-

m o n o hydroxy-

thymoquinone.

7. ) One molecule each

of a-monohy-

d r o x y t hymo-

quinone and thy¬

mol.

8. ) With one molecule

each of jS-mono-

h y droxythymo-

quinone and thy¬

mol.

9. ) With one molecule

each of a-mono-

h y droxythymo-

quinone and car¬

vacrol.

10.) With one mole¬

cule each of j3-

m o n o hydroxy-

t h y m o quinone

and carvacrol.

Quinhydrones

.) With hydrothymo-

quinone.

.) With dihydroxythy-

moquinone.

792 Wisconsin Academy of Sciences , Arts r and Letters.

Taking into consideration only those compounds that have

been isolated, (hydrothymoquinone, thymoquinone, and dihy¬

droxy thy moquinone ) or whose presence has been indicated

( monohy dr oxythymoquinone ) in the Monardas thus far, the

number of possible pigments becomes truly bewildering. A

consideration of these possibilities of easily decomposable phe.no-

quinones and quinhydrones readily explains why a crystalline

pigment, seemingly a chemical unit, upon recrystallization from

such a solvent as ether yields several kinds of crystals of dif¬

ferent shades of red and purple. To attempt the isolation of

a number of these pigments would seem a thankless task. In¬

deed, after they had been isolated the question might pertinently

be asked whether the combination as isolated existed as such

in the plant or whether it had been formed because of a change

of solvents.

However, the subject of the pigmentation of the Monardas

is not solved even after the numerous combinations of pheno-

quinones and quinhydrones have been worked out. Most of

these pigments are phenolic in character and hence can com¬

bine with metallic constituents, ammonia and organic nitro¬

gen bases of the plants giving rise to different shades of the

original pigment.

This is shown by the varying shades of color produced by

treating solutions of these phenols with solutions of basic me¬

tallic compounds, etc. However, nothing definite is known of

the particular kind of metallic and other derivatives which may

be found in the various parts of the several Monarda species.

Another possible influence of basic inorganic material re¬

mains to be referred to, viz: the stimulating influence some of

them, such as potassium hydroxide and calcium hydroxide, exert

on oxidizing reactions, e. g. the oxidation of thymoquinone.

That even very dilute basic solutions exert such an influence

has been shown by the action of lime water upon aqueous thy-

moquinhydrone solution. It has further been demonstrated

• by Sehaer10 and others that traces of basic substances, organic

as well as inorganic, stimulate the action of oxidases.

Assuming that much of the pigmentation of plants contain¬

ing quinones or hydroquinones is due to the formation of

quinhydrones or phenoquinones, the intense coloration of the

10 From a reprint from the Pharm. Inst. Strassburg, 1902.

Wakemaw — Pigments of Flowering Plants. 793

lower surfaces of the leaves, and often of the entire shoots of

Monarda fistulosa, and the general reddish appearance of the

young plants of Monarda punctata in spring can readily be

accounted for by the greater oxidase content of the vigorous

young tissue and the consequent greater chemical activity.1 A

similar phenomenon in the young plants or shoots after the fall

rains may be explained in the same way.

On the other hand, the fall coloration of arbutin containing

foliage may be explained by assuming that as the synthetic

life process of the plant grow sluggish, the reserve carbohy¬

drates stored away in the glucoside are rendered available as

food material by hydrolysis. This latter process would set

free the hydroquinone as well as the sugar. The former (chro¬

mogen) in turn would be oxidized to pigment. If this line of

reasoning may be applied to the madrones as well as to the

other species of arbutus, the brilliant coloration of both the

enormous leaf buds in spring and of the leaves and the freshly

peeled trunk in autumn may be accounted for.

It has been pointed out above that the diethers of the hydro-

thymoquinone, being deprived of their phenolic hydrogen are

no longer prone to oxidation, hence to quinhydrone pigment

formation. It is, therefore, not surprising that plants char¬

acterized by the presence of the dimethyl ether of hydrothy-

moquinone are not conspicuously colored. The only pigmenta¬

tion of the Eupatorium species which could be attributed to

quinhydrone formation is the occasional purplish coloration of

the stems.

This purplish stem coloration though not conspicuous de¬

serves special notice since most of the plants considered in this

chapter are remarkable at some period of their development,

generally late in the season, for conspicuously colored stems,

the members of the Ericaceae, trailing arbutus, winter green,

manzinitas, and mandrones for red or red brown stems, the

characteristic color of benzo quinhydrone, while the stems of

the Monardas are often conspicuously purple, the color of thy-

moquinhydrone.

Many investigators have inferred that ferments — hydrolases,

oxidases, and reductases — play an important role in pigment

1 The oxidase content of the Monardas has been studied both quantita¬

tively and qualitatively by F. Rabak, Ph. Rev., 22, p. 190 ; Swingle, Ph

Rev., 22, p. 193 ; Wakeman, Ph. Rev., 26, p. 314.

794 Wisconsin Academy of Sciences, Arts, and Letters.

formation. No where would this part seem more conspicuous

than in the formation of quinhydrone and pheno-quinone pig¬

ments. Indeed one of the first questions which arises in the

biochemical study of any such series of related compounds as

the cymene, thymol, carvacrol, hydrothymoquinone, monohy¬

droxy thymoquinone and dihydroxy thymoquinone series in the

Monarda species is which of these complex cyclic substances

was first formed from the simple chain products of photo syn¬

thesis? Being accustomed for purposes of classification to

look upon the hydrocarbons as basal compounds and to con¬

sider all other compounds as being derived from the hydro¬

carbons, it is easy to regard such a series as being formed in

this order. However, it is highly improbable that the plant

works in this way. An oxidase which oxidises hydrothymo¬

quinone to thymoquinone exists in several species of Monarda,

but up to the present time no oxygen conveyer has been found

which oxidizes thymol or carvacrol to hydrothymoquinone, all

attempts in this direction having been attended with negative

results, or in the case of thymol, sometimes, with the formation

of dithymol. It is not at all improbable that the monatomic

phenols and the hydrocarbons are reduction products, possibly

by products of autoxidation. The large amounts, however,

in which the monatomic phenols are found in comparison with

the amounts of thymoquinone and its oxidation products pres¬

ent does not encourage this assumption.

Of almost equal interest with the thymoquinone series of

compounds in the Monarda species are the less complete, pos¬

sibly because less closely investigated, series of carvacrol, hy¬

drothymoquinone, and thymoquinone in Callistris quadrivalvis

( Thuja Articulata) and the cymene, hydrothymoquinone series

of Foeniculum vulgare. Another similar example which should

be mentioned here is Thymus vulgaris. The oil of thyme is

known to contain cymene, thymol, and sometimes carvacrol.

Other members of the series, if not present in the original oil,

are possibly produced upon standing, since oil of thyme, quite

colorless when freshly distilled, often, upon standing, takes on

a red color quite similar to the color of the oil from Monarda

fistulosa from which dihydroxythymoquinone has been separ¬

ated.

The fact that so frequently the pigment forming substance

does not occur alone but is associated with other closely related,

Wakeman— Pigments of Flowering Plants.

795

colored or non colored, compounds is of much biochemical sig¬

nificance as will be pointed out in succeeding chapters.

Pigments referable to hydrocarbons of the degree of sat¬

uration Cn H2n __6.

There exist in plants several compounds referable to hy-

drocarbonss falling under this degree of saturation, being sub¬

stitution products of benzene, toluene and cymene, which though

colorless in themselves are readily oxidized to pigments. More¬

over, being hydroquinones, they are capable of forming highly

colored phenoquinones and quinhydrones by addition with their

oxidation products the quinones. These compounds occur in

a large number of plants either in the free state, as alkyl ethers,

or in sugar ether combination as glucosides and they may be

looked upon as pigment forming substances, commonly desig¬

nated chromogens in pigment literature.

While no attempt is being made here at a discussion of the

pigments of non-flowering plants it is interesting to note that

there exist in several species of lichens pigments and pigment

forming substances referrable to the hydrocarbons toluene,

o-xylene, p-xylene and trimethyl 1, 2, 4 benzene.

Benzene Hydroquinone

The only known pigment, or pigment forming substance,

referable to benzene as the underlying hydrocarbon is the or¬

dinary hydroquinone, or hydrobenzoquinone. The occurrence

of hydroquinone as the glucoside arbutin in several species of

Ericaceae and the possibility of its forming the corresponding

quinone and quinhydrone through oxidation thus furnishing

an explanation for the pigmentation of several species has been

referred to under benzoquinone.

Arbutin occurs in Ledum palustre1) ; Rhododendron maxi -

1 Am. Jr. Ph., 46, p. 314.

796 Wisconsin Academy of Sciences, Arts, cmd Letters.

mum,2) Kalmia latifolia,3) Kalmia angustifolia ,4) Gaultheria

procumbens,5) Arctostaphylos TJva Ur is,6) Arctostaphylos

glauca,7) Vaccinium Myrtillus,8) Vaccinium vitis ,9) Vaccinium

macrocarpum,10) Vaccinium arctostaphylos,11) Calluna vul¬

garis,12) Erica herbacea,13) Pinus communis,14) Protea milli-

fera,15) Chimaphila umbellata,16) Chimaphila maculata,17) and

Pirola uniflora.18)

In addition to the above, the mono-ethyl ether of hydroqninone

has been found in the oil of star anise, 1 llicium verum19) Further¬

more it has been pointed out that the pentatomic alcohol of hexa-

hydrobenzene, quercite,20) may lose three of its hydroxy groups

in the form of water and form hydroquinone as indicated by

the following formula:

3H20

CoH7 (OH)5 - -> C„H4 (OH) 2

Pigments referable to toluene

Toluene Hydrotoluquinone

Methyl hydrobenzoquinone

or

Methyl hydroquinow

Orcinol

2 Wehmer, Die Pflansenstoffe, p. 570.

3 Am. J. Ph., 47, p. 5.

4 Am. J. Ph., 58, p. 417.

15 Am. Jr. Fh., 46, p. 314.

« Arch. Pharm., 227, p. 164; Am. Jr. Ph., 46, p. 314.

7 Am. Jr. Ph., 46, p. 314.

8 Monatsh f. Chem., 30, p. 77.

9 Arch, exper. Path., u. Pharm., 50, 46.

19 Chem. News, 52, 78.

1 Apoth. Ztg., 16, 694.

12 Am. Jr. Ph., 46, 314.

33 S. Ber. Wien. Acad., 9, 308.

34 Jr. Pharm. Chim. (7) 2, 248.

15 B. 29, R. P. 416.

19 An. Chim., 129, 203.

17 Am. Jr. Ph., 46, 314.

18 Am. Jr. Ph., 11, 549.

19 Schimmel & Co., Oct., 1895, p. 6.

20 Plant Pigments, p. 11.

Wakeman — Pigments of Flowering Plants. 797

Methyl Kydroquinone occurs as the glueoside methyl arbutin

in several species of Ericaceae.21) It is also known to exist in

several species of Pirola22) and in Pirns communis ,23)

Orcinol an isomer of methyl hydroquinone and referable to

toluene is found in many lichens of the varieties Rocella and

Lecenora. Orcinol24) when allowed to stand exposed to air and

ammonia forms orcein C7H7No3, the principal constituent of the

coloring matter archil, called also persio, cudbear and nurpur.

Azolithmin25) C7H7 No4, the coloring principle of litmus and an

oxidation product of orcein, is also produced from these orcinol

containing lichens by the action of ammonia and potassium

carbonate.

Pigments referable to trimethyl 1, 2, 4 benzene.

In one variety of Rocella there occurs a homologue of erythrin

known as betaerythrin.26) This upon hy-

bined to form the betaerythrin is therefore

drolysis yields not orcinol but beta orcinol,

or methyl orcinol, p-xylol orcinol. At

least one molecule of the simple acids com-

probably methyl orsellinic acid, referable

to trimethyl 1, 2, 3 benzene.

Ann ., 206, 159; Ann., 177, 934.

22 Am. J. Ph., 11, p. 549.

23 Jr. Fharm. Chim., (7) 2, 248; C. r., 151, p. 444.

24 Ann., 41, p. 157; 54, p. 261; 59, p. 72; Jr. Prakt. Chem., 44, p. 18;

25 Ann., 39, p. 25; Czapek, Biochemie der Pflanzen, p. 508.

2<J Czapek Brochemie der Pflanzen, p. 507.

CH,

Methyl orcinol

798 Wisconsin Academy of Sciences, Arts , md Letters.

Pigments referable to o-xylene

0‘Xylene OrseUinic acid

Lecanoric acid,27) another pigment forming substances from

some varieties of Roccella, Lecanora, and Yariolaria, is prob¬

ably a condensation product of two molecules of orsellinie acid,

referable to o-xylene, dimethyl 1, 2, benzene.

Lecanoric acid crystallizes in colorless crystals. With alka¬

lies it gives a beautiful rose like color, with calcium chloride,

a blood red color. It occurs combined with erythrite as the

ester, lecanoryl erythrite, also known as erythrin.

The constituents of other similar pigments found in these

lichens is not known.

Pigments referable to cymene

Cymene llydrothymoquinone

Hydrothymoquinone has already been discussed in connec¬

tion with thymoquinone in the preceding chapter. It occurs

« Ann., 295, p. 278; 41, p. 157; 54, p. 261; 61, p. 72; Jr. Prakt. Chim.

44, p. 18 ; Czapek, Biochemie der Pflanzen, p. 507,

Wakeman — Pigments of Flowering Plants.

799

along with thymoquinone in several species of Monarda, also in

Thuja articulata. Its occurrence as dimethyl ether28) in the

oils of Eupatorium triplinerve and Eupatorium capillifolium ,

as well as in the oil from Arnica Montana has also been noted.

Pigments referable to hydrocarbons of the formula of

SATURATION Cn H2n-8.

The only plant pigments of known constitution referable to

hydrocarbons falling under this degree of saturation are sub¬

stitution products of phenyl ethene and phenyl propene, allyl

benzene.

Pigments referable to phenyl ethene.

CH CH

Phenyl ethene

Indoxyl

CH

Indican

Indican occurs in indigo bearing plants almost exclusively

in the form of the glucoside indican,* a sugar ether of indoxyl,

referable to phenyl ethene. Upon treatment of the herb, or the

indigo producing part thereof, with water the glucoside is ex¬

tracted. This is hydrolized by an enzyme present in the plant.

By contact with the air the indoxyl thus produced is oxidized

to indigotin.

28 See references to preceding chapter.

29 Ann. Chem.f 170, p. 345.

•For references to indican and indoxl see Indigotin, formula of satura¬

tion CnH2n-16.

800

Wisconsin Academy of Sciences, Arts , and Letters.

Pigments referable to allyl benzene

CH

As will be seen from the structural formula, daphnetin may

be looked upon as a dihydroxy cumarin, or as a product of the

inner dehydration, a lactone, of tri-hydroxy cinnamic acid.

Since the occurrence of daphentin in the plant is so frequently

accompanied by that of cumarin, umbelliferone and other cin¬

namic acid derivatives, the importance of recognizing this rela¬

tionship cannot be over estimated.

CH

C CH : CH

C-O— C=0

Cumaric add

CCH : CH HC

C-O— c=o H0C

C CH '.CH

I

c — o— c»o

CH

Cumarin

CH

Umbelliferone

COH

Daphnetin

Daphnetin which is yellow in color, occurs in the yellow flow¬

ers of sweet clover, Mililotus officinalis.1.) together with cumarin,

cumaric acid, and hydro cumaric2) acid. The frequency of

the occurrence of these and related compounds in this and other

members of the Leguminosae will be taken up in the considera¬

tion of pigmentation in that family.

Daphnetin, having two phenol hydrogens, is capable of form¬

ing metallic derivatives which may influence the color of the

pigmented parts. With potassium it forms the socalled “semi-

^erg. Jahresb., 14, 311.

3 Richter, II, p. 280.

Wakeman — Pigments of Flowering Plants. 801

mono potassium salt” C18H1108K and the mono potassium salt

C9H504K. The former crystallizes in bright yellow and the

latter in red crystals. To wools mordanted with chromium,

aluminum, tin and iron it imparts various shades of olive and

yellow.

Daphnetin occurs as the glucoside daphnin, in the bark and

flowers of Daphne mezerum8) and in the leaves, bark and flow¬

ers of Daphne Alpina.4) In these plants, however, the odori¬

ferous principle is not cumarin but umbelliferone, a 4-hydroxy

cumarin.

Daphnin, or a glucoside similar to daphnin has, furthermore,

been reported in Panicum italicum5) (Italian millet.)

Closely related to daphnetin are aesculetin, scopoletin, and

fraxetin, substances which though not colored themselves form

beautifully fluorescent solutions. Moreover, at least some of

their metallic derivatives, in which form they would be likely

to occur in plants, are colored.

Aesculetin is isomeric with daphnetin, being a 4, 5-dihydroxy

cumarin. It forms a bright yellow potassium compound very

similar to the corresponding daphnetin derivative. Its solu¬

tions show a beautiful blue fluorescence. Aesculetin occurs as

the glucoside aesculin in Aesculus hippocastanum ,6) the horse

chestnut, and in Gelsemium semper virens.7) In the free state,

is found in Euphorbia lathy ris.8)

Scopoletin , a methyl ether of aesculetin occurs as the gluco¬

side scopolin in Gelsemium sempervirens10) and in several

species of Solonaceae, Atropa belladonna,* 11) Scopola japon-

ica,12) Mandragora autumnalis,18) and Fabiana imbricata.11)

Scopoletin gives a blue fluorescence in solutions. Many of its

metallic derivatives are colored.

Fraxetin , another beautiful fluorescent substance is a deriva¬

tive of tetra hydroxy cinnamic acid. It may be considered as a

3 Ann., 84, 173.

4 Zwenger’s Ann., 115, 1.

5 Ann. Chem. Jr., 20, 86.

6 Arch. Pharm., 38, 330.

T Ber., 9, 1182.

8 Ber., 23, 3347.

9 Czapek— Biochemie der Pflanzen, p. 563.

10 Am. Jr. Ph., 42, p. 1; 54, p. 337; Arch. Pharm., 236, p. 329.

11 Arch. Pharm. 228, p. 438, 440.

13 Same as 11.

13 Jr. Prakt. Chem., 172, p. 274.

14 Arch. Pharm., 237, p. 1.

51— S. A. L.

802 Wisconsin Academy of Sciences , Arts , md Letters.

methyl ether of hydroxy daphnetin or aesculetin, or as a methyl

ether of trihydroxy cumarin.

Fraxetin occurs along with aesculetin as the glucoside fraxin

in the horse chestnut.15) It occurs as the glucoside fraxin in

Fraxinus excelsior™) Fraxinus ornus,17) also both in the free

state and as glucoside in Fraxinus americana.18)

Fraxetin gives a blue fluorescence in solutions. Many of its

metallic derivatives are colored. The position of the methoxy

group in fraxetin is not known.

Pigments referable to hydrocarbons of the formula of

SATURATION Cn H2n_10.

Under this formula of saturation one pigment of known con¬

stitution, juglone, referable to dihydro naphthalene, and two

others probably derivatives of methyl dihydro naphthalene have

been isolated. All three of these compounds are hydroxy

naphthaquinones, possessing both phenol and quinone proper¬

ties and capable of forming phenoquinones and quinhydrones

with themselves and with the corresponding hydroquinones. In

addition to these naphthaquinone pigments one, referable to di¬

dihydro phenyl ethane has been isolated.

Pigments referable to dihydro naphthalene.

Jaglone

Juglone, a hydroxy derivative of naphtha quinone, is found

in all the green parts of the walnut tree, Juglans regia,1) and

especially in the green shells of the nuts. Associated with it

16 Fogg. Ann., 107, p. 331.

iePog;g. Ann., 98, p. 637.

1TPogg. Ann., 98, p. 637: C. r. 51, p. 31.

18 Am. Jr. Ph., 54, 282; 54, 99.

*C. N., 141, p. 838 ; Ber. Repert., 5, p. 106 ; 7, p. 1 ; Her., 10, p. 1542.

Wakeman — Pigments of Flowering Plants. 803

in the twigs, bark, leaves and shell of the unripe fruit, but not

in the shells of ripe nuts, a and ^-hydrojuglones, trihydroxy

naphthalenes, are also found. These colorless hydrojuglones,

during the ripening of the nuts, are undoubtedly oxidized to

the yellowish red juglone. Indeed the oxidation may well be

carried farther, for juglone is readily oxidized by exposure to

the air into hydroxy juglones which are still darker in color.

There is no record, however, of the hydroxy juglones having

been isolated from the walnut material. Juglone is also found

in the green shells of the nuts and the bark of the twigs of J ug-

lans nigra , the black walnut, Juglans cinerea ,2) the butternut;

in the leaves of Cary a olivaef&i'mis,2) the pecan; and in the bark

of the twigs of Pterocarya caucasia 2)

The possibilities for combination between juglone and the

hydrojuglones must not be overlooked in considering the dark

colored pigments in the walnut shells. Not only is there the

possibility of juglone combining with each « and /3-hydro juglone

to form the corresponding quinhy drones ; but the additional

possibilities of its forming phenoquinones with itself, through

the addition of its phenol group to a carbonyl group, and also

of forming phenoquinones with the hydro juglones. If jug¬

lone be oxidized in the plant to hydroxy juglones the possibil¬

ities for pheno quinone and quinhydrone formation become

fully as great as with the thymoquinones in the Monarda species.

Pigments referable to a Methyl dihydro naphthalene

Cio H9 ch3

Methyldihydro-Naphthalene

C10 H3 02 (OH), CH,

Dihydroxy-methyl

Naphthaquinone

C10 Hfi 02 CH3

Methyldihydro-Naphthaquinone

C10 H2 (OH)3 02 ch3

Trihydroxy-methyl

N aphthaquinone

Two pigments, one orange red, crystallizing in needles, and

the other red, crystallizing in plates, have been isolated from

the root tubers of Prosera Whittakeri. The former is apparently

dihydroxy methyl naphthaquinone and the latter trihydroxy

methyl naphthaquinone.

Pigmentation in Drosera Whittakeri seems to be confined to

2C. r., 141, p. 838.

804 Wisconsin Academy of Sciences, Arts, and Letters.

the tubers. According to Rennie* 1) who has made a study of

these pigments, each plant is provided with one tuber attached

to a stem at a depth of 3 to 4 inches. The tubers vary from %

to % of an inch in diameter. Each consists of an inner solid

but soft nucleus, full of a reddish sap, and an outer series of

thin, more or less dry, layers of an almost black material. Be¬

tween the layers is to be found, in small quantities, a brilliant

red coloring matter, apparently most plentiful in the older

tubers. The flowers of the species are white, resembling those

of the white oxalis. The red pigment gives a violet, the orange

red a deep red solution with ammonia and alkalies.

This remarkable form of pigmentation is doubly interesting

when considered from the view point of the quinhydrone hy¬

pothesis. Both of the substances are quinones, and both have

in addition phenol groups. The presence of the corresponding

hydroquinones has not been indicated, though both substances

may be reduced to hydroquinones. Whether the black outer

layers owe their color to phenoquinones, quinhydrones or higher

oxidation products of the known pigments does not become ap¬

parent from Rennie ’s investigations, though the red crystals be¬

tween the dark layers are apparently the trihydroxy com¬

pound.

Pigments referable to di-dihydropJienyl-ethane .

Di-dlhydro phenyl ethane

Phoenteelne

Phoenieeine1.) occurs as the colorless leueo-compound Phoe-

nin in the heart of wood of Copaiefera bract eat a, the “purpur-

holz” “amaranth wood’5 or “blue ebony” of South America,

comprising about two per cent of the wood. Phoenin,

C14 H16 Ot> upon treatment with mineral acids gives up one

1 Chem. News, 55, p. 115; Jr. Ohem. Soc., 51, p. 371; 63, p. 1083.

1 Kleerekoper, E. Neederl. Tijdschr. Pharm., 13, p. 245 ; 284, 303. (Chem.

Centralbl. 72, II, p. 858, 1085).

Wakeman — Pigments of Flowering Plants . 805

molecule of water forming quantitatively the red phoeniceine

C14 H14 06. This reaction also takes place quantitatively upon

long heating at 100° or heating for one hour at 150°-160°.

Upon exposure to the air at ordinary temperature phoenin

passes slowly to phoeniceine.

Upon treatment with alkalies phoeniceine turns blue, then

violet, and finally brown in color. Its behavior toward alkalies

and acids is similar to that of the flavone compounds containing

two hydroxy groups in ortho position. Kleerekoper1 2) sug¬

gests the formula given above.

Pigments referable to hydrocarbons of the formula of sat¬

uration Cn U2n _ 12

There exist in plants several pigments and pigment forming

substances referable to hydrocarbons of this degree of saturation,

all of which are substitution products of four different hydro¬

carbons, namely, naphthalene, two dihydro naphthalene deriva¬

tives with unsaturated side chains, and phenyl-diphenyl methane.

Pigments referable to Naphthalene.

Naphthalene a Hydrojoglone

Both of the hydro juglones exist, along with juglone, in all

the green parts of the walnut tree, Juglans regia}) Upon oxi¬

dation a hydrojuglone yields juglone. A discussion of the var¬

ious quinhydrones and phenoquinones which may be formed by

combination of the two hydrojuglones with juglone, also with

possible higher oxidation products of juglone, has been given

under juglone.

1 Ber., 10, p. 1544; 17, p. 2411; 18, p. 204; 18, p. 474; 18, p. 2567.

2 Jr. Chem. Soc., 69, p. 1355.

806 Wisconsin Academy of Sciences , Arts , and Letters.

Pigments referable to methyl 2 , butylene 2 , dihydro naphtha¬

lene.

dihydro naphthalene

A hydroxy amylene naphthaquinone, lapachol, yellow in

color, has been found in the lapacho3) wood, obtained from

several species of South American Bignoniaceae, in the green

heart of Surinam4) and in Bethabarra wood.5)

Upon reduction with sodium, lapachol yields an unstable hy-

drolapachol. The metallic derivatives of lapachol are of var¬

ious shades of red and orange red.

Pigments referable to methyl 2 , butylene 3 , dihydro naphtha¬

lene.

A yellow compound, lomatiol,6) hydroxy lapachol or oxyiso-

lapachol, has been isolated from the seeds of Lomatia ilicifolia

and Lomatia longifolia.

The metallic derivatives of lomatiol are red, orange or brown

in color.

8 J ahresb. u. d. Fortsch. d. Chem., (1858) p. 264.

4 Ztsch. f. Chem., (1867) p. 92.

s Am. Chem., Jr., 11, p. 267.

8 Jr. Chem. Soc., 67, 784.

Wakeman — Pigments of Flowering Plants . 807

Pigments referable to phenyl-dihydro phenyl methane.

rivatives of the above named hydrocarbon, has been isolated from

the berries of Rhamnus cathartica .7) These pigments are rham-

nocitrin, /3-rhamnocitrin, rhamnochrisin, rhamnolntin and

rhamnonigrin. As will be seen from the formula assigned to

rhamnocitrin above, these pigments resemble the xanthone de¬

rivatives, falling under the degree of saturation Cn H2n— i4,

more closely than they do the remaining known pigments of

this degree of saturation. They are indeed derivatives of a

reduced xanthone nucleus.

Rhamnocitrin occurs, probably, in the free state. It cry¬

stallizes in golden yellow needles, and it forms metallic deriva¬

tives deeper in color than the compound itself.

/3-Rhamnocitrin has the same empirical formula as rham¬

nocitrin which it closely resembles. To mordanted fabrics it

imparts a more enduring color than does rhamnocitrin.

Rhamnochrysin, C1S H12 07 crystallizes in orange yellow cry¬

stals. It is looked upon as an oxidation product of rhamno¬

citrin. Whether the molecule is of phenyl-dihydro phenyl

7 Bull, de Pharm., 4, p. 64; Journ. de Chim., Med., 6, p. 193; Journ. de

Pharm., et de Chim., 11, p. 666 ; Arch, de Pharm., 113, p. 63 ; Arch, d

Pharm., 238, p. 459.

808 Wisconsin Academy of Sciences, Arts, and Letters.

methanone configuration, or contains the “chromone” group

does not appear to have been determined. Since it contains

two additional hydrogen atoms as well as the additional oxy¬

gen the former appears more probable, that is, the elimination

of the elements of a molecule of water to form a heterocycle

probably has not taken place.

The remaining pigments from Rkamnus cathartica plainly do

not fall under this formula of saturation, therefore, will not be

considered here.

Pigments referable to hydrocarbons of the degree of sat¬

uration CnH2n-14.

All of the pigments of known constitution falling under this

degree of saturation fall into two closely related classes.

I. Derivatives of diphenyl and its homologues.

II. Derivatives of diphenyl methane series and their homo¬

logues.

Not only are the pigments referable to these closely related

hydrocarbons but they are all hydroxy or methoxy— derivatives

of these hydrocarbons. They occur in the plant either in

the free state or as glucosides, and they resemble each other as

closely in properties as they do in general structure.

I. Pigments referable to the diphenyl series and homologues.

1. Pigments referable to ditolyl.

a. Ellagie acid.

II. Pigments referable to diphenyl methane series and their

homologues.

A. Diphenylmethane series.

1. Pigments referable to diphenyl methane.

Cotoin.

Euxanthone.

Maclurin.

Kinoin.

Gentisein.

Gentisin.

Datiscetin.

2. Pigments referable to phenyl-o-ethophenyl-

methane.

Catechin

Cyanomaclurin.

Wakeman — Pigments of Flowering Plants.

809

B. Diphenylethane series.

1. Pigments referable to diphenyl ethane.

Genistein.

C. Diphenylpropane series.

1. Pigments referable to diphenyl propane.

Phloretin.

Butin.

Saponarin and Vitexin.

I. Pigments referable to the diphenyl series of hydro¬

carbons.

The only member of this series to which a plant pigment is

known to be referable is a dimethyl homologue, the ditolpl.

Pigments referable to ditholyl.

Ellagic acid occurs quite widely distributed in plants, usually

accompanied by tannins. It is found in the leaves of Juglans

regia 1 along with gallic acid andjuglone ; in the leaves of Quercus

pedunculata,* 2 Quercus infectoria} 3 4 Caspinus bet ulus* Haema-

toxylon campechianum ,5 * Caesalpina brevifolia ,5 Caesalpinia

coriaria ,3 coriaria myrtifolia ,5 Quebrachia lorentzii? Tamarax

gallica7 Tamarax africana 7 Bonabanga moluccana8 Punica

granatum 8 Terminalia chebula,9 Vaccinium vitis ideaea.10

Ellagic acid forms small yellowish crystals. It dissolves in

concentrated sulphuric acid with a citron yellow color. From

*C. r„ 141, p. 838.

2Z. physiol. Chem., 20, p. 511.

3 Jr. Chem. Soc., 71, p. 1131.

4 Arch. Pharm., 244, p. 575.

6 Proc. Chem. Soc., 16, p. 45 ; Jr. Chem. Soc., 77, p. 426.

* Jr. Chem. Soc., 71, p. 1194.

7 Jr. Chem. Soc., 73, p. 374.

8Nederl. Tijdschr. Fharm., 1887, p. 68.

•Ber., 42, p. 353.

10 Chem. News.. 52. p. 78 ; Pharm. Jr., 16, p. 92.

810 Wisconsin Academy of Sciences , Arts , and Letters.

this solution it is precipitated unchanged by water. With po¬

tassium hydroxide solution it forms a deep yellow solution

which upon exposure to the air goes to a deep red¬

dish yellow. It dyes wools mordanted with chromium a

deep olive yellow color.

The formula for ellagic acid given above was suggested by

Graebe.11. Further work upon the constitution of ellagic acid

by Goldschmidt,12 also by Niernstein,13 and by Herzig14 has con¬

firmed Graebe ’s formula.

II. DERIVATIVES OF THE DIPHENYL METHANE SERIES OF HYDRO¬

CARBONS AND THEIR HOMOLOGUES.

By far the greater number of pigments of known constitution

falling under the degree of saturation Cn H2n__14 are derivatives

of the diphenyl methane series and their homologues. Of these

diphenyl methane derivatives there are representatives of the

diphenyl methane, diphenyl ethane, and diphenyl propane ser¬

ies; but by far the greater number are referable to diphenyl

methane.

II. A. 1. Pigments referable to diphenyl methane.

All the plant pigments of known constitution referable to

diphenyl methane are tri, tetra, penta, or hexa hydroxy sub¬

stitution products of diphenyl methanone. In some instances

it is true methoxy groups are substituted for hydroxy groups,

while in others the elements of a molecule of water has been

eliminated from the hydroxy groups, thus forming an oxide

group. Indeed this latter condensation appears always to have

taken place wherever the hydroxy groups are so located that by

the elimination of the elements of a molecule of water there can

be formed a cycle of six members. Thus some of the pigments

of this group are dicyclic while others are tricyclic compounds,

the third cycle being heterocyclic in as much as it contains an

oxide oxygen. These pigments are all alike in that they form

needle like crystals very similar in character, of a pale yellow

color, (hence the name xanthone,) and of high melting point.

11 Ber., 36, p. 212.

ia Monatsh. f. Chem., 26, p. 1143.

13 Ber., 41, p. 1649.

14 Monatsh. f. Chem., 29, p. 363.

Wakeman — Pigments of Flowering Plants.

811

Authorities differ somewhat as to what part or parts of the

molecule the coloring properties are due. All seem to agree,

however, that it depends largely upon the number of hydroxy

groups. A study of the formulae reveals the fact that the

property of color appears to depend upon the number of free

hydroxy groups, or their oxide equivalent, rather than upon

the number originally introduced into the molecule, the chang¬

ing of the hydroxy groups into methoxy groups appears to

diminish both the color of the compound and its dyeing proper¬

ties. On the other hand the elimination of the elements of

a molecule of water from two hydroxy groups to form the xan-

thone grouping appears to intensify both pigmentation and dye¬

ing quality.

Most writers, in treating of these pigments, distinguish be¬

tween diphenyl ketone and xanthone derivatives. However,

since whether or not a compound falls into the xanthone group

depends merely upon the position of hydroxy groups and the con¬

sequent elimination of the elements of a molecule of water and

the formation of a heterocycle and not upon any more basal

constitutional difference, there appears to be no sufficient point

to this distinction. Therefore for the sake of simplicity as well

as for observing genetic relationships, all of the members of

this group, referable to diphenyl methane, will here be regarded

as hydroxy derivatives of diphenyl methanone.

II. A. 1. Pigments referable to diphenyl methane.

a. Trihydroxides.

Cotoin.

b. Tetrahydroxides.

Euxanthone.

Euxanthonic acid.

c. Penthydroxides.

Maclurin.

Kinoin.

d. H exhydroxides.

Gentiseine.

Gentisin.

Datiscetin.

812 Wisconsin Academy of Sciences, Arts, and Letters.

II. A. 1. a.) Trihydroxy derivatives of diphenyl methanone.

Cotoin,— Dihydroxy-1, 5-methoxy-3-diphenyl methanone.

CH COH

Cotoin is a trihydroxy derivative of diphenyl ketone, referable

to a penthydroxide of the underlying hydrocarbon. It occurs

in the bark of coto 1 and para coto, obtained from Brazil.

Cotoin2 forms colorless or only slightly yellow crystals

which melt at 130°. With caustic alkalies it forms a yellow

solution. In 1894 Ciamician and Silber3 partially determined

the constitution of cotoin. Pollock,4 in 1901, completed this

by determining the position of the hydroxy groups.

In the bark of para coto cotoin is accompanied by a series of

closely related compounds, hydrocotoin, methyl hydrocotoin,

protocotoin and methyl protocotoin. These compounds, all of

which closely resemble cotoin, were first studied by Jobst and

Hesse5 in 1879. In 1891-1892 Ciamician and Silber6 made a

further investigation of this series of pigments and determined

their relation to cotoin and to each other. This relationship is

best illustrated by the following series of partly analyzed for¬

mulae :

Cfi Hs

Cotoin.

Hydrocotoin

0 CH3

COC6 H5

Methyl hydrocotoin

1Neues. Kept. f. Pharrn., 25, p. 23.

2 Ann., 199, p. 17.

3 Ber., 27, p. 1497.

4 Monats., 18, p. 738; 22, p. 996.

6 Ann., 199, p. 17.

6 Ber., 24, p. 299, 2977; 25, p. 1119.

Wakeman — Pigments of Flowering Plants.

813

0 ch3

Protocotoin.

Methyl protocotoin.

It will be seen from the above formulae that hydrocotoin is

not, as the name implies, a reduced cotoin ; but, rather a methyl

cotoin, or monohydroxy-dimethoxy-diphenylmethanone. Methyl

hydrocotoin is dimethyl cotoin, or trimethoxy-diphenylmeth-

anone. Protocotoin is the methylene ether of a dihydroxy-

methylcotoin and methyl protocotoin is a methylene ether of a

dihydroxy-dimethylcotoin.

The three compounds possessing free hydroxy groups form

colored metallic derivatives. Further studies of cotoin, hydro¬

cotoin and their derivatives have been made by Henrich,* 7 Per¬

kin,8 and others.9

II. A. 1. b.) Tetrahydroxy derivatives! of diphenyl methanone.

Euxanthone, — Dihydroxy-4, 5-diphenylene methanone oxide , or

Dihydroxy— 4, 5-xanthone.

CH

Euxanthone exists partly in the free state and partly in com¬

bination with glucoronic acid in “purree,” or Indian yellow.

Indian yellow is prepared from the urine of cattle fed upon

TB., 32, p. 3423.

8 Jr. Chem. Soc., 71, p. 1194.

8 Moants., 18, p. 142 ; Ann., 282, p. 191 ; B., 28, p. 1549 ; Pharin. Post.,

814 Wisconsin Academy of Sciences , Arts , and Letters.

mango leaves. Enxanthone was first studied by Stenhouse1 in

1844 and a little later by Erdman2 who named both the free

euxanthone and the acid compound. In 1889 Graebe3 synthe¬

sized euxanthone and made a study of its structure. The com¬

plete structure of the molecule was determined by Kostanecki4

and Nessler, 1891-1894. As yet euxanthone does not appear to

have been isolated directly from the plant in which it may or

may not exist.

Euxanthone forms pale yellow needle like crystals which melt

at 240°. It forms disodium and dipotassium5 compounds

which are red in color. Its monomethyl ether6 is pale yellow

in color and its dimethyl ether is colorless. Other derivatives

of euxanthone have been studied by Perkin.7

II. A. 1. c.) Penthydroxy derivatives of diphenyl methanone.

Maclurin, — Penthydroxy — 2, 4 , 6 , 3' , 4 ' — diphenyl Methanone.

CH CH

Maclurin, also called penthydroxy benzophenone and moringa

tannic acid, occurs in Morns tinctorian along with morin. Mac¬

lurin has been known for a long time and has called forth a

large number of investigations. It was first isolated by Wag¬

ner2 in 1850. Wagner considered the substance to be a tri-

basie acid isomeric with morin. Illasiwetz and Pfaundler3 in

1863 recognized the fact that maclurin is not an acid. Bene-

1 Ann., 51, p. 423.

3 Jr. Prakt Chem., 33, p. 190.

3 Ann., 54, p. 265.

4 Ber., 24, p. 3980; 27, p. 1989.

“Ann., 290, p. 156.

8 Ann., 318, p. 365.

7 Jr. Chem. Soc., 73, p. 671.

1 Czapek, II., p. 521.

3 Jr. Prakt. Chem., 51, p. 82; 52, p. 449.

3 Ann., 127, p. 354; 134. p. 122.

Wakeman — Pigments of Flowering Plants .

815

diet4 in 1877 confirmed the work of Hlasiwetz and Pfaundler,

Ciamician and Silber5 in 1894 attacked the problem of its con¬

stitution and partially elucidated its structure. Koenig and

Kostanecki6 in the same year completed this task. Other studies

of maclurin have been made by Delffs7 in 1862; Liebig8 in

1860 ; Bedford and Perkin9 in 1895 ; and by Perkin in 1897.

Maclurin forms fine pale yellow crystals which melt at 200°.

It dissolves in caustic alkalies forming a yellow solution which

turns brown upon exposure to the air. Lead acetate gives a

yellow precipitate.

Kinoin, — Tetrahydroxy — 2, 3 , 4 2' — metlnoxy-3' — diphenyl

methanone.

Kinoin* 1 occurs in the dried juice of Pterocarpus erinaceus,

Pterocarpus marsupium, and Coccoloba uvifera , also in several

species of Eucalyptus, and in Butea frondosa.

In 1879, Etti2 isolated from green kino a substance which he

called kinoin and to which he assigned the formula C14H1206.

This substance contains a hydroxy group and upon hydrolysis

yields pyrocatechin and gallic acid. Thomas3 in his book on

the natural dyestuffs has suggested for kinoin the structural for¬

mula given above.

A considerable number of investigations of the various species

of kino have been made. The results of most of these investiga¬

tions do not agree with those of Etti, phloroglucin, pyrocatechin,

* Ann., 185, p. 117.

6 Ber., 27, p. 1627; 28, p. 1393.

«Ber., 27, p. 1996.

7 Chem. Centrlbl., 1862, p. 284.

8Jahresber. d. Chem., 1860, p. 278.

9 Jr. Chem. Soc., 67, p. 933.

10 Jr. Chem. Soc., 71, p. 186.

1 Pharm. Jr., 16, p. 676; Pharm. Ztg., 58, p. 593.

2 Ber., 11, p. 1876; 17, II, p. 2241.

8 Les Matieres Colorantes Naturelles, p. 22.

816 Wisconsin Academy of Sciences, Arts, and Letters.

HC

HOC1

and protocatechuic acid being obtained as the products of hy¬

drolysis.

The principal literature upon kinoin is given in the appended

list.

Literature upon kinoin.

Bergholz, Innaug. Dissert. Dorpat. ; B., 5, p. 1.

Eissfeldt, — Ann., 134, p. 122.

Etti,— B., 11, p. 1879 ; 17, p. 2241.

Flueckiger, — B., 17, p. 2241.

Hlasiwetz, — Ann., 134, p. 122.

Kremler,-— Pharm. Post., 16, p. 117.

White, — Pharm. Jr., 16, p. 676; 17, p. 702.

Gentisein, — Trihydroxy— 1, 3, 2' — diphenyl methanone oxide,

or trihylroxy —, 1, 3, 2f — xanthone.

Gentisein

Gentisein occurs as its methyl ether gentisin in the rhizome

of Gentiana1 lutea, also in the rhizome of Frasera Walteri. Gen¬

tisin was first isolated from the rhizome of Gentiana lutea in

1827 by Henry and Caventon. It was studied by Tromsdorff2

in 1837 and by La Conte3 in 1838. La Conte in his study points

out the fact that the gentian plant from which the pigment is

obtained, derives its name, according to Pliny, from the Illyrian

king Gentis, or Gentius, who appears to have valued the root

very highly as a remedy for certain illnesses epidemic in his

time. In 1847 Baumert4 made an extended study of gentisin

1Jr. de Pharm., (2) 7, p. 125.

2 Am. Jr. Pharm., 52, 7.

3 Jr. Pharm., (2) 7, p. 178.

4 Ann., 21, p. 134.

Wakeman — Pigments of Flowering Plants. 817

and determined its empirical formula. Hlasiwetz5 and Haber-

v mann, in 1874, took up the study of the constitution of gentisin.

In 18766 they found that it contains a methoxy group and ob¬

tained gentisein by hydrolysis. In 1891 Kostanecki7 turned his

attention to the constitution of gentisin and in 18948 succeeded

in synthesizing gentisein from phlorogluein and hydroquinone

carboxylic acid. From this product he readily obtained genti¬

sin by treatment with methyl iodide. The remaining question

of the position of the methoxy group was answered by Perkin9

in 1898.

Gentisein crystallizes in pale yellow crystals which melt at

315°. It is soluble in alkalies with a bright yellow color.

Gentisin forms fine needle like crystals of a pale yellow color.

It forms well defined crystalline salts of sodium and potassium,

C14H9 NaOs and C14H9K05.

II. A. 1. d.) H exhydroxy derivatives of diphenyl methanone.

Datiscetin.

Datiscetin has been known for a long time in southern France

where it has been used as a coloring agent for silk. It was first

studied by Braconnet1 in 1816. Later Stenhouse2 showed that

the substance to which the coloring properties are due is a

glucoside which may be hydrolized into datiscetin and rhamnose.

In 1893 and 1894 Marchlewski3 and Schunk undertook the de¬

termination of the constitution of datiscetin and found thot it

belongs to the xanthone group of pigments, assigning to it the

generally accepted formula C15H1206 with two hydroxy and two

methoxy groups, as shown below. Upon treatment with hy-

driodic acid datiscetin yields a tetra hydroxy xanthone of a

yellow color.

More recently, 1907, Marchlewski4 claims that datiscetin is of

the formula C15H10O6, that it melts at 268°-269° instead of

6 Ann,, 25, p. 200.

6 Ann., 62, p. 106.

7 Monats., 12, p. 205; 12, p. 318.

8Monats., 15, p. 1; 16, p. 919.

9 Jr. Chem. Soc., 73, p. 673.

JAnn. Chim. et Phys., (2) 3, p. 277.

a Ann., 98, p. 167.

3 Ann., 277, p. 261; 278, p. 346.

4 Biochem. Zeit., 3, p. 287; Chem. Centralbl., 1906, II, p. 1265.

52— S. A. L.

818 Wisconsin Academy of Sciences , Arts, and Letters.

at 237° as generally given, and that it contains no methoxy

groups. Also that it does not. reduce Fehling’s solution but

readily reduces an ammoniacal silver solution, and that it forms

tetra acetyl, tetra benzoyl, and tetra benzene sulphonal deriva¬

tives. Furthermore that when the glucoside datiscin is hydro-

lized, dextrose, not rhamnose is formed. Also that it is an

isomer of luteolin and probably a flavone derivative.

COH

Datiscetin

Datiscetin occurs as the glucoside datiscin in Datisca canna-

bina. It crystallizes in clear yellow needle like crystals which

melt at 237°.

II. A. 2.) Pigments referable to phenyletho phenyl methane.

Phenyl etho phenyl methane

One pigment of known constitution, eatechin, is referable to

the above hydrocarbon. Another, cyano maclurin, whose con¬

stitution is not yet fully determined is presumably derived from

the same hydrocarbon. Cyano maclurin is accordingly placed

with eatechin in this classification.

Wakeman — Pigments of Flowering Plants.

819

Catechin.

CH CH

Catechu, also called catechinic acid and catechu tannic acid,

was known by Runge1 to exist in the heart wood of Acacia catechu

as early as 1821. It has long been known as a dyestuff impart¬

ing yellow and brown tints to textile fabrics. The coloring

principle, catechin, was probably first described by Nees van

Esenbeck2 in 1832. It has since been the subject of many

chemical investigations, the results of which were for a long time

so various that the chemistry of catechin remained in a very

unsatisfactory condition. The majority of investigators of this

pigment have considered but one catechin to exist, some, how¬

ever, claim that three different catechins with different melting

points, but with other properties similar, have been isolated.

Perkin,3 in 1902, described two catechins, with melting points

of 175°-176°, and 235°-237° respectively, isolated from

Gambir catechu, and another with a melting point of 204°-

205°, from Acacia catechu.

Many different chemical formulae have been assigned to

catechin by different chemists. The latest work by Perkin4

upon this pigment, as well as the even more recent work of Kost-

anecki5 and his collaborators, indicates C15H1406 with five hy¬

dro xy groups as the correct formula for the anhydrous com¬

pound. Perkin6 calls attention to the great similarity of the

catechins to quercetin, which accompanies them in the plant,

probably as a glucoside. He points out the possibility of their

being reduction products of quercetin. The later work of

Kostanecki and Lampe, however, indicates the presence of a

cumaran group, in which the six carbon ring contains only one

1 Berz. Jahresber., 12, p. 250.

2 Ann., 1, p. 243.

3 Jr. Chem. Soc., 81, p. 1160.

4 P'roc. Chem. Soc., 20, p. 177.

5 Ber., 89, p. 4007, 4014.

0Jr. Chem. Soc., 81, p. 1160.

820 Wisconsin Academy of Sciences, Arts, and Letters.

unsubstituted hydrogen instead of the chroman group implied

by Perkin’s idea. This, they state would make catechin the

cumaran derivative of leuco maelurin.

Perkin’s suggestion.

CH CH CH

Catechin

Kostanecki’s formula.

COH CH COH CH

Leuco maelurin

CH CH

COH

HOC

; C CH2

I

C CH2

^ o^

The more important contributions to the chemistry of catechin

are included in the following list :

Catechin occurs in the heart wood of Acacia catechu, in the

“Gambir” from Ouruparia gambir,7 and in TJncaria gambir,8

7 Czapek, II. p. 573.

8 Jr. Chem. Soc., 81, p. 1160.

Wakeman — Pigments of Flowering Plants.

821

also in mahogany wood, and according to Gautier,9 in various

species of cahous, where he thinks there are several varieties of

catechin of different melting points and characterized by a vary¬

ing carbon content.

In a pure state catechin is composed of fine needle like color¬

less crystals, which by oxidation form dyes imparting yellow

shades to textile fabrics. It is sparingly soluble in cold alcohol,

readily soluble in hot alcohol. Air dried it dissolves in ethyl

acetate, also to some extent in pure ether. Dried at 100° it

is insoluble in both these solvents. In aqueous solutions lead

acetate gives with catechin a colorless precipitate, ferric salts

give a green color. In the presence of sodium acetate ferric

chloride gives with catechin a deep violet coloration.

The more important of the contributions to the chemistry of

catechin are included in the following list:

Literature on Catechin .

Clauser, — B., 36, p. 101.

Dellfs, — Pharm. CentrL, (1846), 604; Berz. Jahresb., 27,

p. 284.

Doebereiner, — N. Jahresb. d. Chem. u. Pharm., (1831), p. 378;

Berz. Jahresb., 12, p. 250 ; Schweigg. Jr., 61, p. 378.

Etti, — Monatsh., 2, p. 547; Wien, akad., 84, p. 553; A., 186,

p. 327.

Gautier, — C. r., 85, p. 342 ; 86, p. 668.

Hagen, — Ann., 37, p. 320.

Hlasiwetz, — Ann., 134, p. 118.

Kostanecki and Lampe, — B., 39, p. 4007, 4014, 4022; 40, p. 720.

Kraut and Delden, — Ann., 128, p. 285.

Liebermann and Tauchert, — B., 13, p. 964.

Loewe, — Zeit. anal. Chem., 13, p. 113.

Ness van Esenbeck, — Ann., 1, p. 243.

Neubauer, — Ann., 96, p. 337.

Perkin, — Jr. Chem. Soc., 81, p. 1160; Proc. Chem. Soc., 20,

p. 177.

Schuetzenberger and Bach, — Bull. Soc. Chem., 4, p. 51.

Swanberg, — Ann., 24, p. 215.

Waekenroder, — Ann., 37, p. 306.

Zwenger, — Ann., 37, p. 320.

®C. r., 85, p. 342 ; 86, p. 668.

822 Wisconsin Academy of Sciences , Arts, and Letters.

Cyanormclurin

Cyanomaclurin was isolated by Perkin and Cope,* 1 in 1895,

from Artocarpus integrifolia, where it exists along with the yel¬

low pigment morin. Cyanomaclurin crystallizes in colorless

crystals which dissolve in sulphuric acid with a beautiful crim¬

son color. Ferric chloride colors an aqueous solution of cyano¬

maclurin a deep violet color. Dilute alkaline solutions, dis¬

solve it with a deep indigo blue color which on standing changes

to green, then brown. It does not combine with mordants to form

a dye.

Cyanomaclurin2 is isomeric with catechin. It is probably a

catechin in which the catechol nucleus is replaced by resorcinol.

II. B. Pigments referable to diphenyl ethane.

Of the pigments of known constitution only one, Genistein,

is believed to be referable to diphenyl ethane.

Genistein.

While the constitution of genistein has not yet been fully de¬

termined it is believed by Perkin and Newbury1 to be represented

by the formula

(OH), C6IP /°^CH C, H, OH

'

II

o

Genistein has been isolated, along with luteolin, from the

leaves of Genista tinctorial It crystallizes in colorless ileedles.

To fabrics mordanted with aluminum salts genistein imparts a

yellow color.

II. C.) Pigments referable to diphenyl propane.

Three pigments, or pigment forming substances, of known

constitution are referable to diphenyl propane. These are

phloretin, butin, and saponarin or vitexin.

1 Jr. Chem. Soc., 67, p. 939.

1 Proc. Chem. Soc., 15, p. 179.

2 Proc. Chem. Soc., 18, p. 138; 20, p. 170.

2 Jr. Chem. Soc., 75, p. 832; 77, p. 1310.

Wakeman — Pigments of Flowering Plants.

823

Plnloretin.

CH

HOC

HC

|c ”C-CH2— ch2~

COH

CH

COH

CH

Phloretin occurs as the glucoside phloridzin in several species

of Rosaceae, especially in the leaf buds and the bark of Pirns

mains,1 the apple tree. Phloridzin was discovered in 1835 by

De Koninck2 and Stas in the bark of the apple tree. Later

Stas,3 1839, made an extended study of phloridzin and recog¬

nized its glucosidal character, isolating glucose and phloretin.

Further studies of phloretin and of phloridzin were made by

Rennie,4 Schiff,5 Hesse,6 and Fischer,7 also by Schunck and

Marchlewski.8 In 1894 Michael9 found that phloretin upon

hydrolysis yields phloroglucin and phloritinic acid. The latter

was at the time believed to be p-hydroxy-hydrotropic acid.

CH CH

CH

Later Bougult10 found phloretinic acid to be identical with

p-hydroeumaric acid.

CH CH

CH CH *

p-Hydroxycumarlc add

1 Jr. Prakt. Chem., 98, p. 205; C. r, 139, p. 294.

2 Ann., 15, p. 75, 258.

3 Ann., 30, p. 200.

4 Jr. Chem. Soc., 49, p. 860; 51, p. 636.

6 Ann., 172, p. 357; 229; p. 374; B., 2, p. 743; 14, p. 303.

8 Ann., 176, p. 288.

7 Ber., 21, p. 288.

8 Ber., 26, p. 942.

8 Ber., 27, p. 2686.

824 Wisconsin Academy of Sciences, Arts, and Letters.

Phloretin crystallizes in small colorless plates. It melts at

253° — 255°. Phloretin forms a tetra-methyl11 and a tetra-

acetyl12 derivative,12 therefore must contain four hydroxy

groups.

Phloridzin crystallizes in fine silky needles, white or faintly

yellow in color. It melts at 108° — 109°. With metals phlor¬

idzin forms colored compounds. Conspicuous among these are

the dark red iron salt and the bright yellow calcium compound.

Butin, — Trihydroxy — 3, 3' , 4' — dihydro — a, ft — flavone.

Butin, a penthydroxy derivative of diphenyl propanone, was

first isolated from the flowers of Butea frondosa by Hummel and

Cavallo* 1 in 1894, and later, by Hill2, in 1903. In 1904 a some¬

what extended study of the pigment was made by Perkin3 who

showed that the substance isolated by Hummel and Cavallo and

called by them butin was not a single compound but a mixture

of two substances, one of which was colorless while the other was

orange red in color. The colored substance Perkin named

Butein, while to the colorless substance he assigned the original

name of butin. , Perkin showed further that while butin is a

trihydroxy dihydro flavanone, butein is a tetrahydroxy deriva¬

tive of diphenyl propene, benzyliden acetophenone (chalkon).

This he proved by the synthesis of butein from monomethyl res-

acetophenone and dimethyl protocatechinic aldehyde according

to the processes of Kostanecki4 and his colleagues in their synthe¬

sis of the chalkon derivatives. After the synthesis of butein,

butin was prepared from it by treatment with dilute sulphuric

19 C. r., 131, p. 43.

11 Ber., 28, p. 1396.

12 Ber. 27, p. 2686.

1 Proc. Chem. Soc., 10, p. 11.

2 Proc. Chem. Soc., 19, p. 133.

3 Jr. Chem. Soc., 85, p. 1459.

4 Ber. 37, p. 773, 779, 784.

Wakeman — Pigments of Flowering Plants. 825

acid when the compound was, presumably, first hydrated and

then dehydrated resulting in a rearrangement of the molecule.

Butin occurs with butein as a glueoside in the blossoms of

Butea frondosa, a leguminous plant of India and Burma. It

crystallizes in small colorless needles melting at 224°-226°. It

is soluble in alcohol, sparingly soluble in acetic acid and ether,

almost insoluble in benzene. With alcoholic lead acetate solu¬

tion butin forms a pale yellow precipitate, with alcoholic ferric

chloride a deep green coloration. With cold sulphuric acid it

first turns red, then goes into solution with a pale yellow color.

On fusion with caustic potash and a little water at 200°-220°,

butin yileds protocatechuic acid and resorcinol.

Though butin is not itself a pigment it dyes mordanted fab¬

rics exactly as buetin does. From this behavior it is believed

that it is changed by the mordants into butein. When boiled

with a solution of potassium hydroxide and then acidified a

bright orange crystalline precipitate of butein immediately sep¬

arates out.

Saponarin.

Certain plants contain in the cell sap of the epidermal cells

of the leaves a substance which turns blue1 with iodine. As

in the case of starch this color disappears upon heating and

returns again upon cooling. For this reason this substance is

often mistaken for starch, as it was by its discoverer Sanio2 in

1857. Schenk,3 in the same year, doubted the identity of this

substance with starch, and Naegeli4 in 1860 showed that the two

are not identical. Dufour,5 in 1885, found this substance in

about twenty species of plants.

In 1906 Barger6 separated the above described substance from

Saponaria officinalis and called it saponarin. He showed that

the substance is a glueoside which upon hydrolysis yields glu¬

cose and another substance C15H1407, identical with vitexin from

Vitex litt oralis.

The substance which turns iodine blue, formerly known as

soluble starch, has been found in Gagea lutea,2 in Ornithogalum

1 Rupe, — Der Natuerlichen Farbstoffe, 2, p. 42.

2 Bot. Zeit., 15, p. 420.

3 Bot. Zeit., 15, p. 497, 555.

4 Zeit. zur. Wissensch. Bot., 2, p. 187.

6 Bull. Soc. Sci. Nat., 21, p. 227.

6 Jr. Chem. Soc., 89, p. 1210.

826 Wisconsin Academy of Sciences , Arts, and Letters.

leaves,7 in Saponara officinalis, 8 and in about twenty other species

of phanerogams.5 The identity of the peculiar substance from

all these plants with saponarin has not been fully established.

Saponarin forms crystals which, dried in the air, are white,

dried in a vacuum they are pale yellow. It is insoluble in cold

water, soluble in solutions of caustic alkalies or alkaline car¬

bonates with an intense yellow color. In mineral acids it gives

a yellow solution. The solution in sulphuric acid has a blue

fluorescence. Upon dilution the saponarin is not precipitated

at once. This acid solution, upon the addition of iodine in

potassium iodide solution, is colored blue or violet. The glu-

coside combines with nine acetyl radicals to form a nonacetyl

derivative of saponarin.

Vitexin.

Yitexin, C15H1407, occurs as a glucoside in the New Zealand

dye wood Puriri, Vitex litoralis,* 1 and as the glucoside saponarin

in saponara officinalis .2

Yitexin crystallizes in microscopic, glistening plates of a pale

yellow color. It melts at 260° with characteristic frothing.

It is insoluble in water, slightly soluble in alcohol, soluble in

pyridine and in solutions of alkalies with a golden yellow color.

Vitexin forms a pentacetyl derivative. Upon treatment with

nitric acid it forms a tetranitro apiginin. By decomposition

with caustic alkalies it forms phloroglucin and p-hydroxy aceto¬

phenone. It is therefore closely related to apiginin from which

it differs by the elements of two molecules of water. Since it

forms phloroglucin and p-hydroxy benzoic acid the additional

hydroxy groups are probably in the pyron cycle, or in a chain

which would give rise to this cycle.

CH

CH CH

HOC

HC

0

1C — o — - c - c

OH

C — CH — CH OH

CH CH

COH

OH

T Bull. Soc. Bot. de France., 5, p. 711.

1 Jr. Chem. Soc., 73, p. 1019; 77, p. 422.

a Jr. Chem. Soc., 89, p. 1210..

Wakeman — Pigments of Flowering Plants.

827

HC

HOC

O

OH OH

II i I

C — CH CH

' C

HC

CH

/\

COH

CH

Both the above formulas have, however, six hydroxy groups,

whereas vitexin forms only a pentacetyl and saponarin only a

nonaeetyl derivative. Dehydration might, however, take place

in the molecule during the process of acetylation.

To account for the formation of only the pentacetyl vitexin

Perkin has suggested the presence of a reduced phloroglucinol

nucleus. This would give a formula of the type shown below.

Pigments referable to hydrocarbons of the formula of sat¬

uration CH2n-16.

Of all the pigments of known constitution occurring in plants

by far the greater number are referable to hydrocarbons of the

formula of saturation CnH2n_16. These pigments when referred

to their underlying hydrocarbons fall into three classes.

1. ) The diphenyl olefin derivatives.

2. ) The dihydroanthracine derivatives.

3. ) The methyl-phenyl hydrindine derivatives and their

oxidation products.

In the first class are found the flavone derivatives, referable

to diphenyl propene, and a large number of compounds refer¬

able to similar hydrocarbons. This group also includes the so-

called anthocyanine pigments, so far as their structure has been

determined.

The second class is made up of the anthraquinone and methyl

anthraquinone derivatives, a group which includes, outside of

the flavone derivatives, of the above class, the greater number

of coloring matters, so far studied, falling under this degree of

saturation.

828 Wisconsin Academy of Sciences , Arts, and Letters.

The third class is a small one made up of the pigment form¬

ing substances brazilin and haematoxylin and the pigments

brazilein and haematein.

I. Pigments referable to Diphenyl olefins and homologues.

It was pointed out in connection with the pigments referable

to hydrocarbons of the formula of saturation CnH2n_14 that a

conspicuously large number of these colored compounds were

derivatives of the diphenyl and diphenyl methane series of hy¬

drocarbons. The same relationship is found to exist among the

pigments referable to hydrocarbons of the degree of saturation

CnH2n_16, for here we find a considerable number of compounds

referable to the diphenyl olefin series of hydrocarbons, having

as their initial members diphenyl ethene, diphenyl propene, and

diphenyl butene.

I. Pigments referable to the diphenyl olefin series of hydrocar¬

bons.

A. Diphenyl ethene.

1 . ) Tolyl-ethophenyl-ethene.

Berberin.

B. Diphenyl 1, 3, propene.

1.) Flavone derivatives.

Chrysin

Tectochrysin

Apiginin

Acacetin

Galangin

Galangin meyhyl ether

Luteolin

Luteolin methyl ether

Lotoflavin

Fisetin

Kaempherol

Kaempherid

Quercetin

Khamnetin

Isorhamnetin

Bhamnazin

Morin

Myricetin

Gossypetin

Wakeman — Pigments of Flowering Plants. 829

2. ) Butein

3. ) Anthocyanins.

Pelargonidin

Cyanidin

Paeonidin

Delphinidin

Myrtillidin

Malvidin

Oenidin

C. Diphenyl 1, 4, butene 2.

Indigotin.

I. A. Pigments referable to the diphenyl ethene series of

hydrocarbons.

1.) The only members of this series to which a plant pigment

is referable is a methyl ethyl homologue, the tolyl-etho phenyl-

ethene.

Berberin, which is a basic plant pigment, an alkaloid, may be

regarded as the product obtained by the deammoniation of a

dimethyl, methylene either of a tetra hydroxy, triamido sub¬

stitution product of the above hydrocarbon. The accepted for-

foirmula1 for berberin is based upon the investigations of the

products which result from the dbbau of the molecule by oxida¬

tion with potassium permangenate.

Berberin was isolated by Buchner2 before 1837 from the root

of Berberis vulgaris and described by him. Since then it has

been the subject of a large number of investigations and has

1 Jr. Chem. Soc., 55, p. 63; 57, p. 992; 97, p. 318.

2 Ann., 24 p. 228.

830 Wisconsin Academy of Sciences, Arts, and Letters.

been found to be widely distributed in nature. In addition to

several species of barberry it is known to exist in Hydrastis

canadensis,3 Coptis trifola ,4 Zanthorrhiza apiifolia,5 Delphinium

saniculaef olium,3 Thalictrum flavum,7 Adonis vernalis7 Mahonia

aequifolium,8 Jatrohiza palmata ,9 Tintospora rumphii,10 Zylopia

polycairpa,* 11 Chelidonium majus,12 Argemone mexicana,13 Cory -

dalis tuberosa,14: Corydalis vernyi,15 Andria inermis,16 Xanthoxy-

lum caribaeum,17 Xanthoxylum perrottetii ,18 Xanthoxylum pi-

peritum,19 Evodia meliifolia20 Orixa japonica 21 Yellow pig¬

ments resembling berberin and' believed to be identical with it

have also been isolated from several other plants.

Berberin crystallizes from water in yellow crystals with six

molecules of water of crystallization, from chloroform with one

molecule of chloroform of crystallization. It is easily soluble

in hot water, difficultly soluble in cold water or chloroform, and

almost insoluble in ether, benzene, ligroin, and acetic acid.

A large number of derivatives of berberin have been prepared.

It forms salts with acids similar to ammonium salts, also gold

and platinum double salts.

Berberin is used for dyeing leather, especially for gloves, also

silk and wool.

The following list includes the more important of the many

chemical investigations of berberin:

Ahrens, — B., 29, p. 2996.

Bernheimer, — Gazz. Chim. Ital., 13, p. 345.

Buchner and Herbeiger, — Ann., 24, p. 288.

Chevalier and Pelletan, — Jr. Chem. Med., 2, p. 314.

3 Pharm. Z. F. Hussl., 33, p. 770; Pharm. Jr. Trans., 3, p. 546.

4 Arch. Pharm., 222, p. 747.

5 Pharm. Jr. Trans., 3, p. 546 and 567.

6 New Commerc. Drug. 1887; Draendorff, Heilpflanzen, p. 227.

7 Monat. Scient., 5, p. 483.

8 Pharm. Centralh., 1882, nr. 28.

9 Arch. Pharm., 240, p. 146, 450.

10 Bull. Inst. Botan. Buitenzorg., 1902, 14, p. 11.

11 Ann., 105, p. 360.

12 Am. Jr. Ph., 1902; Botan. Centralbl., 45, p. 187.

13 Jr. Am. Chem. Soc., 24, p. 238.

14 Beitr. z. Kennt. d. Corydalis cava., Disser. Dorpat., 1890.

15 Arch. Pharm., 246, p. 461.

16 B. Neues. Repert. Pharm., 14, p. 211.

17 Jr. Chem. Soc., 15, p. 339.

18 C. r., 98, p. 999.

19 Dragendorff, Heilpflanzen, p. 350.

20 Chem. News., 71, p. 207; Arch. Pharm., 213, p. 337.

21 Nederl. Tijdschr. Pharm., 1884, p. 228.

Wakeman — Pigments of Flowering Plants.

831

Dobbie and Lander, — Proc. Chem. Soc., 17, p. 255.

Fleitmann, — Ann., 59, p. 160.

Freund, — Ann., 397, p. 1.

Freund and Beck, — B., 37, p. 4673.

Freund and Meyer, — B., 40, p. 2604.

Gadamer, — Chem. Ztg., 26, p. 291, 385; Arch. Pharm., 239, p.

648 ; 243, p. 12, 31, 43, 89, 246.

Gaze,- — Beilstein, Handb. organ. Chem., 3, p. 800.

Gordin, — Arch. Pharm., 39, p. 638; 240, p. 146.

Hlasiwetz and Gilm, — Ann., 115, p. 45 ; 122, p. 256; Suppl.

II. p. 133.

Henry, — Ann., 115, p. 133.

Link, — Arch. Pharm., 230, p. 734.

Mosse and Tauz, — Chem. Centralbl., 1901, II. p. 786.

Perkin, A. G., — Jr. Chem. Soc., 67, p. 413; 71, p. 1189.

Perkin, H. W.,— Jr. Chem. Soc., 55, p. 78; 57, p. 1037.

Perkin, W. H. and Robinson, — Jr. Chem. Soc., 97, p. 305.

Perrins, — Ann., Suppl. II. p. 176.

Schlotterbeck, — Jr. Am. Chem. Soc., 24, p. 238.

Schmidt, — Handb. Organ. Chem., 3, Aufl. 3, p. 798.

Troege and Linde, — Arch. Pharm., 238, p. 6.

Weidel, — B., 12, p. 410.

I. B. Pigments referable to diphenyl — 1 , 3 — propene series of

hydrocarbons.

Just as the larger number of natural coloring matters of the

degree of saturation Cn H2n_14, may be referred to diphenyl

methane, so by far the greater number of those of this degree

of saturation, the flavone derivatives, may be referred to a sim¬

ilar hydrocarbon, diphenyl propene. Indeed the relationship

of the flavone group to the xanthone group is much closer than

would be inferred by simply referring the individual compounds

to their underlying hydrocarbons. By comparing the struc¬

tural formula of xanthone with that of flavone it will be seen

that both compounds contain the y-pyrone group : more than

this, they contain the benzo y-pyrone group, designated by

Bloch and Kostanecki1. the chromone group. In the xanthone

derivatives the chromone group is condensed with another ben¬

zene nucleus forming dibenzo y-pyrone, while in the flavone

derivatives it is united with a phenyl group forming phenyl-

benzo-y-pyrone. With this similarity in' structure it is by

1 B., 33, 471.

Wisconsin Academy of Sciences , Arts, and Letters.

no means remarkable that flavone and xanthone derivatives so

closely resemble each other in coloring properties.

CH

O

CH- G— CH

CH

CH— C — CH

II

O

Y-pyrone

CH

Chromone

O

Xanthone

There is some confusion as to the numbering of the carbon

atoms in the benzo-y-pyron group, called by Kostaneeki the

chromon group, and consequently in the numbering of those of

the flavon and xanthon groups. According to Richter’s Lexi-

kon der KoMenstoff-Verbindungen the oxide oxygen in the

chromon group occupies position 1, and the carbon atoms are

numbered from this. Kostaneeki, however, assigns to the car¬

bon atom adjacent to the carbonyl group the a position and the

one adjacent to the oxide oxygen the (3 position, while the car¬

bon atoms of the carbocyclic nucleus he numbers 1, 2, 3, and 4

respectively. This gives us two systems of numbering as in¬

dicated by the following structural formulae :

Chromon group numbered according to

Richter Kostaneeki

Whichever of these methods of numbering is followed, the

positions of the carbon atoms of the phenyl group in the flavone

Wakeman— Pigments of Flowering Plants.

833

molecules are V , 2', -3', 4', 5', 6', beginning with the carbon atom

attached to the benzopyron group.

Flavon group numbered according to

O

Richter

O

Kostanecki

Though the chromon grouping occurs in the xanthon mole¬

cule, as has been shown above, this fact does not seem to be

recognized in the outline of cyclic systems as given in Kichter’s

Kohlenstoff-Verbindugen, for here an entirely different scheme

of numbering is employed for the xanthon grouping.

Xanthon group numbered according to

O

Richter

O

Kostanecki

While it might appear more rational than either of these sys¬

tems to begin with some differentiated carbon atom and number

each succeeding carbon atom in connection with which sub¬

stitution can take place 1, 2, 3, - ,8, 9, 10, etc., without re¬

sorting to other symbols yet Kostanecki ’s method undoubtedly

53— S. A. L.

834 Wisconsin Academy of Sciences, Arts, and Letters.

has its advantages since there are three different nuclei in

which substitution may take place.

In naming the derivatives of these compound nuclei a distinc¬

tion is sometimes made between hydroxy derivatives of the

carbocyclic nuclei and the heterocyclic nucleus. The former

are always regarded as flavones viz. hydroxy flavones, the

latter, sometimes as flavonols.

The Pigments referable to diphenyl — 1, 3 — propene may be

classified as follows:

1. The flavone derivatives (in the broader sense.)

a. ) Dihydroxides,

Chrysin.

Tectochrysin.

b. ) Trihydroxides.

Apiginin.

Acaeetin.

Galangin.

Galangin methyl ether.

c. ) Tetrahydroxides.

Luteolin.

Luteolin methyl ether.

Lotoflavin.

Fisetin.

Kaempherol.

Kaempherid.

d. ) Penthydroxides.

Quercetin.

Rhamnetin.

Isorhamnetin.

Rhamnazin.

Morin.

e. ) Hexhydroxides.

Myricetin.

Gossypetin.

2. Butein.

3. Anthocyanin pigments.

a. ) Tetrahydroxides.

Pelargonidin.

Wakeman — Pigments of Flowering Plants.

835

b. ) Penthydroxides.

Cyanidin.

Paeonidin.

c. ) Hexhydroxides.

Delphinidin.

Myrtillidin.

Mai vi din.

Oenidin.

•Classified with reference to the position of one of the hydroxy

groups, i. e. as to whether or not it is in a position thus pro¬

ducing a flavonol group, the flavone pigments, as already pointed

out, fall into two classes.

1. The true flavones.

2. The flavonols.

This classification appears desirable inasmuch as Willstaetter

looks upon the anthocyanin pigments as related to the flavonols

but not to the true flavones.

True Flavones Flavonols

Tetrahydroxides of Chalkon

Dihydroxy flavones

Chrysin

Tectochrysin

Penthydroxides of Chalkon

Trihydroxy flavones

Apiginin

Acacetin

Dihydroxy-flavonols

Galangin

Galangin methyl ether

Hexhydroxides of Chalkon

Tetrahydroxy-flavones

Trihydroxy -flavonols

Luteolin

Fisetin

Kaempherol

Kaempherid

Luteolin methyl ether

Lotoflavin

836 Wisconsin Academy of Sciences , Arts, and Letters.

Hepthydroxides of Chalkon

Tetrahydroxy-flavonols

Quercetin

Rhamnetin

Isorhamnetin

Rhamnazin

Morin

Octhydroxides of Chalkon

Penthydroxy-flavanols

Myricetin

I. B. 1.) The Flavone Pigments.

The flavone group constitutes the largest known group of

plant coloring matters. All of its members are di-, tri-, tetra-,

pent-, and hexhydroxy substitution products of flavone or

methyl ethers of these substitution products. Flavone itself

is a dehydration product of a hydroxy derivative of diphenyl -1,

3-propene-l-one 3, (chalkone)1 a compound which is yellow in

color and the hydroxy derivatives of which (also yellow in color)

have been used for the synthesis of practically of all of the mem¬

bers of this group.

The flavone derivatives are all, as the name indicates, yellow

in color. The intensity of the coloration appears to depend

somewhat upon both the number and the position of the OH

groups and varies from the pale yellow, or almost colorless,

apigenin and acacetin to the deep orange yellow myricetin — a

hexhydroxy flavone.

The pigments belonging to this group are found in nearly all

parts of the plant and both in the free condition and as glu-

cosides. Chrysin, galangin, luteolin and kaempherid are re¬

ported as occuring only in the free state ; quercetin, fisetin and

kaempherol both as such and as glucosides, quercetin being

found as the glucosides quercitrin, robinin, rutin, myticolorin,

osyritrin. While luteolin is reported only in the free state, its

(3) methyl ether occurs as glucoside in the leaves of parsley.

All the other members of this group of coloring matters are re¬

ported as occurring potentially in the plant as glucosides,

1 So called by Kostanecki to whose syntheses of the flavone coloring matters

we are indebted for much of our knowledge of the structure of these com¬

pounds.

Wakeman — Pigments of Flowering Plants. 837

While the flavone pigments are found in all parts of the plant

they occur most frequently in the roots, wood, bark and leaves.

When they appear to be the pigment to which the flower owes

its color, the blossoms are either pale yellow or almost white.

In some instances, as the occurrence of kaempherol in the blue

flowers of Delphinium consolida and Delphinium zali it is plainly

evident that the color is not due to the presence of the flavone

derivative but to some other pigment or pigments.

Willstaetter in his work upon anthocyanin has shown that in

the Delphiniums the color is due to delphinidin, probably a po¬

tassium salt of delphinidin. Delphinidin, according to Will¬

staetter, is isomeric with quercetin and morin, both of which

are hydroxy substitution products of kaempherol.

The flavone derivatives are not quinoid in character. All

can be, however, theoretically, and some have been, actually,

oxidized to quinoidal compounds (See Chrysin2. and quercetin3.).

These quinones are deep red in color and closely resemble, in

their behavior toward reagents, the red and blue pigments of

flowers (anthocyanins). These quinones can be reduced to the

corresponding hydroquinones which form either colorless or pale

yellow crystals.

From a consideration of the above reactions, also as a result

of observations upon the distribution of anthocyanin, and from

experimental evidence on the concentration of sugars and glu-

cosides in various tissues, on the existence of enzymes, and on

sugar feeding, there has recently been formulated a hypotheses

(Miss Muriel Wheldale4) that: The soluble pigments in flower¬

ing plants, termed anthocyanin, are oxidation products of

colorless chromogens, existing in the tissues as .glucosides. The

production of the glucoside from the ehomogen and sugar is in

the nature of a reversible enzyme reaction : chromogen + Sugar

= glucoside + water, and the oxidation of the chromogen, which

is effected by one or more enzymes, can take place only after its

liberation from the glucoside.

According to Miss Wheldale this hypothesis brings the forma¬

tion of anthocyanine into line with that of pigments formed

after the death of the plant (indigotin etc.) It is not opposed

to the quinhydrone hypothesis of pigmentation and it is in ac-

2 Ber., 45, 499.

3 Ber., 44, 3,487.

4 Jr. Genetics, 1, 133, (Jr. Chem. Soc., A. II, 80).

838 Wisconsin Academy of Sciences, Arts, and Letters.

cord with the observations of Kastle5. and Hayden on the bine

coloring matter of chicory blossoms. It is not in harmony,

however, with the recent work of Willstaetter upon anthocyanins.

According to Willstaetter it ought to be possible to produce

anthocyanins by the reduction (not oxidation) of quercetin or

other flavonols. Such an anthocyanin would be, not the querce-

tone or similar quinone of Niernstein and Wheldale, but an

oxonium compound of a reduced quercetin or other flavonol.

Dihydroxy flavones

Chrysin , — Dihydroxy-1, 3-Flavone.

CH CH CH CH

Diphenyl*!, 3-propene

Chrysin was probably first isolated by Hallwachs* 1 in 1857

from the buds of Populus nigra or Populus dilatata. In 1864

Piccard2 extracted chrysin from several varieties of poplar

where he found it in the growing leaf buds. He named it

6i chrisinsaeure' ’ to indicate both its yellow color and its salt

forming properties. Several years later Piccard3 undertook

5 Am. Chem. Jr., 46, 315.

1 Ann., 101, p. 872.

2 Jr. f. Prakt. Chem., 93, p. 369.

3Ber., 6, p. 884; 7, p. 888; 10, p. 176.

Wakeman — Pigments of Flowering Plants.

839

a study of chrysin. In a series of articles he described its

principal properties and attacked the problem of its constitu¬

tion. This was determined later by Kostanecki4 and his as¬

sociates. (1893-1904) The work of Kostanecki was confirmed

by that of Darier5 in 1895.

Our present conception of the constitution of chrysin is based

upon its decomposition by caustic alkalies into phloroglucin,

acetic acid and benzoic acid, with small quantities of aceto¬

phenone. Also upon its synthesis from phloracetophenone

trimethyl ether and ethyl benzoate.

Chrysin occurs in the buds of many species of poplar, including

Populus pyramidalis ,6 7 Populus nigra,1 Populus monolifera8 and

Populus balsamifera.9

Chrysin forms clear yellow crystals. It melts at 275 and

sublimes in fine needles at a temperature a little above the melt¬

ing point. It is insoluble in water but soluble in both hot and

cold alcohol, in aniline and acetic acid. It is difficultly soluble

in ether and almost insoluble in carbon disulphide. In alka¬

line solutions it dissolves with a yellow color. Chrysin is pre¬

cipitated from alcoholic solutions by lead acetate but dissolves

in an excess of the reagent.

Treated with chromic acid and acetic acid chrysin is oxidized

to chrysone,10 a red amorphous powder which crystallizes in deep

red needles melting above 360. Chrysone is insoluble in the

ordinary organic solvents. It dissolves in concentrated sulph¬

uric acid with a red color, in alkalies with a blue color. It

forms a monoacetyl derivative which crystallizes in red needles.

The acetyl derivative when reduced with zinc and acetic acid an¬

hydride forms a white acetylated hydroxychrysin which, when

hydrolized, crystallizes in small crystals melting at 304-305.

Tectochrysin , a methyl ether of chrysin.

Tectochrysin11 was first obtained by Piccard in the purifica¬

tion of chrysin. He called it tectochrysin from a Greek word

4 Ber., 26, p. 2901; 32, p. 2260, 2449; 37, p. 3167.

6 Ber., 27, p. 21.

6 Ber., 6, p. 884.

7 Ann., 101, p. 372.

8 Ber., 6, 890; 7, p. 1485.

9 Ber., 16, p. 176.

10 Ber., 45, p. 499.

11 Ber., 6, p. 888.

340 Wisconsin Academy of Sciences , Arts, and Letters.

which means fusible, because its melting point is much lower

than that of ehrysin. Tectochrysin may be prepared synthe¬

tically by treating ehrysin in alcoholic solution with methyl

iodide. It is more readily soluble than ehrysin, being easily

soluble in benzine (distinction from ehrysin.) Tectochrysin is

sulphur yellow in color.

Trihydroxy fiavones

Apigenin, — Trihydroxy — 1, 3, 4' — flavone.

The glucoside apiin, of which apiginin is a component, seems

to have been first isolated by Rump1 in the course of his work

on the chemical analysis of Apium petroselinum, but it was not

until 1843 that Braconnot2 first hydrolised this glucoside.

Braconnot also applied the name apiin to the glucoside but

made no analysis of the products of hydrolysis. In 1850 Planta

and Williams3 analysed apigenin and described it under the

name of pure apiin. In 1867, Lindenhorn4 showed the glu-

cosidal character of apiin, and that by hydrolysis it gave glucose

and a new substance to which he gave the name apigenin.

Gerichten,5 in 1876, took up the study of the constitution of

apigenin, basing his conclusions upon its decomposition in the

presence of alkalies. He ascribed to apigenin the formula

C15H10O5, a formula which has since been verified by the work

of Perkin,6 and more recently by that of Kostanecki and -

Tambor.7

Apigenin occurs as the glucoside apiin in Petroselinum

1 Rep. f. Fharm., 6, p. 6.

2 Ann. d. Phys. et Chim., 9, p. 250.

8 Ber., 9, p. 112.

4 Innaug. Dissert. Wuerzburg, 1867.

c Ber., 9, p. 259, 1121, 1477.

6 Jr. Chem. Soc., 71, p. 807; 77, p. 420.

7 Ber., 33, p. 1990.

Wakeman— Pigments of Flowering Plants. 841

sativum, Apium graveolens , and perhaps in other species of urn-

bellifera.

Apigenin forms crystals of a pale yellow color which melt

at 212-215. It is difficultly soluble in water and in ether, more

readily in alcohol. Alkalies dissolve it with a yellow color. In

alcoholic solution it yields with lead acetate a yellow precipi¬

tate, with ferric chloride a red brown coloration.

Acacetin, a monomethyl ether of apigenin was named by

Perkin1 who first obtained it from the leaves of Robina pseud-

acacia.

Acacetin occurs in the leaves of the false acacia, Robina pseud-

acacia. It forms almost colorless needle like crystals which

dissolve in alkaline solutions with a pale yellow color. From

alcoholic solutions it is precipitated by lead acetate. With

ferric chloride it gives a reddish brown color. It forms a

diacetyl derivative which crystallizes in colorless needles which

melt at 195-198. Fused with alkalies, acacetin yields phloro-

glucin and parahydroxybenzoic acid.

Galangin, — Trihydroxy — 1, 3, — flavone or

Dihydroxy-— 1, 3—flavonol.

Galangin was first obtained by Brandes,1 in 1839, together

with kaempferid, from Galanga root, Alpinia officinarum. It

was not, however, recognized by him as a distinct compound,

and it was not until Jahns,2 in 1881 showed that the kaempferid

of Brandes was composed of a mixture of three substances which

he called kaempferid, galangin, and alpinin, that galangin was

actually isolated. In a later study (1900) of the colored com¬

pounds of Galanga root, Testoni3 met with nothing correspond-

1 Proc. Chem. Soc., 16, p. 45; Jr. Chem. Soc., 77, p. 430.

1 Arch, der Pharm., (2) 19, p. 52.

2 Ber., 14, p. 2305 ; 2807 ; Arch, der Pharm., 220, p. 161.

3 Gazz. chim. ital., 30, (2) p. 327.

842 Wisconsin Academy of Sciences , Arts, and Letters.

ing to the alpinin of Jahns, but found a methyl ether of galangin.

Jahns in his study of the constitution of galangin found its

formula to be C15H10O5, also that it has three hydroxy groups,

and that upon fusion with potassium hydroxide it yields

benzoic acid, oxalic acid and a phenol like substance. Kostanecki4

and his associates by the hydrolysis, and subsequent synthesis of

galangin, established its formula as given above.

Galangin crystallizes in yellowish white needles which melt

at 214-215, and sublime with partial decomposition. It is al¬

most insoluble in water, easily in ether, slightly in chloroform

and benzene. It dissolves in alkalies with a yellow color. It

yields a triacetyl and a tri methyl derivative, the latter, treated

with acetic acid, yields a monoacetyl compound.5 6 7

Galangin methyl ether.

— o —

— C —

it

o

A galangin methyl ether, probably with the methyl group in

the position indicated above, 6 occurs along with galangin in the

root of Alpinia officinarum.7

Tetrahydroxy flavones.

Luteoline , — Tetra hydroxy — 1, 3, 3', 4' — flavone.

C- —

1

CH

I)

O

Luteoline was first isolated by Chevreul,1 in 1830, and named by

him from its source, 1 Reseda luteola. Since that time it has been

4 Ber., 37, p. 2803.

5 Ber., 14, p. 2807.

6Czapek, Biochemie der Pflanzen, vol. 2, p. 523.

7 Gazz. chim. ital., 30 (2) p. 327.

xJr. Chim. Med. 6, p. 157.

Wakeman — Pigments of Flowering Plants. 843

studied by a number of chemists, Moldenhauer,2 Schuetzen-

berger3 and Paraf, Halsiwetz4 and Pfaundler, Roechleder,5

Adrian6 and Trillot, Herzig,7 Perkin,8 and Kostanecki.9

Our present conception of the constitution of luteoline,

like that of the other members of the flavone group, is based

upon its decomposition by alkaline fusion when it yields phoro-

glucine and protocatechuic acid. Perkin, therefore ascribed to

luteoline the foregoing formula which has since been verified

by the synthesis, effected by Kostanecki10 and his associates,

of luteolin from phloracetophenone trimethyl ether and the

diethyl ether of dihydroxy — 3, 4 — benzoic acid.

Luteoline occurs, as such, in Reseda 11 luteola in the leaves of

Digitalis12 purpurea , and in Genista 13 tinctoria. The 3-methyl

ether of luteoline occurs as a glucoside in the leaves of parsley,

Petroselium sativum.

Luteoline forms small quadrangular needles of a yellow color

and bitter, astringent taste. They melt at 350° and sublime

with partial decomposition. They are slightly soluble in cold

water, better in warm water, alcohol, ether, and warm acetic

acid.

Dry luteoline treated with phosphoric acid anhydride is

changed to a red substance which dissolves in ammonia with

a violet coloration. The aqueous solution of luteoline is colored

first green, then reddish brown by ferric chloride, olive green

by copper acetate. Luteoline dissolves in concentrated sul¬

phuric acid with an orange red color and is precipitated un¬

changed by dilution. If to a saturated solution of luteolin in

boiling acetic acid sulphuric acid is added, small orange red

crystals, insoluble in acetic acid and decomposed by water into

luteoline and sulphuric acid, are formed. Hydrobromides are

formed in a similar manner with hydrobromide acid.

3 Jr. Prakt. Chem., 70, p. 428.

3 Bull. Soc. Chim., (1) p. 1861-18.

4 Ann., 112, p. 107.

5Zeit. Anal. Chem. (1886) p. 602.

6C. r., 129, p. 889.

7 Ber., 29, 1013; Monats., 17, p. 926.

8 Jr. Chem. Soc., 69, p. 206, p. 1439.

8 Ber., 32, p. 1184; 3j4, 1453; 37, 2625.

10 Ber., 33, p. 3415.

11 Ann., 100, p. 150‘; Jares., (1861) p. 707.

13 Arch. Pharm., 383, p. 313; B., 32, p. 1184.

13 Euler (1), p. 105.

844 Wisconsin Academy of Sciences, Arts, and Letters.

Luteolin — methyl — ether is found as a glucoside in the green

herb of parsley.

Loto flavin, — Tetrahydroxy—~l , 3, 2' , 4' — flavone.

CH

CH COH

Lotoflavin was first met with in 1900 by Dunstan1 in Lotus

arabicus, a small leguminous plant growing abundantly in

Egypt. This plant, which very closely resembles the com¬

mon vetch, is commonly known as kuther. From the fact that

fused with alkalies it yields /3-resorcylic acid and phloroglucin,

Dunstan and Henry2 conclude that the structure of lotoflavin is

as above.

Lotoflavin occurs in the Lotus arabicus in the form of a gluco¬

side, lotosin, which by the action of dilute acids, or of a special

enzyme, lotase, is hydrolised yielding lotoflavin, sucrose, and hy¬

drocyanic acid.

Lotoflavin is a yellow crystalline substance readily soluble in

alcohol or hot glacial acetic acid. It dissolves also in alkalies

with a bright yellow color. It does not combine with mineral

acids, but it forms a triacetyl derivative and two isomeric tri¬

methyl ethers. By the action of fused alkalies it is converted

into phloroglucin and resorcylic acid.

Fisetin, — Tetrahydroxy a — 3r, 4f, a — flavone, or

Trihydroxy — 3, 3' , 4' flavonol.

1 Proc. Roy. Soc., 67, p. 22-f; 68, p. 374.

2 Chem. News., 8, p. 301; 84, p. 26.

Wakeman — Pigments of Flowering Plants.

845

Chevruel1 probably first extracted fisetin in the form of a tan¬

nin; though perhaps impure, from the fustel wood. Some

years later it was again obtained from the same source by

Bolley.2 It was later isolated and studied by Schmidt,3 Her-

zig,4 Perkin,5 and Kostanecki.6

Our ideas of the constitution of fisetin are based upon the

work of Hirzig who showed that by boiling with alcoholic po¬

tassium hydroxide fisetin did not yield phloroglucin, but fisetol

and protocatechuic acid, with traces of resorcin. By the syn¬

thesis of fisetol (ethylresorcylic acid), Kostanecki and Tambor

confirmed the work of Herzig.

coc2h.

c

coo H

Fisetol.

Fisetin occurs as a glucoside in Rhus cotinus ,7 Rhus rhodan-

thema8 and Querbracho Colorado .9 It also occurs free in Rhus

rhodanthema,10 and in the blossoms of Butea frondosa.11

Crystallized from dilute alcohol fisetin forms small lemon

yellow needle like crystals. From acetic acid it crystallizes in

yellow prisms with six molecules of water of crystallization.

Fisetin is almost insoluble in water, easily soluble in alcohol,

acetone and acetic acid. It is difficultly soluble in ether, ben¬

zene, petroleum ether and chloroform. Ferric chloride when

added to fisetin solutions produces a dark green coloration and

1 Zeit. anal. Chem., 12, p. 127.

3 Bull. Soc. Chim., 2, p. 479.

8 Ber., 19, p. 1734.

4 Monatsh., 12, p. 177.

5 Jr. Chem. Soc., 67, p. 648; 69, p. 1304.

6 Ber., 28, p. 2302; 37, p. 784; 38, p. 3587.

1 Ber., 19, p. 1703.

8Jr. Chem. Soc., 71, p. 1194.

9 Chem. News, 74, p. 120.

10 Jr. Chem. Soc., 71, p. 1194.

11 Proc. Chem. Soc., 19, p. 183; Jr. Chem. Soc., 85, p. 1459.

846 Wisconsin Academy of Sciences, Arts, and Letters.

upon the addition of ammonia, a black precipitate. Lead

acetate added to fisetin solutions forms an orange yellow preci¬

pitate which is easily soluble in acetic acid.

Fisetin forms tetramcthyl, tetraethyl, tetrabenzoyl, and tetra-

acetyl derivatives. By fusion with alkalies it yields phloro-

glucin, resorcinol, and protocatechuic acid. Treated with

chromic acid12 it does not yield an oxidation product corres¬

ponding to those produced from chrysin and quercetin under the

same condition. To fabrics mordanted with aluminum fisetin

imparts an orange color, with tin a bright red or yellow red color,

with chromium a brown color.

Kaempherol, — Tetrahydroxy a — 1, 3, 4, — flavone , or —

Trihydroxy— 1, 3, 4r—flavonol.

Kaempherol was probably first extracted by Zwenger* 1 and

Dronk, in 1861, as the glucoside robinin from Robinia pseud-

acacia. It was considered by them, however, to be a glucoside

of quercetin. It was first prepared from kaempherid, its

3-methyl ether, in 1897 by Gordin2 3 who treated the crystal¬

line kaempherid with strong hydriodic acid solution thus se¬

curing the free kaempherol. It was later isolated by Perkin

(1900) from the flowers of Delphinium consolida 3 and by him

identified. Perkin also isolated the glucoside robinin from the

flowers of Robinia pseudacacia .4 The constitutional formula of

kaempherol follows from its preparation from kaempherid, and

from its synthesis, along with that of kaempherid, by Kostanecki

and others.

Kaempherol occurs both as such and combined as the gluco-

12 Ber., 45, p. 499.

1 Ann., Sup. 1, (1861) p. 257.

2 Ber., 34, p. 3723.

3 Jr. Chem. Soc., 81, p. 585.

4Proc. Chem. Soc., 17, p. 87.

Wakeman — Pigments of Flowering Plants.

847

side in the blue flowers of Delphinium consolida 5 and Delphin¬

ium zali,Q as the glucoside in the white flowers of Rohinia pseud-

acacia,7 and, along with quercetin in the blossoms of prunus

spinosa ,8 Alpina officinarum ,9 and Rumex eckonianus.10 It has

also been isolated from the indigo producing plants,11 Poly¬

gonum tinctorium and Indigofera amicta, as the glucoside

kaempheritrin. Scutellarein,12 probably identical with kaem-

pherol, is formed by the hydrolysis of the glucoside scutellarin

which occurs in the epidermis of Scutellaria caleopsis , and

Teucrium species.

Kaempherol crystallizes in pale yellow crystals which melt

at 276-277. It is readily soluble in boiling alcohol, and

soluble in alkalies with a pale yellow color. Alcoholic lead

acetate solutions yield an orange red precipitate with kaemph¬

erol; alcoholic ferric chloride a greenish black coloration.

Kaempherol dissolves in concentrated sulphuric acid forming

a yellow solution which in a short time gives a blue fluorescence.

To wools mordanted with aluminum kaempherol imparts a yellow

color; with tin, a yellow color; with chromium, a brownish red

color; and with iron, a deep olive brown.

Kampherid,— Trihydroxy— 1, 3, a-methoxy-4'-flavone, or

Dihydroxy-1, 3-methoxy-4 ' -flavonol.

Kampherid, the 4' -methyl ether of kaempferol, was first ex¬

tracted by Brandes1 in 1839 from the rhizom of Alpina offici¬

narum. Later, as has been shown in the chapter on galangin,

5 Jr. Chem. Soc., 81, p. 585. -

6 Jr. Chem. Soc., 73, p. 267.

7 Proc. Chem. Soc., 20, p. 172.

8 Ann. (Sup.) 1, p. 257.

9 Arch. d. Pharm., 247, p. 447.

10 Jr. Chem. Soc., 97, p„ 1.

11 Jahresb. d. Chem., (1886) p. 573; Proc. Chem. Soc. 20, p. 172; 22, p. 198.

12 :Euler, p. 105.

1 Arch, der Pharm., 67, p. 52.

848 Wisconsin Academy of Sciences, Arts, and Letters.

this kaempferid of Brandes was found by Jahns2 to be a mix¬

ture of three substances which he called kaempferid, galangin,

and alpinin. Our ideas of the constitution of kaempferid, and

also of kaempferol, are based upon its behavior with oxidizing

substances and alkalies. By the action of oxidizing agents it

yields para hydroxy benzoic acid and oxalic acid, fused with

alkalies, oxalic acid, formic acid, and phloroglucine.

This conception of the formula of kaempferid and kaemp¬

ferol is supported by the work of Kostanecki3 and his associates,

also by that of Gordin,4 and of Cimician and Silber,5 and it is

confirmed by its synthesis by Kostanecki, Lampe and Tambor.6 7

In this synthesis hydroxy-2 '-trimethoxy-4', 6', 4-chalkon,8

synthesized from phloracetophenone-dimethyl ether and anise

aldehyde, treated in alcoholic solution with dilute sulphuric

acid, yielded trimethoxy-1, 3, 4'-flavonon, which in turn gave

the trimethoxy-1, 3, 4'-flavonol, and that gave the trihydroxy —

1, 3, 4— flavonol.

Kaempherid occurs, as has been already pointed out, in the

rhizom of Alpina officinarum.

Kaempferid crystallizes in yellow plates which melt at 224r-

225. It is insoluble in water, slightly soluble in cold alcohol,

chloroform and benzene, readily soluble in hot alcohol, ether,

and sulphuric acid. It dissolves with an intense yellow color

in solutions of the alkalies and the alkaline carbonates. In con¬

centrated sulphuric acid it dissolves with a yellow color and a

blue fluorescence. The alcoholic solution gives an olive green

precipitate with ferric chloride, and a yellow precipitate with

lead acetate. It reduces Fehling’s solution when warmed.

* Ber., 14, p. 2305, 2807; Gazz. chim ital., 30 (11) p. 327.

8 Ber., 32, p. 318; 34, 3723; 28, p. 2302.

4 Ber., 34, p. 3723; Dissertation, Berne, 1897.

6 Ber., 32, p. 861.

6 Ber., 37, p. 2096.

7 Ber., 37, p. 192.

Wakeman- . Pigments of Flowering Plants.

849

P entity dr oxides of flavone.

Quercetin f — P entity dr oxy — 1 , 2y 3', 4 a-j flavone y or

Tetrahydroxy-—!, 2 , 3' , 4’ -flavonol.

Quercetin which occurs very widely distributed throughout

the plant kingdom, both in the free state and as a glucoside, has

probably been more widely studied than any other vegetable

coloring matter except chlorophyll and, perhaps indigo and

alizarin. Quercetin was first extracted as a glucoside querei-

trin by Chevreul1 from the inner bark of Quercus tinctoria and

later from the same source, also from the horse chestnut, by

Rochleder.2 The free quercetin was first obtained from the

glucoside by Rigaud,3 in 1854. The names of the various

chemists who have since contributed to the literature of querce¬

tin, with references to their published works are given in the ap¬

pended list, which, although it contains the more important ar¬

ticles upon quercetin, is probably not at all complete.

Our conception of the structure of quercetin comes from the

work of Hirzig,4 also that of Kostanecki5 and his associates.

Fused with alkalies it yields phloroglucin, Protocatehuic acid,

and glycolic acid.

C15H10O7 + 3H20 =C6H3 (OH), + C6H3 (OH)2 COOH+ CH2

OH COOH.

Quercetin has been synthesized by Kostanecki and his colla¬

borators in a manner quite similar to their synthesis of fisetin.6

Quercetin occurs very widely distributed in the free state, as

alkyl ethers, and as glucosides. As a glucoside it is most

1 Logons de Chemie appliquee £ la Teinture.

a Wien. Acad. Ber., 33, p. 565.

* Ann., 90, p. 283.

* Monatsh., 12, p'. 177; 14, p. 38.

‘Ber., 37, p. 784, 793.

•Ber., 37, p. 784, 793.

54— S. A. L.

850 Wisconsin Academy of Sciences , Arts , and Letters.

frequently met with combined with rhamnose though it often

combines with other sugars, sometimes forming mixed gluco-

sides with one or more molecules of rhamnose and one or more

of another sugar, glucose or galactose.

As a glucoside quercetin is found in the bark of Quercus tine -

toria, Q. digitata, or Q. trifida 1 in the bark of Cary a tomentoria,8

in grape leaves,9 Viola tricolor,™ leaves of Eucalyptus macror-

rhyncha,11 leaves of Ruta graveolens,12 buds of Sophora japon-

ica,13 leaves of Colpoon compressum ,14 Arctostaphylos uva ursa ,15

in North American Chimaphila species,16 in Calluna vulgaris,11

in the blossoms of Tagetes patula,18 in horse chestnut,19 in the

leaves and blossoms of Cherianthus cheri20 and of Crataegus

oxycanthus 21 in the blossoms of Viola tricolor var. evensis 22

and in the blossoms of the cotton plant.23

In its free state quercetin has been found by Perkin23 in Rham-

nus (fruit), Hippophae (berries), Rhus cotinus (bark), Apple

(bark), Prunus spinosa (blossoms), Aesculus (leaves and flow¬

ers), Cornus (flowers), Grape (leaves), Allium cepa, Podophyl¬

lum , and the fruit of Rumex obtusifolia 21 It has been found

by Horst25 in Polygonum persecaria, by Weiss26 in Trifolium

repens, Acacia, Gambir catechu, flowers of Crataegus, and leaves

of Myrtus checken; by Loewe27 in Catechu ; by Hummel28 in the

leaves of Cherianthus cheri; by Pilgrim29 in the coloring mat¬

ter of Delphinium zali; and by Perkin and Wood30 in the leaves

7 Ann., 37, p. 101; Monatsh, 5, p. 72.

8 Am. Jr. Pharm., 51, p. 118.

0 C. Neubaur, Versuchrt, 16, p. 427.

10 Jr. Chem. Soc., 71, p. 1131.

“Jr. Chem. Soc., 73, p. 697.

12 Ann., 82, p. 197; Apoth. Zeit., (1901 p. 351.

13 Jr. Chem. Soc., 67, p. 30.

“Jr. Chem. Soc., 71, p. 1131.

15Proc. Chem. Soc., 16, p. 295.

18 Am. Jr. Fharm., 64, p. 295.

17 Froc. Chem. Soc., 15, p. 179.

18 Bull. Soc. Chim., 28, p. 337.

19 Wien. Acad. Ber., 33, p. 565.

20 Jr. Chem. Soc., 69, p 1295.

21 Jr. Chem. Soc., 81, p. 477.

23 Jr. Chem. Soc., 95, p. 2181.

23 Proc. Chem. Soc., 19, p. 284 ; Jr. Chem. Soc., 49, p. 1295, 1556.

24 Jr. Chem. Soc., 71, p. 1194.

25 Chem. Ztg., 25, p. 2055.

28 Arch. Pharm., (3) 26, p. 665.

27 Zeit. f. Anal. Chem., 12, p. 127.

28 Jr. Chem. Soc., 69, p. 1568.

29 Jr. Chem. Soc., 73, p. 273.

39 Jr. Chem. Soc., 73, p. 381.

Wakeman — Pigments of Flowering Plants. 851

of Ailanthus glandulosa, also in the leaves of Rhus rhodaw-

thema31

Pure quercetin presents the appearance of a lemon yellow

crystalline powder made up of tiny needle like crystals. It is

almost insoluble in cold water, soluble in alcohol, very difficultly

soluble in ether, and easily soluble in dilute alkalies. It crystal¬

lizes with three molecules of water of crystallization which it

loses at 130°. In alcoholic solution it gives a dark green coloration

with ferric chloride which turns black upon heating. With

lead acetate it gives a red precipitate. It reduces silver solu¬

tions when cold and Fehling’s solution when heated. Quercetin

melts at 250°. When treated with chromic acid and acetic acid

it is oxidized to quercetone.

To fabrics mordanted with aluminum quercetin imparts a

brownish yellow color; with chromium, a deep orange color;

with iron, a dark olive ; and with tin, a bright orange yellow.

Quercetone .

Quercetone,32 the oxidation product of quercetin, crystallizes

in small deep red needle like crystals which melt above 360°.

It dissolves in alkalies with a blue, and in concentrated sul¬

phuric acid with a red coloration. When heated with acetic

acid and zinc dust acetylated hydroxy quercetin is obtained as

a colorless, amorphous powder which yields upon hydrolysis

penthydroxy-1, 3, 4, 3', 4,-flavonol. This crystallizes in small

yellow needles which lose a molecule of water at 160°, and melt

at 352°-355°. Both alkaline hydroxides and sulphuric acid

dissolve it with a yellow color. Pentmethoxy flavonol forms,

small colorless crystals which melt at 147°-149°.

31 Jr. Chem. Soc., 73, p. 1017.

32 Ber., 44, p. 3487.

852 Wisconsin Academy of Sciences, Arts, and Letters.

Literature on Quercetin.

Bartolloti, — Gazz. chim. ital., 24, II. p. 480.

Bolley, — Ann., 37, p. 101 ; 125, p. 54.

Bolley and Mylinns, — Schweitzerische Poly. Ziet., 9, p. 22.

Bolley, —-Jahresber d. Chem., 1861, p. 709.

Chevreul, — Lecons de Chem, app. a la Teinture.

Dnnstan and Henry, — Jr. Chem. Soc., 73, p. 219.

Foerster, — Ber., 15, p. 214.

Gintl, — Jahresber. d. Chem., 1868, p. 801.

Herzig, — C. r., 5, p. 72 ; 6, p. 863 ; 9, p. 537 ; 548 ; 10, p. 561 ; 12,

p. 172; 14, p. 39, 53; 15, p. 683; 16, p. 312; 17, p. 421; 18,

p. 700.

Herzig, — Monatsh., 6, p. 863 ; 9, p. 541 ; 15, p. 696.

Hlasiwetz, — C. r., 29, p. 10.

Hiasiwetz, — Ann., p. 102.

Hlasiwetz, — Jahresber. d. Chem., 1864, p. 564; 1867, p. 732.

Kostanecki, — Ber., 37, p. 793, 1402.

Liebermann, — C. r., 16, p. 180.

Liebermann and Hamburger, — B., 12, p. 1179.

Liebermann and Hoerman, — Ann., 196, p. 299, 338.

Loewe, — Zeit. f. analyt. Chem., 12, p. 127, 233.

Lushing, — Dingier ’s Poly. Jr., 139, p. 1319.

Mandeline, — Pharm. Ztg. f. Russ., 22, p. 329.

Niernstein and Wheldale, — - B., 44, p. 3487.

Perkin, — Jr Chem. Soc., 67, p. 644 ; 69, p. 1295 ; 71, p. 1131,

1135, 1191; 73, p. 2-1, 237, 381, 1017, 1135; 74, p. 278;

75, p. 837 ; 77, p. 426 ; 81, p. 477 ; 85, p. 56 ; 95, p. 1855, 2181.

Rigaud, — Ann., 90, p. 283.

Roechleder, — C. r., 33, p. 365.

Roechleder, — Jahresber. d. Chem., 1859, p. 523; 1866, p. 654;

1867, p. 731.

Rudolph, — Pharm. Post., 26, p. 529.

Schuetzenberger and Paraf, — - Zeit. f. Chem., 1826, p. 41.

Schunck, — Chem. Gazette., 399, p. 20.

Stein, — Zeit. f . prakt. Chem., 1863, p. 467.

Stein, — Jr. f. prakt. Chem., 58, 399; 85, p. 351; 88, p. 280; 89,

p. 491.

Wagner, — Chem. Centrlbl., 1873, p. 586.

Zwenge^ and Dronke, — Ann., (Suppl. I.) p. 257.

Wakeman — Pigments of Flowering Plants.

853

Rhamnetin, — Quercetin-3 -monomethyl ether , or

Trihydroxy-1, 3' , 4' -methoxy -3-flavonol.

CHsOC

CH

C — O — C - C

II

c- C — COH

:oh

HC

CH CH

M

o

COH

Rhametin was known as early as 1841 in the form of gluco-

side then called rhamnin1 but now known as xanthorhamnin.

It was hydrolized in 1858 by Gellatly,2 and the sugar was identi¬

fied as rhamnose by Berend3 in 1878. Later Tanret4 found

that xanthorhamnin was a mixed glucoside containing two mole¬

cules of rhamnose and one of galactose. The constitution5 of

rhamnetin and other methyl ethers of quercetin has been the

subject of considerable chemical study, the question under con¬

sideration being the position of the methoxy groups. Perkin,6

in 1902 showed that by careful decomposition with alkalies the

monomethyl ether of phloroglucin is obtained and that the

methoxy group must therefore be in that part of the molecule

from which the phloroglucinol is obtained. The formula for

rhamnetin according to Perkin is given above.

According to Czapek, rhamnetin occurs as the glucoside in the

fruit and in the bark of several species of Rhamnus. Kane,7

Gellatly,8 Schuetzenberger,9 and Liebermann10 find it in the

“Gelbeern” or * ‘ Avignonkoerner, ’ ’ the fruit of Rhamnus in-

fectoria and R. tinctoria.

Rhamnetin crystallizes best from phenol, in which it is easily

soluble when heated. It separates on cooling in small bright

lemon yellow crystals. It is sparingly soluble in warm water

and very slightly soluble in the ordinary organic solvents. It

1 Jr. Chem. Soc., 27, p. 666.

2 Chem. Centrlbl., 29, p. 477.

8 Ber., 9, p. 1353.

4 C. r., 129, p. 725; Bull. Soc. Chim., (3) 21, p. 1073.

6 Monats., 4, p. 889; 9, p. 548; 10, p. 561.

* Jr. Chem. Soc., 81. p. 569.

7 Berz. Jahresb. 24, 505.

8Jahresb., 1838, p. 474.

"Jahresb., 1868. p. 774.

10 Ann.. 196. p. 313.

854 Wisconsin Academy of Sciences, Arts, and Letters .

dissolves readily in alkalies with a yellow color. In alcoholic

solutions it yields a brownish green color with ferric chloride,

an orange yellow color with lead acetate and a reddish brown

precipitate with lime or baryta water. It reduces an ammonical

silver solution in the cold, Fehling’s solution when warmed.

Isorhamnetin, — Quercetin-3' -monomethyl ether, or

Trihydroxy- 1, 3, 4' -methoxy-3' -flavonol.

Isorhamnetin was first isolated by Perkin and Hummel* 1 in

1896, from the petals of the yellow wallflower, Cherianthus cheri,

and later by Perkin and Pilgrim2 from the flowers of Delphinium

zali. Because by oxidation in alkaline solution isorhamnetin

yields vanillic acid, Perkin3 concludes that it has the methoxy

group in position -3'- as given above.

Isorhamnetin occurs, as stated above, in the flowers of cher¬

ianthus cheri and of Delphinium zali, along with quercetin. It

crystallizes in masses of fine, brilliant yellow, needle like cry¬

stals which are difficultly soluble in boiling alcohol and in acetic

acid. With lead acetate it gives an orange red preciptate, with

ferric chloride a greenish black coloration. Fused with alka¬

lies it yields protocatechuic acid and phloroglucin.

Rhamnazin, — Quercetin-3, 3’ -dimethyl ether , or

Dihydroxy-1 , 4' -dimethoxy-3, 3' -flavonol.

Rhamnazin was first found by Perkin1 in ‘ ‘ Persian berries,

the fruit of various species of Rhamnus, while trying to purify

rhamnetin, in 1895, and shown by him to be dimethyl-3, 3'-

quercetin, as below.

*Jr. Chem. Soc.. 69, p. 1566.

2 Jr. Chem. Soc., 73. p. 267.

8 Proc. Chem. Soc., 14, p. 56.

1 Jr. Chem. Soc., 67, p. 496; 71, p. 819.

Wakeman — Pigments of Flowering Plants.

855

Rhamnazin occurs in the fruit of Rhamnus infectoria,1 and

perhaps in other species of Rhamnus. Pure rhamnazin forms

yellow needle like crystals which melt at 214°-215° and some¬

what resemble anthraquinone in appearance. They are less

soluble in acetic acid than are those of quercetin and very

slightly soluble in alcohol. Prom acetic acid rhamnazin cry¬

stallizes with one molucule of water of crystallization which it

loses at 100°. It dissolves easily in alkalies with an orange red

color, with lime or baryta water it gives an insoluble orange red

precipitate. The alcohol solution gives an olive green coloration

with ferric chloride. ' It forms a triacetyl, also a trobenzoyl

derivative.

Morin , — Penthydroxy- 1, 3 , 2', 4' , a-flavone, or

Tetrahydroxy- 1, 3 , 2', 4 ' - flavonol .

Morin was first found by Chevreul1 in yellow wood, Morns

tinctoriat in 1830, and later by Perkin and Cope2 in the Indian

dye stuff Artocarpus tinctoria. It closely resembles quercetin

in appearance and reactions. Perkin3 in his work on morin in

1896 assigned to it the constitutional formula of quercetin with

the catechol nucleus replaced by a resorcinol group. This for¬

mula was verified by the work of Kostanecki4 in 1904, and further

‘Jr., Chim. Med., 6, p. 158.

3 Jr. Chem. Soc., 67, p. 937.

3 Jr. Chem. Soc., 69, p. 792; Chem. News., 73, p. 253.

4 Ber., 37, p. 2350.

856 Wisconsin Academy of Sciences , Arts, and Letters.

confirmed by his final synthesis5 of morin from hydroxy-2'- tet-

ramethoxy-4, 5, 2', 4' -chalkon in 1906.

Morin occurs in fustic wood, Morns tinctorial the wood of

chloropJiora tinctorial and of Artocarpus integrifolia,2 and

maclura tinctorial

Morin crystallizes in long needle like crystals which are very

slightly soluble in water, easily soluble in alcohol and less easily

soluble in ether. It is not at all soluble in carbon disulphide,

but soluble in alkalies with a yellow color. In alcoholic solu¬

tions it gives an olive green color with ferric chloride. It re¬

duces an ammoniacal silver solution in the cold, Fehling’s so¬

lution when warm. Treated with potassium salts a yellow pre¬

cipitate is obtained which corresponds to the formula C15H907K.

With sodium acetate the corresponding sodium salt is obtained.

Fused with alkalies morin yields phloroglucine and /?- resorcyclic

acid. To wools mordanted with aluminum morin imparts a

yellowish olive color; with chromium, a deep brown; with tin,

a bright yellow ; and with iron, a dark olive brown color.

Besides those mentioned above, morin has been prepared and

studied by the following chemists :

Wagner, — Jr. f. prakt. Chem., 50, p. 182.

Hlasiwetz and Pfaundler, — Ann., 127, p. 351.

Loewe, — Zeit, anal. Chem., 14, p. 119.

Benedikt, — B., 8, p. 606.

Benedikt and Hazura, — ■ Monatsh., 5, p. 167.

Perkin, — Jr. Chem. Soc. 67, p. 649; 69, p. 792; 75, p. 433.

Herzig, — Monatsh., 18, p. 702.

Hexhydroxy flavones.

Myricetin, — Hexhydroxy-1, 3, 3' , 4' , 5' , a -flavone, or,

P entity dr oxy- 1, 3, 3’ , 4', 5' - flavonol .

Myricetin was first isolated by Perkin,1 in 1896, from Myrica

nagi, an Indian dye stuff, and named by him from its source.

• Ber., 39, p. 81; 95, 627.

Wakeman — Pigments of Flowering Plants . 857

It was later isolated, by Perkin2 and his associates, from a num¬

ber of other dye stuffs and has been found to be a hydroxy

quercetin.

Myricetin occurs as the glucoside myricitrin in the bark of

Myrica nagi 1 and M. gale.2 In the leaves of Rhus coriaria2 R.

cotinus 2 and R. metopium2 It also occurs in Pistachia lentis-

cuSy 2 Haematoxylon campechianum2 and in the leaves of Arcto-

staphylos uva ursi2

Myricetin crystallizes in small clear yellow crystals which melt

with decomposition above 300°. It dissolves with difficulty in

boiling water, more easily in alcohol, and almost not at all in

chloroform and acetic acid. It dissolves in potassium hydrox¬

ide solution with a yellow color which changes in the air to

bluish, and becomes finally dull violet red in color. Concen¬

trated alkali solutions give a permanent red color which goes

through all the above changes upon dilution. Ammonia gives

a more reddish color, lead acetate, a reddish orange color which

becomes yellow upon boiling. Myricetin is dissolved with a

red color in sulphuric acid and is precipitated upon the addi¬

tion of water. Ferric chloride gives a black color in alcoholic

solutions. Fused with alkalies myricetin rapidly becomes

brown and yields principally gallic acid and phloroglucin.

Myricetin dyes fabrics mordanted with aluminum a brownish

orange; with chromium, a red brown; with tin, a deep orange

red ; and with iron, an olive black.

Gossypetin.

In 1899 Perkin* 1 isolated from the yellow flowers of the Indian

Cotton- -Gossypium herbaceum a yellow pigment which he

called gossypetin. This substance has the molecular composi¬

tion C15 H10 08. It is isomeric with myricetin with six hydroxy

groups, two of which are in relatively ortho-position. In its be¬

havior it closely resembles the flavone derivatives. It is prob¬

ably a member of the flavone group.

Gossypetin occurs principally in the form of the glucoside

gossypitrin in the flowers of Gossypium herbaceum,1 the Indian

•Czapek, p. 521.

*Jr. Chem. Soc., 69, p. 1287.

a Jr. Chem. Soc., 81, p. 203; 77, p. 424, 427.

1 Jr. Chem. Soc., 75, p. 825.

* Jr. Chem. Soc., 95, p. 1855.

858 Wisconsin Academy of Sciences , Arts , and Letters.

cotton, and in the flowers of Hibiscus sabdariffa2 The Indian

cotton flowers are used by the natives as a dye stuff. The seeds

of the plant also contain a somewhat feeble yellow dyestuff, not

identical with gossypetin, which by the action of acid is con¬

verted into the so called cotton seed blue.3 Moreover, in the

bark of the stem there exists a dye4 which somewhat rsembles

gossypetin.

Gossypetin crystallizes in glistening yellow needles. Its

hexacteyl derivative melts at 222° -224°. Treated with sulphuric

acid in acetic acid solution it forms a gossypetin sulphate con¬

sisting of glistening orange-red needles. This compound is de¬

composed by water into gossypetin and sulphuric acid. The

hydrochloride prepared in the same way forms orange crystals

and is very unstable. The hydriodide which forms orange red

crystals is more stable. The hydrochloride could not be

analyzed but the others are evidently formed by addition of one

molecule of the acid to one of the pigment. This behavior sug¬

gests the oxonium formation.

Gossypetin is very soluble in alcohol and slightly soluble in

water. It dissolves in alkalies with an orange red color. Fused

with alkalies it yields phloroglucin and protocatechuic acid. To

wools mordanted with aluminum it gives a pale orange brown

color; with tin, an orange red color, with chromium, a dull

brown and with iron a deep dull olive color.

The dyeing properties of the flowers of the Indian cotton are

very distinct from those of gossypetin, due to the fact that they

contain the glucoside and not the free coloring matter. With

the ordinary mordants the following shades are obtained :

Aluminum, dull yellow; tin, orange brown; chromium, dull

brown-yellow; iron, dull olive.

[. B. p.) Butein.

While not a flavone derivative, butein is nevertheless referable

to the same hydrocarbons as the flavone derivatives, being a

tetrahydroxy-4, 5, 3', 4'-diphenyl-l-3-propene-l-one-3, or tetrahy

droxy chalkon.

3 C. r., 53, p. 444; Anzeiger der Akademie der Weissenschafter iti Krakaw,

Nov. 1897.

Wakeman— Pigments of Flowering Plants.

859

CH CH CH COH

Butein1 occurs in glucosidal formation, either as such or in

the form of butin, in the flowers of Butea frondosa. Its synthe¬

sis from dimethylprotocatechuic aldehyde and monomethyl re-

sacetophenone as well as its formation from butin2 have been dis¬

cussed in a previous chapter.

Butein crystallizes in needle like crystals which melt at

213°-215°. It is readily soluble in alcohol, somewhat soluble

in ether, more sparingly soluble than butin in hot water. It

dissolves in alkaline solutions with a deep orange red color. In

alcoholic solutions with lead acetate it gives a deep red precipi¬

tate, with ferric chloride an olive brown coloration. In cold

sulphuric acid it dissolves with an orange color, upon the addi¬

tion of water the butein is precipitated unchanged.

Butein dyes wools mordanted with aluminum a beautiful

orange color, with chromium a deep terra cotta, with tin a beau¬

tiful yellow, and with iron a brownish olive.

I. B. 3.) The anthocyanin pigments.

The so called anthocyanin pigments have long attracted the

attention of both chemists and botanists, and have called forth

considerable work from both classes of investigators. From

time to time colored substances have been extracted from plant

organs supposed to be colored by anthocyanin pigments and

have been made the subject of special investigation. These

colored substances, though sometimes crystalline, were probably

seldom pure, so that little chemical knowledge was gained either

of the special pigment studied or of the anthocyanins as a class.

In' addition to the above, many theories, all of which have been

more or less unsatisfactory, have been advanced to account for

both the appearance and the disappearance of color in flowers,

fruits, and autumn foliage.

The recent exhaustive study, by Willstaetter, of anthocyanin

1 Froc. Chem. Soc., 10, p. 11; 19, p. 133; 85, p. 1495.

2 See Butin, Formula of saturation CnH,n-14.

860 Wisconsin Academy of Sciences , Arts, and Letters,

pigments in some plants, while not satisfactory in every detail,

is a long step in advance. This work not only explains much

concerning the chemistry of the anthoeyanin pigments that has

hitherto been unexplained; but it places the anthocyanins in

a class, and shows the close chemical relationship between the

various anthoeyanin pigments studied, and also between the

anthocyanins and other pigments occurring with them in the

plant.

Anthocyanins are the red, blue and purple pigments extracted

from flowers, fruits, and leaves by water and dilute alcohol.

They are insoluble in ether, are turned red by acids, blue or

green by alkalies, and give green, green-blue, gray-green, or yellow

precipitates with lead acetate. It is commonly supposed that

the purple color of flowers and fruits is due to the free pigment,

the blue color to an alkaline combination, and the red color to

an acid combination of the pigment.

The anthocyanins, according to Willstaetter, are present in

the plants only as glucosides, sometimes as mono- and some¬

times as diglucosides. The sugar molecule with which the pig¬

ment is combined is generally that of glucose, though in at

least one instance galactose is present. The anthocyanins all

exhibit a characteristic reaction, the anthocyanidin reaction.

An anthoeyanin dissolved in a normal or twice normal solu¬

tion of sulphuric acid is unaffected by shaking with amyl alco¬

hol. After hydrolysis, however, the colored anthocyanidin is

quantitatively extracted by the amyl alcohol, forming a reddish

violet solution which slowly, more rapidly in the presence of

sodium acetate, changes to a bluish violet.

All of the anthocyanins so far studied are very closely related,

the color bases of the various glucosides being hydroxy and

methoxy derivatives of pelargonidin, the least highly oxygen¬

ated of the known anthocyanins. They are also closely re¬

lated to the flavone derivatives, so many of which constitute

the yellow plant pigments, and many of which occur -side by

side with the anthoeyanin pigments in the plants. Accord¬

ing to Willstaetter the free anthoeyanin pigments are isomers

of some of the flavone pigments, the isomerism between them ex¬

isting, not in the position of substitution in one or the other of

the two benzene nuclei, but in the transformation, by the chang¬

ing of valence of the ether oxygen from' two to four, of the

pyron to a pyrylium grouping, and of a difference in the posi-

Wakeman— Pigments of Flowering Plants. 861

tion of the hydroxyl group in the pyrylium cycle, all of the

anthocyanin pigments so far known possessing a hydroxyl group

in the flavonol position. For example, luteolin and cyanidin

are both represented by Ahe formula C15H10O6.

The formula for free cyanidin is not known.

The hydrochloride of luteolin Willstaetter represents by for¬

mula I, and that of cyanidin by formula II. below.

While this difference of position of a hydroxy group may be

sufficient to explain the difference in properties of the two

groups of pigments in acid combination, something more seems

to be required to explain this difference in the acid free form,

since many of the flavone pigments as well as the anthocyanin

pigments are flavonols. Moreover it does not appear to be

sufficient to explain the difference between such isomers as,

862 Wisconsin Academy of Sciences, Arts, and Letters .

for example, delphinidin hydrochloride and quercetin hydro¬

chloride, quercetin having an hydroxy group in the flavonol

position.

CH row

The anthocyanin pigments have long been thought of as being

of a quinoidal character. This supposition was encouraged

by the oxidation of quercetin and chrysin, by Niernstein and

Wheldale,1 to quercetone and chrysone respectively, these oxi¬

dation products being “anthocyanin like.” Willstaetter and

Everest2 sought to explain the constitution of cyanin by assum¬

ing a quinoidal arrangement and classifying the anthocyanins

as paraquinoidal flavone derivatives, as below :

From such a molecule one would expect a hydroxy hydro-

quinone as one of the products of abbau. Since no such pro¬

duct, but phloroglucine just as with the majority of flavone

1 Ber., 44, p. 3487; 45, p. 499.

* Amn., 408, p. 18.

Wakeman — Pigments of Flowering Plants. 863

pigments, is obtained, the qninoidal configuration as a possible

explanation was abandoned and the arrangement of double

bonds of the pyrylium grouping adopted instead. Whether

or not the difficulties in the way of accepting Willstaetter’s

furmula are more easily explained away than are those in the

way of accepting the quinoidal formula is still a matter of

opinion.

Among the anthocyanins thus far studied pelargonidin is

isomeric with apiginin and galangin. Cyanidin is isomeric

with luteolin, lotoflavin, fisetin, and kaempherol. Paeonidin,

a methyl ether of cyanidin is isomeric with kaempherid, a

methyl ether of kaempherol. Delphinidin is isomeric with

quercetin and morin, while myrtillidin, a methyl ether of del¬

phinidin is isomeric with rhamnetin and isorhamnetin, both

methyl ethers of quercetin, and malvinidin and oenidin,

dimethyl ethers of delphinidin are isomeric with rhamnazin,

a dimethyl ether of quercetin.

The isomerism of the above named compounds is probably

not to be doubted. That this isomerism consists only in the

different position of a hydroxyl group in the pyrylium ring,

even in acid combination, is open to question, since no such

marked difference in properties exists between the flavonols

and the true flavones as is found to exist between the flavone

derivatives and the anthocyanins.

None of the neutral pigments, isomeric with the flavone pig¬

ments appear to have been isolated as such. They have been

obtained as oxonium salts formed by the addition of a mole¬

cule of acid to a molecule of the pigment, as the colorless pseudo

base, obtained by the elimination of the elements of hydro¬

chloric acid and the addition of the elements of a molecule of

water, and as the color base, a colored modification of the pseudo

base into which it changes upon standing in concentrated solu¬

tion.

According to Willstaetter red and pink colors in the organs

examined are due to acid compounds of the pigment, oxonium

salts; purple and violet colors to the free pigments; and blue

colors to metallic derivatives of the pigment. The blue corn¬

flower is probably colored by the potassium salt of the cyanin,

and the scarlet geranium by the compound of pelargonin with

tartaric acid, while the purple delphinum is supposed to be col¬

ored by the neutral delpninin.

804 Wisconsin Academy of Sciences , Arts , and Letters.

Tetrahy dr oxides.

Pelaogonidin.

According to Willstaetter pelargonidin chloride, the oxonium

salt of pelargonidin, is probably represented by formula I.

given below, though he also recognizes the possibility of its being

represented by formula II. Willstaetter prefers the first fomula

because he regards the second as the structural formula of a

fiavone derivative.

Pelargonidin exists in the blossoms of the red geranium,

pelargonium zonale, combined with two molecules of glucose as

the glucoside pelargonin.

The geranium pigment was isolated by Griffiths1 from the

blossoms of the red geranium in 1903. Griffiths decided that

the pigment has the formula C15Hia06 and that it forms a red

diacetyl derivative.

In 1908 Wenzell2 again isolated the crystalline red pigment

from the flowers of Pelargonium zonale, but he made no chemi¬

cal study of the compound.

During the winter of 1911-1912 the writer, having access to

large quantities of geranium blossoms, again isolated the red

crystalline pigment. The substance crystallized in fine needle

1 Ber., 36, p. 3956.

2 Pacific Pharmacist, 1908.

Wakeman — Pigments of Flowering Plants. 865

shaped crystals of a high melting point and a bright red color.

The crystals dried in masses of a brownish color with a beauti¬

ful green reflection. This substance was no glucoside. If it

existed as such in the plant, it was hydrolized in the process of

preparation by the sulphuric acid used to decompose the lead

precipitate. The crystalline substance was insoluble in ether,

chloroform, hydrocarbon oils, and carbon disulphide, almost in¬

soluble in hot water and in 95 per cent alcohol, but easily soluble

in 60-70 per cent alcohol when heated. It was possibly the

pelargonidin sulphate described by Willstaetter.

This compound gave a yellow acetyl derivative when heated

with acetic acid anhydride and anhydrous sodium acetate. This

acetyl derivative, computed upon Griffith’s formula of C 15H10Q 67

contained five acetyl groups. This, interpreted in the light of

Willstaetter ’s formula would probably mean that the sulphate,

in the process of aeetylimtion, was changed to the acetate and

that all four of the hydroxy groups were acetylized. When

heated in alcoholic solution with zinc and acetic acid the red

color of the crystalline pigment disappeared leaving a colorless

solution. This, after standihg exposed to the air, gradually

became deep red in color. No crystals could be induced to

separate from this red solution.

Willstaetter criticises severely the old method of attempting

to separate anthoeyanln pigments by precipitation with lead

acetate. However just this criticism may be when applied to

anthocyanins in general the writer will not venture to say. The

above described pigment, however, was easily obtained, appar¬

ently in a pure condition, by precipitating an aqueous extract

of fresh geranium blossoms with lead acetate and decomposing

the precipitate with sulphuric acid. The exact details of the

process need not be given here.

In 1911 Grafe3 isolated what he considered as two pigments

from the scarlet geranium, one glueosidal and the other not

glucosidal in character. Willstaetter says that as a matter of

fact both of Grafe ’s pigments are glucosides, and that only one

is present in the plant, the second being a mixture of the pig¬

ment with other substances.

Willstaetter ’s pelargonidin was separated in the form of the

oxonium salt of the glucoside pelargonin. This upon hydroly-

8 SitzungBtoer. d. Wien Akad, Wiss. math. nat. ki, 120, p. 765.

55— S. A. L.

866 Wisconsin Academy of Sciences , Arts , and Letters.

sis yields pelargonidin chloride which crystallizes in three dif¬

ferent forms. The sulphate crystallizes in needles.

Willstaetter’s idea of the structure of pelargonidin is ob¬

tained from its abbau with 50 per cent potassium hydroxide

solution when phloroglucin, p-hydrohy benzoic acid, and small

quantities of protocatechuic acid are obtained. It is isomeric

with apiginin and galangin.

Willstaetter found pelargonin in the scarlet flowers of pelar¬

gonium zonale ,4 also in the scarlet red varieties of dahlia,5 known

as “Uakete” and f< Alt Heidelberg,” also in a violet red variety

of dahlia.

PentJiy dr oxides.

Cyanin.

The above formula represents the constitution of cyanidin

hydrochloride according to Willstaetter’s more favored formula.

As early as 1854 Fremy and Cloez* 1 isolated a blue pigment

from the cornflower which they called cyanin. According to

these investigators there are three kinds of pigments in plants,

the green, called chlorophyll, the yellow known as xanthine and

xantheine, and the red and blue, which they called cyanin. The

red and rose colored flowers owe their color to the cyanin col¬

ored by acids in the juice of the plant.

In 1913 Willstaetter and Everest2 again isolated the blue

pigment from cornflowers and made it the subject of an exhaus¬

tive investigation. They found that cyanin, the pigment, is a

glucoside which they obtained as the hydrochloride. Upon

hydrolysis this glucoside gave cyanidin chloride. To the hydro-

4 Ann., 408, p. 42.

6 Ann., 408, p. 151.

1 Jr. de Pharm., 58, p. 249.

2 Ann., 401, p. 189.

Wakeman — Pigments of Flowering Plcmts.

867

chloride of the glucoside they assigned the formula C2SH33017C1.

3H20, to that of the cyanidin C16H1307C1. As the result of a

later determination these formulae were changed to C27H31016C1.

21/2 H20 and C15HV06C1. respectively, with the structural for¬

mula as given above.

Cyanidin exists as the glucoside cyanin in Centauria cyanus ,

the corn flower, in the dark red varieties of the cactus dahlia3 4

known as “ J. H. Jackson/’ “Harold,” “Matchless,” “Othello,”

and “Night,” in the petals of Rosa gallica, and in the fruit of

the whortleberry, Vaccinium vitis idaea , as the glucoside idaein,

a compound of one molecule of cyanidin with one of galactose.

Cyanidin is isomeric with lotoflavin, luteolin, fisetin, and kaem-

pherol.

Paeonidin , — a monomethyl ether of cyanin.

Paeonidin1 exists in the paeony blossoms as the glucoside

paeonin, a compound of paeonidin with two molecules of glucose.

Treated with hydriodic acid it yields cyanin and methyl iodide.

The formula for paeonidin hydrochloride favored by Willstaetter

is given above. Paeoninin is isomeric with luteolin methyl

ether and kaempherid.

H exhydroxides.

Delphinidin.

Delphinidin1 occurs as the glucoside delphinin in the blossoms

of Delphinium consolida where it exists along with the isomeric

3 Ann., 408, p. 1.

4 Ann., 408. p. 151.

1 Ann., 408, p. 136.

'Ann, 408. p. 61.

■ /

868 Wisconsin Academy of Sciences , Arts, and Letters .

quercetin and the closely related kaempherol.2 The glucoside

delphinin is a compound of one molecule of delphinidin with two

of glucose. •

Delphinidin is isomeric with quercetin and morin. The struc¬

tural formula most favored by Willstaetter is given above.

Myrtillidin,

CH

monomethyl ether of delphinidin.

CH _ COH

r>i v-u

=A_c_c/^>

c= c

I

H

COH

CH

COH

Myrtillidin hydrochloride

Myrtillidin was found by Willstaetter to exist in the form of

the glucoside myrtillin in combination with one molecule of

glucose in the fruit of the bilberry, Vaccinium my rt illus;* 1 also

as the glucoside althaein in the blossoms of Althaea rosea,2 the

wild mallow. Myrtillidin is isomeric with rhamnetin and

isorhamnetin, monomethyl ethers of quercetin.

2 Jr. Chem. Soc., 73, p. 275; 81, p. 585.

1 Ann., 408, p. 103.

a Ann., 408, p. 110.

Wakeman — Pigments of Flowering Plants.

869

Oenidin, — a dimethyl ether of delphinidin.

The pigment from grapes had been separated in a more or

less impure state many times before Willstaetter undertook his

study of anthocyanin pigments. Mulder,1 in 1856 obtained the

pigment in the form of a bluish black mass, Mawmene,2 in 1856,

obtained the same substance and named it t ‘ oenocyanin. ” In

1858 Glenard obtained the pigment as an amorphous substance

which he called ‘ ‘ oenolin ’ ’ and to which he assigned the formula

C20H20O10. Gautier4 made several investigations of the coloring

matter of grapes, continuing his studies for a number of years.

Gautier traced a close relationship between the grape pigment

and the tannins. Willstaetter,5 in 1915, found the pigment to

exist in the form of the glucoside oenin in Vitis vinifera. To

the product of hydrolysis he gave the formula above.

Oenidin is an isomer of rhamnazin, a dimethyl ether of quer¬

cetin.

Malvinidin, — a dimethyl ether of delphinidin.

OCH,

1 Die Chemie des Wines, 44, p. 228.

2Le Travail des Vins.

3 C. r., 47, p. 268; Ann. Chim. Phys., (3) 54, p. 366.

4C. r., 86., p. 1507; 87, p.' 64; 114, p. 623.

5 Ann. 408, p. 87.

870 Wisconsin Academy of Sciences, Arts, and Letters.

Malvinidin was found by Willstaetter to exist in the violet

flowers of the wild mallow, or wood mallow, Malva sylvestris,

where it occurs in combination with two molecules of glucose

as the diglucoside malvin. Malvinidin is isomeric with oenidin,

also with rhamnazin, a dimethyl ether of quercetin.

II. PIGMENTS REFERABLE TO DIHYDRO ANTHRACENE AND HOMO-

LOGUES.

A. Pigments referable to dihydroanthracene.

B. Pigments referable to homologues of dihydroanthracene.

1. Pigments referable to methyl -1- dihydroanthracene.

2. Pigments referable to methyl -2- dihydroanthracene.

Most if not all of the plant pigments referable to dihydro-

anthacene and its homologues, are derivatives of anthraquinone

and its homologues, the quinones being tetrahydroxy derivatives

of the underlying hydrocarbons.

O

1 Ann., 408, p. 122.

Wakeman — Pigments of Flowering Plants.

871

There exist in plants a large number of compounds, referable

to these three hydrocarbons, most of which are used as dyestuffs.

So far as is known, all except possibly the aloins, are hydroxy

derivatives, and their alkyl or sugar ethers, of quinone oxida¬

tion products of these hydrocarbons, viz. anthraquinone and

methyl anthraquinones. The aloins are possibly hydroxy de¬

rivatives of dihydro methyl anthracene.

Anthraquinone, which forms pale yellow crystals, is a quinone

having its two carbonyl groups in p - position with reference to

each other, a configuration which in itself is supposed to give

color to a molecule. The intensity of the color, and especially

the dyeing property, of the substance appears to depend upon

the number and the position of free hydroxy groups introduced

into the molecule.

As in the Xanthone and Flavone groups the compound ap¬

pears to be more highly colored and to possess better dyeing

properties when there is a hydroxy group in position -1- rela¬

tively ortho to the carbonyl group, so the anthraquinone pig¬

ments used particularly as dyes contain at least one hydroxy

group in ortho position to one of the quinone oxygens. In 1887

872 Wisconsin Academy of Sciences , Arts, and Letters.

Liebermann and Kostanecki1 undertook a study of a large num¬

ber of hydroxy anthraquinones in order to ascertain the re¬

lation between the number and position of the hydroxy groups

and the dyeing properties of the compound. The result of their

investigations may be summarized as follows: At least two

hydroxy groups are necessary in order that the anthraquinones

may become dye stuffs. This is shown by the fact that no mono¬

hydroxy anthraquinones have dyeing properties. Of the known

dihydroxy anthraquinones, only alizarin with the hydroxy

groups in positions 1 and 2 has strong dyeing properties.

Hystazarin, which was not known at this time, 2, 3, dihydroxy

anthraquinone, does, it is true, combine with mordants but its

dyeing properties are weak and it is not satisfactory as a dye

stuff. That the dyeing property of alizarin is not dependent

on only one of the two hydroxy groups is shown by the fact that

the monomethyl or mono ethyl ether of alizarin does not dye mor¬

danted fabrics. From these facts Liebermann draws the conclusion

that in order to have dyeing properties the polyhydroxy anthra¬

quinones must have two of their hydroxy groups in positions 1

and 2.

All of the known trihydroxy anthraquinones which have the

property of dyeing mordanted fabrics have two of their hy¬

droxy groups in positions 1 and 2 or in similar positions. The

same holds true for the tetrahydroxy derivatives. Those with

hydroxy groups in positions 1, 4, 1', 4', have no dyeing proper¬

ties whatever, and those with hydroxy groups in 1, 3, 2', 4',

possess very weak dyeing properties. It is theoretically im¬

possible to have pent- and hexhydroxy derivatives in which two

of the hydroxy groups are not connected to carbon atoms in

position 1 and 2. All of the known pent- and hexhydroxy an¬

thraquinones are good dye stuffs.

An exception to Liebermann ’s rule seems to be found in chry-

sophanic acid. The formula for chrysophanic most favored

at present represents the compound as possessing two hydroxy

groups in positions 1' -4', while none of the formulas consid¬

ered have hydroxy groups in positions 1 - 2.

Although Liebermann has shown that all the hydroxyanthra-

quinones which have dyeing properties, with possibly a few

exceptions, have hydroxy groups in positions 1 and 2, he has

* Ann., 240, p. 245.

Wakeman — Pigments of Flowering Plants. 873

apparently made no attempt to explain why this is so. Brandel1

in his monograph on Plant Pigments offers such an explanation.

“It is well known that the mordants which are used in dye¬

ing with these substances are salts of aluminum, iron and

chromium, in other words salts of trivalent metals. The pro¬

cess of dyeing with mordants depends upon the formation of

the aluminum, iron or chromium derivative and its deposition

in the fiber. This being true, one would possibly not expect

the monohydroxyanthraquinones to have dyeing properties,

inasmuch as the union of three molecules of the monohydroxy-

anthraquinone with one atom of aluminum, might hardly be

expected to take place very readily.

“On the other hand, by the introduction of more OH groups

into the same molecule the tendency to form these trivalent

metallic derivatives would be increased and it would be expected

to be the greatest in those cases in which the OH groups are

connected to neighboring carbon atoms. The bonds of the

aluminum atom would be subject to a less strain as it were,

than when they united with bonds from different molecules or

from widely separated bonds in the same molecule. From this

standpoint, the 2, 3, dihydroxyanthraquinone

o

CH II CH

as well as the 1, 2, dihydroxyanthraquinone

O

1 Brandel — Plant Pigments, p. 29.

874 Wisconsin Academy of Sciences , Arts, and Letters.

should have dyeing properties. Both of these compounds are

dyestuffs, the former not agreeing with the rule as laid down

by Liebermann.

‘ ‘ In those compounds in which the OH groups are not connected

to neighboring carbons atoms as is the case in the dihydroxanthra-

quinones, 1, 3, 1, 4; 1, 5, etc., the separation of the OH groups

from one another decreases the tendency to form metallic de¬

rivatives with trivalent metals and therefore these compounds

have no dyeing properties.

“On the basis of the same reasoning, the least strain of all

would result and, therefore, an aluminum, iron or chromium

derivative would be most readily formed in those cases in which

there are three OH groups connected to neighboring carbon

atoms. This is substantiated by the fact that anthragallol, 1,

2, 3, trihydroxanthraquinone.

has more intense dyeing properties than alizarin, 1, 2, dihydroxy

derivative. ’ ’

Of greater interest to the biochemist, however, than the re¬

lation of number and position of hydroxy groups to the color

and dyeing properties of the compound is the coexistence of a

number of these closely related compounds in the same or closely

related plants and the possibility of the formation of one from

another, or of all of them from simpler products of plant meta¬

bolism. From the root of Oldenlandia umbellata there have

been isolated monohydroxy -2- anthraquinone; alizarin, dihy¬

droxy -1, 2-anthraquinone and its monomethyl ether ; hystazarin,

dihydroxy -2, 3- anthraquinone and its monomethyl ether ; anth¬

ragallol, -1, 2, 3- trihydroxy anthraquinone and three of its

dimethyl ethers (A. B. C.). From Rubia tinctorium there have

been isolated alizarin, dihydroxy -1, 2- anthraquinone; xanth-

opurpurin dihydroxy -1, 3- anthraquinone; purpurin, trihydroxy

Wakeman — Pigments of Flowering Plants. 875

1-, 2, 4-anthraquinone ; rubiadin, methyl -1-dihydroxy -2, 4-

anthraquinone ; and pseudo purpurin, trihydroxy -1, 2, 4-

methyl -2- anthraquinone, ali as glucosides. In several other

instances several of these anthraquinone derivatives are known

to exist side by side in the plant. In Rheum officinale are

found emodin, isoemedin, rhein and chrysophanic acid, while

in Rhamnus purshiana are found emodine, chrysophanic acid

and chrysarobin, a reduction product of chrysophanic acid. Of

how the plants build up any or all of these related compounds,

or pass from one to the other, nothing appears to be known.

By the aid of structural formulae it can be shown how the plant

might be able to synthesize anthraquinone from two molecules

of carbonic acid and two of benzene.

O

il

/

\

C

il

o

By the substitution of phenols or homologues of benzene for

one or both of the benzene molecules the various anthraquinone

pigments might be formed. Unfortunately for the probability

of any such hypothesis little or nothing is known of the volatile

constitutents of the anthraquinone producing plants. A large

number of them contain tannic acid, gallic acid, and cinnamic

acid however. By the condensation of two molecules of gallic

acid a molecule of the anthraquinone configuration with six

hydroxy groups would result.

Unfortunately, again, such an anthraquinone derivative has

not been isolated from plants. By the substitution of a mole-

876 Wisconsin Academy of Sciences , Arts, and Letters.

cule of benzoic acid for one of gallic acid anthragallol results,

and by substituting benzoic acid or its homologues, and various

hydroxy benzoic acids for the gallic acid molecules any of the

anthraquinone derivatives might be produced, just as any of

the xanthone derivatives might be obtained by condensation

of a molecule of benzoic acid or its derivatives with a phenol or

of two molecules of phenols with one of carbonic acid.

II. A. Pigments referable to dihydro anthracene.

Six plant pigments of known constitution are referable to

dihydroanthracene as the underlying hydrocarbon. These are

all anthraquinone pigments, being mono- di- and tri- hydroxy

derivatives of anthraquinone. The relation of anthraquinone

to dihydroanthracene is shown on p. 870. The position of the

hydroxy groups is here indicated by numbers in the usual way.

1 . ) Monohy droxyanthraquinones

Monohydroxy -2- anthraquinone

2. ) D ihy dr oxy anthraquinones

a. ) Alizarin

b. ) Hystazarin

c. ) Xanthopurpurin

3. ) Trihy droxyanthraquinones.

a. ) Anthragallol

b. ) Purpurin

W akeman — Pigments of Flowering Plants.

877

II. A. 1.) Monohydroxy anthraquinone pigments.

Of this group of dihydroanthracene derivatives only one

representative, the monohydroxy -2- anthraquinone, is known.

O

iCH

COH

Monohydroxy -2- anthraquinone was first isolated from Olden -

landia umbellata by Perkin and Hummel1 in 1893. It crystal¬

lizes in glistening yellow needles which melt at 302°. Solu¬

tions of the alkali hydrates dissolve it, forming a red liquid

from which it separates, when very concentrated, in thin red

plates of the corresponding salts. Sulphuric acid dissolves it

with a red color.

Monohydroxy -2- anthraquinone does not combine with mor¬

dants to form a dye.

II. A. 2.) Bihydroxy anthraquinone pigments.

Of this group of dihydroanthracene derivatives three repre¬

sentatives have been isolated from plants. These are dihydroxy

-1, 2- anthraquinone, alizarin; dihydroxy -2, 3- anthraquinone,

hystazarin; and dihydroxy -1, 3- anthraquinone, xanthopur-

purin.

Alizarin — Dihydroxy -1, 2- anthraquinone.

HC

1 Jr. Chem. Soc., 63, p. 1178; 67. 820.

878 Wisconsin Academy of Sciences , Arts, and Letters.

Alizarin, the first known pigment of this group was discovered

by Colin and Robiquet1 in 1826 in the rhizorn of Ruhia tine -

torium where it exists principally as the glucoside ruberythric

acid. This glucoside was isolated by Rochleder2 and Schunk3

almost simultaneously in 1851. The relationship of alizirin

to anthracene was recognized by Graebe and Liebermann4 when

they obtained anthracene by the reduction of alizarin. After

a further study of the properties of alizarin they were able to

pronounce it a derivative of anthraquinone. In 1869 they ef¬

fected a synthesis of the compound.

Alizarin occurs in the rhizorn of Oldenlandia umbellata ,5 and

Rubia tinctorium.1

Alizarin crystallizes in red needles which melt at 289°-290°.

It sublimes in orange red needles. It is easily soluble in alco¬

hol and carbon disulphide but difficultly soluble in water. It

dissolves in alkaline solutions with a violet blue color. Sul¬

phuric acid dissolves it unchanged: Alizarin combines with

most mordants. To cotton mordanted with aluminum it gives

a garnet red color ; with tin, a light red ; with iron, violet ; with

chromium, a brownish purple color.

o- Methyl alizarin - — The methyl ether of alizarin occurs with

alizarin in the root of Oldenlandia-umbellata and in Morinda

longiflora .7 It crystallizes in orange colored crystals which melt

at 178°. It does not dye mordanted fabrics, but it dissolves

in solutions of the alkalies, also barium and calcium hydroxide

with a red color.

Hystazarin, 2, 3 - Dihydroxy anthraquinone.

O

'Ann. chim. phys., (2) 34, p. 225.

2 Ann., 80, p. 321.

2 Ann.. 81, p. 336.

* Ber., 2, p. 332.

* Proc. Chem. Soc., 23, p. 288.

•Jr. Chem. Soc.. 64, p. 1160.

* Jr. Chem. Soc.. 91. p. 1913 ; Proc. Chem. Soc., 23, p. 248.

Wakemaffr— Pigments of Flowering Plants.

879

Hystazarin exists in the Chay root, Oldenlandia umbellata,1

in the form of its monomethyl ether.

Hystazarin crystallizes in orange yellow needles which mell

at 260°. It is difficultly soluble in hot alcohol,* ether, acetone,

and acetic acid; insoluble in benzene and toluene; soluble in

solutions of alkalies with a blue color, of ammonia with violet,

and of acids with a red color. It forms a dark violet cal¬

cium2 salt and a dark blue barium salt. It is not satisfactory

as a dye.3

Hystazarin monomethyl ether crystallizes in orange yellow

needles which melt at 232°. It is soluble in alkalies with a red

color.

Xanthopurpurin or Purpuroxanthin.

Xanthopurpurin the dihydroxy -1, 3- anthraquinone exists in

the rhizome of Rubia tinctorium d

Xanthopurpurin crystallizes in yellow needles and sublimes

in yellowish red needles. It melts at 262°-263°. It is easily

soluble in alcohol, benzene, and acetic acid. By heating with

alkali in contact with air it is transformed into purpurin, tri¬

hydroxy -1, 2, 4- anthraquinone. Xanthopurpurin imparts

a rather fugitive yellow color to fabrics mordanted with alum¬

inum.

1 Rroc. Chem. Soc., 23, p. 228 ; Jr. Chem. Soc., 63, p. 1160.

2 Ber., 28, p. 118.

* Ber., 35, p. 1778; 21, p. 2501.

* Bull. Soc.. Chim., 4, p. 12.

3 Ann. de Chim. et de Fhys., (5) 18, p. 224.

880 Wisconsin Academy of Sciences , Arts , and Letters.

II. A. 3.) Trihydroxy anthraquinone pigments.

Of this group of dihydroanthracene derivatives two repre¬

sentatives are known in plants, trihydroxy -1, 2, 3- anthraquin-

one or anthragallol, and trihydroxy -1, 2, 4- anthraquinone or

purpurin.

Anthragallol — Trihydroxy — 1 , 2, 3 — anthraquinone.

O

Anthragallol exists in the Chay root, Oldenlandia umbellata /

in the form of three different dimethyl ethers, the dimethyl-1, 3-

ether, known as the A ether, the dimethyl-1, 2-ether, known as

the B ether, and the dimethyl-2, 3-ether, known as the C ether.1 2

Anthragallol itself forms orange red crystals and is an ex¬

cellent dye stuff, producing the anthracene brown of commerce.

It’s monomethyl-3-ether no longer colors mordanted fabrics

brown, but in shades of red similar to those produced by alizarin.

The two dimethyl ethers have no dyeing properties.

O

Anthragallol dimethyl ether A, Dimethyl-1, -3-hydroxy-2-

anthraquinone.

1 Jr. Chem, Soc., 63, p. 1160; 91, p. 2066.

aJr. Chem. Soc., 67, p. 826.

Wakeman — Pigments of Flowering Plcmts. 881

This compound is found in the root of Oldenlandia umbellata.1

It crystallizes in yellow needles which melt at 209°. It is

slightly soluble in alcohol and acetic acid, insoluble in chloro¬

form and carbon disulphide. In solutions of alkaline carbonates

it dissolves with a bright red color. It has no dyeing properties.

Antlnragallol dimethyl ether B, Dimethyl-1, 2-hydroxy-3-an-

thraquinone.

This compound occurs also in the root of Oldenlandia um¬

bellata. It crystallizes in long pale straw colored crystals

which melt at 230°-232° and are difficultly soluble in alcohol,

acetic acid, and ether; but soluble in alkali solutions with a

red color.

Anthragallol dimethyl ether C, Dimethyl-2, 3-hydroxy-l-an-

thraquinone.

This third dimethyl ether also occurs in the root of Olden¬

landia umbellata. It forms a barium salt melting at 212°-213°

and a lead salt.

56— S. A. L.

882 Wisconsin Academy of Sciences , Arts, and Letters.

Purpurin, — TriJiydroxy-1 , 2, 4-anthraquinone.

O

u

o

Purpurin exists in Rubia tinctorium 1 and other species of

Rubia,2 probably as a glucoside, along with alizarin. Purpurin

crystallizes in long orange yellow crystals which melt at 253°.

It is soluble in water with a deep yellow color, soluble in ether

and carbon disulphide, acetic acid and hot benzene ; but almost

insoluble in alkaline solutions. It imparts to fabrics mordanted

with aluminum a violet red color, with iron a violet blue, and

with chromium a reddish brown color. These colors are not

so permanent as those given by alizarin.

II. B.) Pigments referable to the homologues of dihydroan¬

thracene.

The plant pigments referable to the homologues of dihydro¬

anthracene are derivatives of two different monomethyl ethers

of dihydroanthracene, the methyl-l-anthraquinone and the

methyl-2-anthraquinone. Of the former five representatives

and of the latter three representatives are found in plants.

1. Methyl-l-anthraquinone.

a.) D'ihydroxy methyl-l-anthraquinones.

Rubiadin.

Chrysophanic acid.

b.) Trihydroxy methyl-l-anthraquinones.

Emodin.

Aloeemodin.

c.) Penthydroxy methyl-l-anthraquinones.

Bhein.

1 Ann., 2, p. 34; Jr. prakt. Chem., 5, p. 366; Ann., 66, p. 351.

3 Jr. Chem. Soo., 63, p. 1157.

Wakeman — Pigments of Flowering Plcmts. 883

2. Methyl-2-anthraquinone.

a. ) Trihydroxy methyl-2-anthraquinones.

Morindon.

b. ) H exhydroxy methyl-2-anthraquinones.

Pseudo purpurin.

II. B. 1.) Pigments referable to methyl-l-anthraquinone.

Five pigments of known constitution are referable to methyl-

i-anthraquinone. These are rubiadin, a dihydroxy-2, 4-methyl-

1-anthraquinone ; chrysophanic acid, a dihydroxy-1', 4'-methyl-

1-anthraquinone ; emodin, a trihydroxy-3, 1', 4 ' -methyl-l-anth-

raquinone ; aloeemodin, a trihydroxy-3, 4', 5-methyl-l-anthra-

quinone, and rhein, a dihydroxy-3, 4'-carboxy-l-anthraquinone.

Dihydroxides of methyl-l-anthraquinone.

Two pigments which are dihydroxides of methyl-l-anthra¬

quinone are known to exist in plants. These are rubiadin,

dihydroxy-2, 4-methyl-l-anthraquinone, and chrysophanic acid,

dihydroxy-1', 4 '-methyl-l-anthraquinone. As would be ex¬

pected from their similar constitutions the two compounds re¬

semble each other quite closely in properties, though chryso¬

phanic acid has the better dyeing properties. The fact that

chrysophanic acid possesses dyeing properties appears to be an

exception to Liebermann?s rule regarding the relation between

dyeing properties and the number and position of hydroxy

groups, since of the three structural formulae assigned to it by

different investigators none have the two hydroxy groups in

relatively 1, 2, positions, while the formula which appears to be

preferred at present has its hydroxy group in 1', 4', relatively

para position, a position which is supposed to give no dyeing

properties to anthraquinone derivatives.

Rubiadin , — -Dihydroxy-2, 4-mtehyl-l-anthraquinone.

884 Wisconsin Academy of Sciences , Arts, and Letters.

Rubiadin occurs as a glueoside in the root of Rubia tine -

torium.1 It crystallizes in yellow needles which melt at 290°.

It is easily soluble in alcohol, ether, and benzene, but insoluble

in water and carbon disulphide, also in lime water. In solu¬

tions of alkalies it dissolves with a red color.

Chrysophanic acid, — Dihydroxy-1', 4' -methyl-1 -ant hraquin-

one (?).

i. ii.

Chrysophanic acid occurs in the root of Rheum officinale,1

Rheum rhaponticum,2 Rumex obtusifolius,3 4 Rumex ecklonianus,3

Cassia angustifolia,5 * Cassia speciosa 1 Rhamnus purshiana,7

Rhamnus japonica ,G Rhamnus frangulafi and Tecoma ochraceae8

Chrysophanic acid crystallizes in yellow leaflets and melts

at 196°. It is insoluble in water, soluble in alcohol, ether,

acetone, benzene, chloroform, and petroleum ether. These so-

1 Jr. Chem. Soc., 63, p. 969, 1137; 65, p. 182; Chem. News, 67, p. 299.

1 Ann., 309, p. 32; Arch. d. Pharm., 245, p. 680; Ann., 9, p. 85; 50, p. 196;

107, p. 324.

2 Berl. Jahres., 23, p. 252; Jahresb. f. Pharm., 1882, p. 262.

3 Jr. Chem. Soc., 97. p. 1.

4 Arch. Pharm., 184, p. 37.

6 Chem. Centralbl., 1864, p. 622; Jr. Pharm. Chirm, 12, p. 505.

* Apoth. Ztgr., 15, p. 537; 16, p. 257, 538; 17, p. 372.

7 Proc. A. Ph. A., 52, p. 288.

* Z. oestei'. Apoth. Ver., 12, p. 31.

Wakeman — Pigments of Flowering Plants.

885

lutions color animal tissues deep yellow. It is soluble in so¬

lutions of alkaline hydroxides with a red color. Chrysophanic

acid colors unmordanted silk and wool yellow. Wools mor¬

danted with aluminum are colored orange red ; with chromium,

bright red ; and with iron, bright brown.

The constitution9 of chrysophanic acid is probably as indi¬

cated in formula I. above. This formula was first suggested

by Hesse in 1899, and afterwards by Jowett and Potter in 1903.

Attention should here be called to the fact th&t none of the above

formulae are in accord with Liebermann ’s rule for a eolored

molecule.

The principal investigations of chrysophanic acid are men¬

tioned in the following list:

Literature on Chrysophanic Acid.

Aweng, - — Pharm. Centralbl., 1898, p. 776; Apoth. Ztg., 15, p.

537; 17, p. 372.

Brandes, — Ann., 9, p. 85.

Dulk, — Arch. d. Pharm., 17, II. p. 26.

Geiger, — Ann., 9, p. 91.

Gilson, — Arch, internal, de Pharm et Therap., 11, p. 487.

Grandis, — Jahresb. d. Chem., 1892 p. 1654.

Grothe, — Chem. Centralbl., 1862, p. 107.

Hesse, — Ann., 291, p. 306; 309, p. 32.

Jowett and Potter, — Jr. Chem. Soc., 81, p. 1528; 83, p. 1327.

Le Prince, — C. r., 129, p. 60.

Liebermann, — Ann., 183, p. 169 ; 212, p. 36 ; Ber., 11, p. 1607.

Limousin, — Jr. de Pharm et de Chem., 1885, p. 80.

Marfori, — Chem. Centrlbl., 1900, I. p. 1292.

Oesterle, — Arch. d. Pharm., 243, p. 434.

Pelz, — Jahresber. d. Chem., 1861, p. 392.

Rochleder, — Ber., 2, p. 373.

Rue and Mueller, — Jahresber d. Chem., 1857, p. 516.

Rupe, — Chem. der nat. Farbs., 2, p. 117.

Schoeller, — Ber., 32, p. 683.

Scholzberger, — Ann., 50, p. 196.

Thann. — Ann., 107, p. 324.

Tschirch and Cristofoletti, — Arch. d. Pharm., 243, p. 434.

9 Jr. Chem. Soc., 83, p. 1327; Ann., 309, p. 32.

886 Wisconsin Academy of Sciences, Arts, and Letters.

Tschirch and Heuberger, — Arch. d. Pharm., 240, p. 605.

Tschirch, — B., 8, p. 189.

Tutin and Clewer, — Jr. Chem. Soc., 97, p. 1.

Yogel, — Arch. d. Pharm., 134, p. 37 (1868).

Trihydroxides of menthyVl-anthraquinones.

Two trihydroxides of methyl-l-anthraquinone, emodin, and

aloeemod'in, are known to exist in plants. These two isomeric

pigments occur together in various species of aloes and senna,

along with chrysophanic acid, of which emodin is a hydroxy

substitution product.

Emodin,1 a methyl -l-trihydroxy-2, 1', 4 ' -anthraquinone, or

methyl-l-trihydroxy-3, 1', 4 '-anthraquinone is an hydroxy sub¬

stitution product of chrysophanic acid.

Emodin occurs in various species of aloe,2 including Aloe

ferox,3 Aloe vulgaris ,4 and Aloe chinensis ;5 in Rheum officinale,6 7

Rheum palmatum,1 Polygonum cuspidatum,8 Cassia occiden¬

talism Cassia sophora,9 Cassia tora,10 Cassia angustifolia 9

Xanthoxylon tingoassuiba,11 Rhamnus cathartica,12 Rhamnus

japonica,13 14 Rhamnus purshiana,14: and Rhamnus frangula ,15

1 Jr. Chem. Soc., 83, p. 1327.

a Jr, Fharm. Chim., 28, p. 529.

8 B. Pharm. Ges., 1898, p. 174.

4 Arch. Pharm., 236, p. 200.

5 Arch. Pharm., 241, p. 340.

6C. r., 136, p. 385.

7 Ber., 1882, p. 902; Pharm. Jr. Trans., 15, p. 136.

8 Bull. Sci. Pharm., 14, p. 698.

9 Apoth. Ztg., 1896, p. 537.

10 Pharm. Jr. Trans., 3, p. 242.

11 B. Pharm. Ges., 9„ p. 162.

13 Jr. Russ. Phys. Chem. Ges., 40, p. 1502.

13 Apoth. Zt g., 1896, p. 537.

14 Arch. Pharm., 246, p. 315; Jr. Pharm. Chem., 246, p. 315.

16 Ber., 9, p. 1775; Pharm. Jr., 20, p. 558; Arch. Pharm.., 246, p. 315.

Wakeman — Pigments of Flowering Plants.

887

It will be seen from the above that ernodin not only resembles

chrysophanic acid in constitution but closely accompanies it in

the plant as well. Ernodin occurs both free and as a gluco-

side. It crystallizes in silky needles of an orange red color

which melts at 250°. It is soluble in alcohol, amyl alcohol,

and acetic acid, slightly soluble in benzene, and soluble in

alkalies and ammonia with a red color. With sulphuric acid

it gives an intense red solution which turns yellow, separates

a flocculent precipitate, and becomes colorless upon standing.

A considerable number of derivatives of ernodin have been

prepared.

The principal investigators of ernodin are listed below.

Combes, — Bull, de Soc. Chem., (4) 1, p. 800.

Hesse, — Ann., 284, p. 194 ; 309, p. 41.

Krassowski, — Jr. d. russ. phys. chem., Ges., 40, p. 510; Chem.

Centrlbl. 1919, I. p. 773.

Le Prince, — C. r., 129, p. 60.

Liebermann, — B., 9, p. 1775 ; 21, p. 436.

Oesterle, — Arch. d. Pharm., 237, p. 699.

Oesterle and Tisza, — Arch. d. Pharm., 246, p. 112, 432 ; Chem.

Centrlbl. 1908, I. p. 1548 ; II. p. 1441.

Tschirch and Pool, — Arch. d. Pharm., 246, p. 315.

Warren — Jr., Chem. Soc., 10, p. 100.

Rochleder, — B., 2, p. 373.

Frangulin.1 — A glucoside of ernodin, known as frangulin, oc¬

curs in the bark of RJiamnus frangula.2 It crystallizes in lemon

yellow crystals which melt at 226°. It is insoluble in water

and in ether, soluble in alcohol and in benzene. Upon hydroly¬

sis it yields ernodin and rhamnose.3

Polygonin . — A second glucoside of ernodin, known as poly-

gonin, occurs in the root of Polygonum cuspidatum .4 It

crystallizes in fine orange yellow needles which melt at 202°-

203°. It is insoluble in water, difficultly soluble in alcohol,

also in hot water. When hydrolized it yields ernodin and a

sugar.

»C. r., 134.

a Rep. f. Pharm., 104, p. 151; Ann., 104, p. 77.

3 Ann., 165, p. 230.

4 Jr. Chem. Soc., 67, p. 1084.

888 Wisconsin Academy of Sciences , Arts , and Letters .

Aloeemodin. — TriKydroxy-2, 4\ 5-methyl-l-anthraquinone.

Aloeemodin, a primary alcohol, occurs with aloin in various

species of aloes,1 senna2 and rhubarb.3 It crystallizes in orange

red needles which melt at 224°. It is easily soluble in ether,

hot alcohol, and benzene, soluble in concentrated sulphuric acid

with a cherry red color. Aloeemodin yields a triacetyl and a

tribenzoyl derivative. Upon reduction it forms methyl anth¬

racene. Oxidized with chromic acid mixture it yields rhein.

O COOH

CH C

Since rhein is produced upon the oxidation of aloeemodin,

one of its hydroxy groups must be in the side chain. The po¬

sitions of the other hydroxy groups is uncertain. Robinson

and Simonson4 have suggested for it the formula given above.

P entity dr oxides of methyl-1 -anthraquinone.

Only one penthy dr oxide of methyl-l-anthraquinone is known

to exist in plants. This is rhein, a dihydroxyanthraquinone

carboxylic acid. Rhein is an oxidation product of aloeemodin

which it accompanies in several species of aloes, and also of

rhubarb.

1 Whemer, Die PflanzenstofEe, p. 90; C.r., 150, p. 983 ; Arch. f. Pharm.

247, p. 413.

2 Rupe, Natuerliche Farbstoffe, 2, p. 134.

8 Arch. Pharm., 243, p. 443 ; 247, p. 413.

4 Proc. Chem. Soc., 25, p. 76 ; Jr. Chem. Soc., 95, p. 1085.

Wdkeman — Pigments of Flowering Plants.

889

Rhein. — Dihydroxy-3, 4' -carboxyl-l-anthraquinone.

Rhein occurs in Rheum officinale;1 English rhubarb ;2 Rheum

rhaponticum ;3 Rheum palmatum ;4 and Aloe vulgaris .5 It may

be formed by oxidation of Aloeemodin which occurs with it in

several species of Rhubarb.

Rhein crystallizes in small yellow needles which melt at

321°-322°. It is difficultly soluble in most ordinary solvents.

It is soluble in concentrated sulphuric acid with a red color,

also soluble in ammonia with a red color, upon exposure to the

air this color goes through violet into blue. In dilute alkaline

solutions it is readily soluble. Acids precipitate it from these

solutions as a yellow mass. It forms esters6 and ethers,6 the

former with alcohol, the latter with dimethyl sulphate in the

presence of potassium hydroxide. It dyes wools mordanted

with chromium a yellow color.7

The structural formula given is that suggested by Robinson

and Simonsen.6

II. B. 2.) Pigments referable to methyl-h -anthracene.

a. Trihydroxides of methyl-2-anthraquinone.

One pigment which is a trihydroxide of methyl-2-anthra-

quinone is known to exist in plants, this is morindon.

b. Hexhydroxides of methyl-2-anthraquinone.

One pigment, pseudo purpurin, which is a hexhydroxide of

methyl-2-anthraquinone, is known to exist in plants.

1 Pharm. Post., 37, p. 233, Arch. Pharm., 245, p. 150.

3 Arch. Pharm., 245, p. 141.

3 Arch. Pharm., 243, p. 443.

* Schweiz. Wochenschs. Pharm., 1904. Nr. 40.

5 Arch. Pharm., 247, p. 413.

"Jr. Chem. Soc., 95, p. 1085.

7 Rupe. Natuerliche Farbstoffe, 2, p. 143.

890 Wisconsin Academy of Sciences, Arts, and Letters.

Trihydroxides of methyl-2-anthraquinone.

Morindon, — A trihydroxy methyl-2-anthraquinone, isomeric

with emodin, occurs in the rind of the root of Morinda citri-

folia,1 Morinda umhellata,2 and Morinda tinctoria,3 along with

the glucoside morindin and other similar coloring principles.

It was first isolated by Anderson1 in 1849. It has sometimes

been mistaken for alizarin which it resembles in many of its

properties.

Morindon crystallizes in reddish brown crystals and sublimes

in long orange red needles. It melts at 272°. It is easily

soluble in alcohol ether, ethyl acetate, benzene and similar hy¬

drocarbons. Ferric chloride colors a solution of morindon

dark green, alkalies a violet blue. Morindin is soluble in con¬

centrated sulphuric acid with a violet blue color.

Literature on Morindin and Morindon.

Anderson, — Ann., 71, p. 216.

Oesterle and Tisza, — Arch. d. Pharm., 245, p. 534.

Perkin and Hummel, — Jr. Chem. Soc., 65, p. 851.

Rochleder, — Ann., 82, p. 205.

Steenhouse, — Jahresber. d. Chem., 97, p. 234

Stockes, — Jahresber. d. Chem., 17, p. 543.

Stockes and Stein, — Jahresber. d. Chem., 19, p. 645.

Thorpe and Greenall, — Jahresber. d. Chem., 40, p. 2299.

Thorpe and Smith, — Jahresber. d. Chem., 40, p. 2363.

Tschirch, — Arch. d. Pharm., 222, p. 129.

Tunmann, — Chem. Centralbl., 1909. 1. p. 199.

Hexh'ifdroxides of methyl-2-anthraquinone.

Pseudopurpurin, — Trihydroxy-1, 2, 4-carboxyl-2' -?anthra-

quinone, or Trihydroxy-1, 2, 4-carboxyl-3 ' -anthraquinone.

OH O

Unn., 71, p. 216; 82, p. 205 ; Chem. News.,: 54, p. 293.

a Jr. Chem. Soc., 63, 1160; 65, 851.

8 Whemer, Die Pflanzenstoffe, p. 737.

Wakeman — Pigments of Flowering Plants.

891

Pseudo purpurin occurs along with purpurin in the root of

Rubia tinctorium,1 It comprises a large part of the purpurin

of commerce. The constitution of the molecule does not ap¬

pear to have been yet definitely established. From the work

of Rosenstiehl,2 also that of Liebermann and Platt,3 we learn

the number and relative positions of the hydroxy groups.

Perkin4 has shown that the carboxyl group is in the second ben¬

zene nucleus, corresponding to one of the formulae given above.

Pseudo purpurin crystallizes in small red leaflets. It melts

at 218°-219°. It is almost insoluble in water and in alcohol,

difficultly soluble in chloroform and hot benzene, easily soluble

in solutions of alkaline carbonates with an orange color. Its dye¬

ing properties are almost identical with those of purpurin.

The Aloins.

Substances crystallizing in yellow needles and soluble in con-

eentrated sulphuric acid with a red, in alkaline hydroxides and

carbonates with an orange color, are found in various species of

aloes. These are known as aloins. The formula of aloin has been

variously given as C16H1607, C16H1809, C17H1807. Accord¬

ing to Jowett and Potter who have performed some of the most

recent work upon aloin, •C16H1807 is probably correct.

The aloins, known as aloin, barbaloin, isobarbaloin, and na-

taloin are closely related to the anthraquinone pigments.

Jowett and Potter think, however, that instead of the anthra¬

quinone nucleus being present there is probably a reduced an¬

thraquinone nucleus.

Upon treating aloin with sodium peroxide aloeemodin is

produced.

III. PIGMENTS REFERABLE TO PHENYL- HYDRINDINE AND HOMO-

LOGUES.

CH

rH rw

CH

fi -methyl- y -phenyl hdyrindine

1 Bull. Soc. Chim., 4, p. 12.

aC. r., 79, p. 680; 84, p. 559, 1902.

8 Ber., 10, p. 1618.

* Jr. Chem. Soc, 65, p. 842.

892 Wisconsin Academy of Sciences, Arts, and Letters.

No pigments referable to the above hydrocarbons are found

in plants; but two pigment forming substances, brazilin and

haematoxylon, which upon oxidation yield the pigments

brazilein and haematein, are referable to it. The pigments

themselves are referable to an isomer of methyl-phenyl hydrin-

dine, falling under the same degree of saturation.

CH CH

C H

H 3 Brazilin

Brazilin was first discovred by Chevreul,1 in 1808, in the heart

wood of Cisalpina echinata where it exists in the form of a glu-

coside. It was not until one-hundred years later, however, that

its constitution was definitely established when Perkin,2 in 1908,

after a long series of investigations, by the synthesis of brazil-

inic acid and other derivatives of brazilin, showed the formula

to be that given above. Besides in Cisalpina echinata, brazilin

occurs in another species of Cisalpina, C. sappari .3 According

to Rupe4 a number of woods, known as red woods, employed as

dyestuffs contain brazilin. These are all the products of var¬

ieties of Cisalpinia species and are known as Femanabose or

Brazil wood, Bahia red wood ; St. Martha wood ; Nicaragua wood,

Sapan wood, Lima wood and Braziliette wood.

Brazilin crystallizes in colorless crystals which color readily

upon exposure to the air. It is soluble in water, alcohol and

ether, these solutions color quickly upon exposure to the air.

Brazilin and its derivatives have been the subject of a large

number of chemical investigations, the principal ones of which

are listed below.

‘Ann. Chim. et Phys., 66, p. 225.

3 Proc. Chem. Soc., 79, p. 1396; 81, p. 221, 235, 1008; 91, 1073; 93, p. 489.

3 Ber., 5, p. 572.

4 Chemie der natuerlichen Farbestoffe., 1, p. 224.

Wakeman — Pigments of Flowering Plants.

893

Literature on Brazilin.

Benedict, — Ann., 178, p. 100.

Bolley, — Schweiz polytech. Zeit., 9, p. 267.

Buchka, — Ber., 17, p. 685 ; 18, p. 1140.

Chevreul, — Ann. Chem. Phys., 66, p. 225.

Dralle,— Ber., 17, p. 375; 20, p. 3365; 21, p. 3009; 22, p. 1547;

23, p. 1430 ; 25, p. 3670 ; 27, p. 527.

Herzig, — Montsh. f. Chem., 19, p. 738; 23, p. 241; 25, p. 871.

Herzig and Poliak, — B. 36, p. 398.

Kostanecki, — Ber., 35, p. 1674; 36, p. 2202.

Liebermann and Burz, — B. 9, p. 1885.

Perkin, — Jr. Chem. Soc. 79, p. 1396; 81, p. 225, 1008, 1057;

91, p. 1073 ; 93, p. 489, 1115 ; 95, p. 385.

Rein, — Ber., 4, p. 334.

Schall, — B. 27, p. 529 ; 35, p. 2306.

Haemafoxlyn

Haematoxlyn was discovered by Chevreul,1 in 1812, in the

heart of Haematoxylon campechianum. It has also been re¬

ported in the bark of Sancta indica,2 another leguminous plant.

Haematoxylon, being a hydroxy brazilin, resembles it closely

in physical and chemical properties. Its history also has been

almost identical with that of brazilin since the work which

proved the constitution of one compound proved also that of

the other. According to Perkin3 the formula of haematoxylon

is as given above. Kostanecki and Lampe4 have suggested

another formula which differs only in the position of one ben¬

zene nucleus and one hydroxy group. The later formula of

Perkin and his associates is probably to be preferred.

1 Ann. Chim et Fhys., 66, p. 225 (2) 82, p. 53, 126.

2 Pharm. Post., 1887, p. 778.

3 Jr. Chem. Soc., 93, p. 496.

4 Ber., 35, p. 1674.

894

Wisconsin Academy of Sciences , Arts , and Letters .

PIGMENTS REFERABLE TO /?-METHYL-y-PHENYL-ISOHYDRADINDlNE..

/3 - methyl* y -phenyl isohydrindine

Two pigments, brazilein and haematein, oxidation products

of brazilin and haematoxylon are referrable to the above hydro¬

carbon.

Wakeman — Pigments of Flowering Plants.

895

Brazilein occurs along with brazilin in various species of

“red wood,” Cisalpinia. It crystallizes in microscopic reddish

brown crystals with a metallic reflection. It is very slightly

soluble in cold water, better in hot water. The solution is

bright red with an orange fluorescence. It is soluble in alka¬

line solutions with a bright red color which turns brown upon

standing in contact with the air.

Brazilein dyes fabrics mordanted with aluminum a blueish

red; with chromium, grayish brown to violet gray; with tin,

orange red ; with iron and aluminum mixed, a dark purplish red.

Brazilein has been the subject of a large number of chemical

investigations and a large number of derivatives have been pre¬

pared.

Literature on Brazilein.

Herzig, — Monatsh. f. Chem., 19, p. 739 ; 20, p. 461 ; 22, p. 207 ;

23, p. 165 ; 25, p. 734 ; 27, p. 743.

Kostanecki, — B., 32, p. 1042 ; 41, p. 2373.

Perkin, — Proc. Chem. Soc., 22, p. 132 ; 23, p. 291 ; 24, p. 54, 148 ;

93„ p. 489, 1115 ; 95, p. 381.

Liebermann, — Ber., 9, p. 1866.

Scholl and Dralle, — Ber., 17, p. 375 ; 20, p. 3365 ; 21, p. 3009 ; 22,

p. 1547; 23, p. 1430; 25, p. 18; 27, p. 524.

Haematein.

Haematein occurs in the “blue wood” of Haematoxylon cam -

pechianum, forming the characteristic pigment of the logwood

dye stuffs. It crystallizes in microscopic crystals of a reddish

brown color with a yellowish green metallic reflection. It is

very slightly soluble in water, difficultly soluble in alcohol,

ether, and acetic acid, insoluble in chloroform and benzene. It

is soluble in alkaline solutions, in sodium hydroxide with a bright

red and in ammonia with a violet red color. It dyes fabrics

mordanted with aluminum a grayish blue to black color; with

iron, black; with chromium, blue black; with copper, greenish

black and with tin, a violet color.

896 Wisconsin Academy of Sciences , Arts , and Letters .

Literature on Haematein.

Baeyer, — Ber., 4, p. 457.

Erdmann, — Ann., 44, p. 294 ; 216, p. 236.

Halberstadt, — B., 14, p. 611.

Hesse, — Ann., 109, p. 337.

Mayer, — €hem. Centralbl., 1904, I. p. 228.

Perkin, — Ber., 15, p. 2337; Jr. Chem. Soc., 41, p. 368; 93, p.

1115; 95, p. 381.

PIGMENTS REFERABLE TO HYDROCARBONS OF THE DEGREE OF SATU¬

RATION CnH2n-18.

There occur in plants pigments referable to four hydrocar¬

bons of four distinct structural configurations, falling under

this degree of saturation, as follows:

I. Nine double bonds and one cycle.

The chlorophylls.

II. Eight double bonds and two cycles.

Pigments referable to diphenyl-1, 7-hep tadiene-1, 6.

III. Seven double bonds and three cycles.

Pigments referable to phenyl-dihydronaphthalene.

IV. Six double bonds and four cycles.

Pigments referable to anthracene.

With the exception of the first configuration under which we

find the two chlorophylls chlorophyll-a and chlorophyll-b, so far

as is known only one pigment under each structural configura¬

tion has been isolated. These are II. Curcumin, III. Trifoletin,

IY. Chrysarobin.

I. Pigments referable to hydrocarbons of the configuration

NINE DOUBLE BONDS AND ONCE CYCLE.

The Chlorophylls.

The chemistry of chlorophyll has attracted more attention and

has been the subject of more investigations than that of any

other plant pigment. This is due not only to the extremely

wide distribution and abundant occurrence of chlorophyll in

plants but also to its physiological importance and the role

Wakeman — Pigments of Flowering Plants. 897

which it appears to play in photosynthesis. Notwithstanding,

however, the abundance of material available, the importance of

the problem and the attention paid to it, np until quite recently,

but little light has been thrown upon the subject and even now

the chemistry of chlorophyll is far from being elucidated.

It is not at all the purpose of this paper to discuss the com¬

plex chemistry of chlorophyll, nor is this necessary in view of

the very thorough revision of the subject by MarchiewsM,1 pub¬

lished in 1909, and the yet more recent one by Willstaetter2 in

1913. A brief mention of the subject, however, is not out of

place and seems desirable in order to place chlorophyll in its

class among the plant pigments.

Chlorophyll, according to Willstaetter, is a complex magne¬

sium compound, or rather, a mixture of at least two such com¬

plex compounds, the blue green chlorophyli-a, C55H7205N4Mg,

and the yellow green chlorophyll-b, C55H70O6N4Mg.

Both of these chlorophylls are esters of phytol, which is a

constant constituent of chlorophyll. Phytol is an open chain

primary alcohol of the formula of saturation CnH2n. The fol¬

lowing structural formula has been suggested for phytol :

CHa—CH— CH— CH-—CH— OH — CH— CH — C = C— CH2 O H

ill i i i i i i

OH3 CH, CH3 CH3 CH3 CHa CH, CH3 CH3

Making it, according to the Geneva Congress system of

nomenclature, nonmethyl-2, 3, 4, 5, 6, 7, 8, 9, 10-undecene-2-ol-l.

By the action of an anzyme, chlorophyllase, chlorophyll-a is

hydrolised yielding phytol and chlorophyllid-a

C20H39OH MgN4O32H80OCOOCH3COOH

Phytol Chlorophyllid-a

while chlorophyll-b yields phytol and chlorophyllid-b.

C20H39OH MgN4C32H 0 COOCH8COOH

Phytol Chlorophyllid-b

Phytol is a non-colored substance and appears to play no di¬

rect part in pigmentation.

sDle Chemie der Chlorophyll, Braunschweig, 1909.

* Untersuchungen ueber Chlorophyll, Berlin, 1913.

57— S. A. Ii.

898 Wisconsin Academy of Sciences, Arts, and Letters.

Chlorophyllid-a and chlorophyllid-b, heated with caustic alka¬

lies, after passing through a number of intermediate stages, both

yield aetiophyllin, C31H34N4Mg, which appears to be the basic

colored portion of the molecule. For aetiophyllin Willstaetter

has suggested the following structural formula :

CH

-Ci

■<

I

CH,

CH

\

N-

CH = CH

l l

C - — C

,<

' e —

/ S

7" \

c — c

Mg - - - |

C ==.C

I

CH,

\ /

\ '

Referring aetiophyllin, as represented above, to the underly¬

ing hydrocarbon it is found to be derived from C31H44, a

duodeactetrene derivative with six side chains, and falling un¬

der the formula of saturation CnHn2-18 as below.

CHa— CH=C— C - CH — C-

I I II

CHa CHa CH

I I

CHa CHaCHaC

II

CHaC

I

CHa

-C— CH - C— C = CH— CHa

II I I

CH CH2 CH3

I I

CH CHa

II

C— CHa

I I

HC=CH

Aetiophyll itself is the product of the deammoniation and

combination with magnesium, of a dec ami do substitution pro¬

duct of the above hydrocarbon.

Wakeman— Pigments of Flowering Plants .

899

H

N

~EH2CH=CH

^Lnh,

I I l/HH,

CHa C C— C

II II

CH3CH,C CH CHa

CHa

I

KH, CHa CHa NHa

I I I I

CHa— C = C— C = C—

C HH, C HHa NHa CHa CHa NH,

II II I I I I

-c - C - C = C— C = C— CH,

By deammoniation of tlie above compound and subsequent

substitution of magnesium for imdio hydrogen aetiophyllin

would be formed.

II. Pigments referable to hydrocarbons of the configura¬

tion EIGHT DOUBLE BONDS AND TWO CYCLES.

Pigments | referable to diphenyl- 1, 7 -heptadiene- 1, 6.

/

CH,

CH, — CH ==' CH.— — C<C '> CH

W

CH CH

CH, - CHs=s» CH — - C< ^ ^CH

Diphenyl*), Mieptttiiened, 0 Oil CH

CHa

//

■c-

CH

CH^== CH

CnremniRf

COH

CH CO CH3

900 Wisconsin Academy of Sciences, Arts, and Letters .

Curcumine occurs in the rhizom of Curcuma longa, C. viridi-

fiora, and probably in other species of Zingiberaceae. It was

first obtained in the crystalline form by Daube,1 in 1870, though

it had been studied by Yogel and Pelletier2 as early as 1815.

In 1881 Jackson and Menke3 made the first correct analysis of

curcumine and ascribed to it the formula C14H1404. After mak¬

ing an extended study of its reactions they ascribed to it the

structural formula, -

CH COOH CH

This formula was accepted until 1897 when Ciamician and

Silber4 concluded that the molecule contained two hydroxy and

two methoxy groups and should be represented by the formula

C21H30O6 instead of C14H1404. Molecular weight determina¬

tions made by Perkin5 * and his associates in 1904 sustained the

conclusion of Ciamician and Silber. Jackson and Clarke,® in

1905-1908, made another examination which they interpreted

as proving the correctness of Jackson’s earlier formula. In 1910

Milobendzki, Kostanecki, and Lampe7 by a series of synthesis

proved the correctness of Camician and Silber ’s formula, assign¬

ing to the molecule the structural formula given above. In 1914

Jackson and Clarke8 by further work confirmed this formula.

Curcumine crystallizes in orange yellow crystals with a bluish

reflection, and a melting point of 178°. It is insoluble in

water and ligroin, almost insoluble in benzene, somewhat soluble

1 Ber., 3, p. 609.

•Jr. de Pharm., 60, p. 259.

8 Ber., 14, p. 485; 15, p. 1761; 17, (Ref.) p. 332.

4 Ber., 30, p. 192; Gazz. chim. ital., 27, I. p. 561.

•Jr. Chem. Soc., 85, p. 68.

•Ber., 38, p. 2712; 39, p. 3269; Am. Chem. Jr., 39, p. 699.

T Ber., 43, p. 2163.

•Am. Chem. Jr., 45, p. 48.

W akeman— Pigments of Flowering Plants.

901

in cold alcohol, ether and carbon disulphide. The solution in

ether gives a green fluorescence. Its reddish brown reaction is

well known.

In the course of the various investigations of which cureumine

has been the subject a large number of derivatives have been

formed.

The more important of the many investigations of cureumine

are given in the following list :

Literature on Cureumine.

Bolley, Suida and Daube, — Jr. prakt. Chem., 103, p. 474.

Ciamician and Silber, — B., 30, p. 192 ; Gazz. chim. ital., 27, 1. p.

561.

Daube and Claus, — Jr. prakt. Chem., (2) 2, p. 86; B., 3, p. 609.

Iwanon, — Ber., 3, 624.

Jackson, • — Ber., 14, 485.

Jackson and Mencke, ~ B.. 15, 1761; Am. Jr. Chem., 4, 368.

Jackson and Mencke, — Pharm. Jr. Trans. III. 13, 839.

Jackson and Mencke, — Ber., (Ref.) 17, 332.

Jackson and Warren, — - Am. Chem. Jr., 18, 111.

Jackson and Clarke, • — Ber., 38, 2712.

Jackson and Clarke, — Ber., 39, 2269.

Jackson and Clarke, — Am. Chem. Jr., 39, 699.

Jackson and Clarke, — Am. Chem. Jr., 45, 48.

Kachler, — B., 3, 713.

Leach, — Jr. Chem. Soc., 26, 1210.

LePage, — Arch. Pharm. (2) 97, 240.

Milobendzki, Kostanecki and Lampe, — ■ Ber., 43, 2163.

Perkin, — Jr. Chem. Soc., 85, 63.

Rupe, — Ber., 40, 4909.

Thompson, — Pharm. Jr. Trans. 23.

Vogel and Pelletier, — Jr. de Pharm., 50, 259.

Vogel, — Ann., 44, 297, B. Report. Pharm., 27, 274.

902 Wisconsin Academy of Sciences , Arts, and Letters.

III. PIGMENTS REFERABLE TO HYDROCARBONS OF THE CONFIGURA¬

TION SEVEN DOUBLE BONDS AND THREE CYCLES.

Pigments referable to phenyl- dihydronaphthalene .

One pigment apparently a derivative of the above hydrocarbon

has been isolated from plants. This is trifolitin, probably a

tetrahydroxy derivative of phenyl-naphthaquinone.

O

PhenyPnaphthaqulnone

Trifoletin was first isolated by Power and Solway,1 in 1910,

from the flowers of red clover, Trifolium pratense. Trifolitin,

which crystallizes in yellow crystals, is apparently a tetrahy¬

droxy derivative of phenyl-naphthaquinone. It is readily

soluble in alcohol and glacial acetic acid, sparingly soluble in

chloroform, ether, and benzene. In alkaline solutions it dis¬

solves with a bright yellow color, in sulphuric acid with a yel¬

low color. It dyes mordanted cotton a bright yellow.

1 Jr. Chem, Soc.» 97, 241.

Wdkeman— Pigments of Flowering Plcmts.

903

IV. Pigments referable to hydrocarbons of the configura¬

tion SIX DOUBLE BONDS AND FOUR CYCLES.

Pigments referable to methyl-anthracene.

CH,

i

CH®

QH CH OOH

Chryiarobin

CH CH * CH

Methyl Anthracene

Chrysarobin 1 — a trihydroxy derivative of methyl-anthracene

occurs along with dichrysarobin, dichrysarobin methyl ether and

another similar substance C17H1804 in Goa powder, obtained

from Andira araroba,* 2 also along with chrysophanic acid and

emodin in Rhamnus purshiana .3 *

Chrysarobin and chrysophanic acid were formerly thought to

be identical but the work of Hesse4 and later that of Jowett and

Potter5 have shown the latter to be a derivative of methyl

anthraquinone, while the former is a derivative of methyl anth¬

racene. Chrysorobin is however readily oxidized to chryso¬

phanic acid.

Chrysorobin crystallizes in small yellow tabular crystals and

needles. It melts at 177°. It is easily soluble in chloroform,

acetic acid and benzene, more difficultly soluble in alcohol and

ether. It is insoluble in water and ammonia but soluble in

sulphuric acid with a yellow color, insoluble in very dilute po¬

tassium hydroxide but soluble in a stronger solution with a yel¬

low color. Upon exposure to the air in alkaline solution it goes

to chrysophanic acid.

•Jr. Chem. Soe., 81, p, 1575.

2 Ber., 11, p. 1603; Ann., 309, p. 32, Pharm. Jr., 5, p. 721.

•Am. Pharm. Assoc., 52, p. 288 (1904).

•Ann., 309, p. 32.

•Jr. Chem. Soc., 81, p. 1573; 83, p. 1327.

904 Wisconsin Academy of Sciences, Arts, and Letters.

PIGMENTS REFERABLE TO HYDROCARBONS OF THE FORMULA OF SAT¬

URATION CnH2n-24.

Falling under this degree of saturation are the isomeric car¬

otin and lycopin, hydrocarbons of unknown constitution, prob¬

ably derivatives of fulvene.1

CH - CH

CH CH

fetes*

Carotin is the yellow pigment of the carrot, Dances carota. It

is supposed to be very widely distributed in the plant kingdom,

being the yellow pigment which almost universally accompan¬

ies chlorophyll. Carotin was probably isolated by Fremy2 as

early as 1865 and later by others investigators who obtained red

crystalline substances from green leaves. It is probable that

the chrysophyll of Hartsen,3 the erythrophyll of Bougarel4 and

the xanthin of Dippel5 were identical with carotin.

In 1885 Armand6 easily obtained from dried green leaves,

by extraction with petroleum ether a yellow pigment which, puri¬

fied with ether, formed orange red crystals. To this substance

which corresponded with the pigment from carrots Armand

assigned the formula C26H38. Later investigations by Will-

staetter7 have shown the true formula to be C40H56.

Lycopin, isomeric with carotin is the red pigment of the to¬

mato, Lycopersicum escnlentum. This pigment was formerly

supposed to be identical with caroten. In 1904, Montanari8

recognized its difference from carotin and called it dicarotin,

C52H74 (Carotin C26H37). According to the later work of

1 Zeit. Physiol. Chem., 64, p. 47.

2C. r., 61, p. 189.

8 Arch., Pharm., 207, p. 136.

4 Ber., 10, p. 1173.

B Flora, 1878, p. 18.

«C. r., 100, p. 751; 102, p. 1119, 1319.

7 Ann., 355, 1.

8 Staz. sperim. arga. ital., 37, p. 909. Wehmer, p. 686.

W aheman— Pigments of Flowering Plants. 905

Willstaetter2 it is isomeric with carotin, the formula of each be-

ing C40H66.

Xanthophyll8 (C40H56O2) is probably referable to a hydro¬

carbon of this degree of saturation. It appears to accompany

chlorophyll and carotin. Xanthophyl crystallizes in yellow

crystals. It is easily soluble in acetone but difficultly soluble in

petroleum ether and easily affected by light.4 Whereas carotin is

easily soluble in petroleum ether, difficulty in acetone, and is

unaffected by light.

Other studies of Carotin have been made by Hansen,8

Tschirch,® Sehunck 10 and Tsweth.* 11

PIGMENTS REFERABLE TO HYDROCARBONS OF THE DEGREE OF SAT¬

URATION CnH2n-34.

One pigment of known constitution falling under this degree

of saturation has been isolated. This pigment is dichrysorobin,

referable to di (methyl-dihydroanthracyl. )

* Zeit. Physiol. Chem.» 64, p. 47.

* Czapek, Biochemie der Pflanzen (1913) I. p. 683.

* B., Bot. Ges., 22, p. 414.

•Site, her. phys. med. Ges., Wuerzburg (1888).

* B. Bot. Ges., 14, p, 76 ; Bot. Zentr., 67, p. 78.

1# Froc. Roy. Soc., 63, p. 389; 66, p. 177; 72, p. 166.

11 B. Bot Ges., 24, p. 384.

906 Wisconsin Academy of Sciences , Arts, and Letters.

COH

C6H2(OH):

,/ n,

\,„/

'COH

QH3CH3 c6h2(oh)2;

CH

L

\™/

CH

J

Dichrysarobin is a partial dehydration product of octahydroxy

di ( methyldihy droanthracyl ) .

Dichrysarobin1 and the methyl ether of dichrysarobin occur

along with chrysarobin in goa powder obtained from Andira

araroba.2

Dichrysarobin crystallizes in orange colored tabular crystals

which are soluble in ethyl acetate and acetic acid but insoluble in

benzene (distinction from chrysarobin) it is more readily oxi¬

dized to chrysophanic acid, in alkaline solution than chrysarobin.

note. The writer wishes to acknowledge her indebtedness to

Mills College, the woods and gardens of which were generously

opened to her for the collection of plant material. She also

desires to extend thanks to her colleagues at Wisconsin, who have

freely criticised her work, especially to Professor E. R. Miller,

who has kindly placed at her disposal the results of his obser¬

vations along this line, and to Professor L. R. Ingersoll of the

Department of Physics, who read and criticised part of the

introductory chapter. Above all she wishes to express her

gratitude to Professor Edward Kremers, who first introduced

her to the study of plant pigments, and whose enthusiastic in¬

terest and patient supervision have been her inspiration and

guide.

1 Jr. Chem. Soe., 81, p. 1575.

* B., 11, p. 1603; Ann., 309, p. 32.

Du Mez — The Galenical Oleoresins.

907

A CENTURY OF THE UNITED STATES PHARMA¬

COPOEIA, 1820-1920.

I — The Galenical Oleoresins.

By Andrew G. Du Mez.

908

Wisconsin Academy of Sciences, Arts, and Letters ,

CONTENTS

PART I— GENERAL

Page

Historical Introduction .

Definition .

Drugs used .

Solvents used .

Methods of preparation .

Apparatus employed .

Yield .

Chemistry .

Physical and chemical proper¬

ties . .

Physical properties . . .

Color . . .

Odor .

Taste . . .

913 Consistence . .

918 Solubility .

920 Specific gravity .

921 Refractive index .

926 Chemical properties .

933 Loss in weight on heating. .

952 Ash content .

952 Acid number . .

Saponification value .

953 Iodine value . . .

953 Special tests .

953 Qualitative tests .

954 Quantitative tests .

954 Adulterations .

PART II— INDIVIDUAL OLEORESINS

Page

Oleoresin of aspidium . 965

Synonyms . 965

History . 967

Drugs used, its collection, pres

ervation, etc . 968

U. S. P. text and comments

thereon . 973

Yield . 980

Chemistry of the oleoresin and

of the drug from which

prepared . 985

Constituents of therapeutic

importance . 992

Physical properties . 992

Color . . 992

Odor . 993

Taste . 993

Consistence . 993

Solubility . 993

Specific gravity . 994

Refractive index . 996

Chemical properties . 998

Loss in weight on heating . . 998

Ash content . 999

Acid number . 1900

Saponification value . 1001

Iodine value . 1003

Other properties . 1004

Special qualitative tests .

Tests for filicin .

Austrian Pharmacopoeia. .

Netherlands Pharmacopoeia

Hungarian Pharmacopoeia

Test for starch .

German Pharmacopoeia. . .

Test for oleoresin of Dryop-

teris spinulosa .

Hausmann’s method .

Test for castor oil .

Test for copper .

Special quantitative tests .

Methods for the determina¬

tion of fllix acid .

Method of Kremel .......

Method of Bocchi .

Method of Kraft .

Method of Fromrne (orig¬

inal) . . .

Method of Fromrne (im¬

proved) . .

„ Method of Stoeder .

Comparison of above

methods .

Methods for the determin¬

ation of crude filicin . . .

Method of Rulle .

Page

954

955

956

957

959

960

961

962

964

Page

1005

1095

1006

1007

1097

1908

1008

1009

1010

1011

Du Mez—The Galenical Oleoresins.

909

Page

Method of Daccoma and

Scoccianti . 1011

Method of Schmidt . . 1011

Method of Fromme . 1011

Influence of different alka¬

lies on yield of crude

filicin . 1012

Crude filicin content of

laboratory properations 1013

Crude filicin content of

commercial samples ... 1014

Physiological tests ......... 1015

Method of Yagi . 1015

Adulterations . 1016

Oleoresin of capsicum . 1017

Synonyms . 1017

History . 1017

Drugs used, its collection,

preservation, etc . 1017

U. S. P. text and comments

thereon . . . 1018

Yield . . . 1023

Chemistry of the oleoresin

and of the drug from

which prepared . 1027

Constituents of therapeutic

importance . . 1030

Physical properties . . 1030

Color . . . 1030

Odor . . . 1030

Taste . . . 1030

Consistence . . 1030

Solubility . 1031

Specific gravity . 1031

Refractive index . 1032

Chemical properties . 1033

Loss in weight on heating 1033

Ash content . . . 1033

Acid number . . . 1034

Saponification value . 1035

Iodine value . 1036

Special quantitative tests ... 1037

Physiological test . 1037

Adulterations . 1038

Oleoresin of cubeb . 1038

Synonyms . . 1038

History . . . . . 1038

Drug used, its collection,

preservation, etc. ...... 1040

U. S. P. text and comments

thereon . 1040

Yield . 1045

Chemistry of the oleoresin

and of the drug from

which prepared . 1049

Constituents of therapeutic

importance ........... 1053

Page

Physical properties . 1053

Color . . 1053

Odor . . 1053

Taste . 1054

Consistence . 1054

Solubility . 1054

Specific gravity . 1054

Refractive index . 1055

Chemical properties . 1956

Loss in weight on heating 1056

Ash content . . 1057

Acid number . 1057

Saponification value . 1058

Iodine value . 1059

Other properties . 1060

Special qualitative tests .... 1060

Method of Dietrich . 1061

Method of Gluccksmann . . 1062

Austrian Pharmacopoeia . . 1062

French Pharmacopoeia ... 1062

Swiss Pharmacopoeia .... 1062

Hungarian Pharmacopoeia 1062

German Pharmacopoeia . . 1063

Special quantitative tests ... 1963

Kremel’s method for the

determination of cube-

bic acid . 1063

Adulterations . . 1063

Oleoresin of ginger . 1064

Synonyms . 1064

History . . 1064

Drug used, its collection,

preservation, etc . 1064

U. S. P. text and comments

thereon . 1066

Yield . 1069

Chemistry of the oleoresin

and of the drug from

which prepared . . . 1073

Constituents of therapeutic

importance ............ 1076

Physical properties . 1077

Color . . 1077

Odor . 1077

Taste . . . 1077

Consistence . 1977

Solubility . 1077

Specific gravity . . 1078

Refractive index . . 1078

Chemical properties........ 1079

Loss in weight on heating 1079

Ash content . 1080

Acid number . 1081

Saponification value . 1081

Iodine value . 1082

Special qualitative tests .... 1083

Tests for oleoresin of cap¬

sicum . 1083

910 Wisconsin Academy of Sciences, Arts, and Letters .

Page

Method of Garnet and

Grier . . 1084

Method of La Wall ...... 1084

Method of Nelson . . . 1084

Special quantitative tests ... 1085

Methods for the estimation

of the gingerol content 1085

Method of 'Garnet and Grier 1085

Physiological tests ....... 1086

Adulterations . . 1087

Oleoresin of lupulin. . . . , 1087

Synonyms . . 1087

History . . 1087

Drug used, its collection

preservation, etc. ...... 1088

U. S. P. text and comments

thereon ............... 1089

Yield . . 1092

Chemistry of the oleoresin

and of the drug from

which prepared ....... 1093

Constituents of therapeutic

importance . . 1096

Physical properties . 1097

Color . . 1097

Odor ... _ ............ 1097

Taste . . 1097

Consistence ............. 1097

Solubility ............... 1097

Specific gravity .......... 1098

Refractive index ........... 1098

Chemical properties ........ 1099

Loss in weight on heating 1099

Ash content ............. 1100

Acid number ............ 1101

Saponification value ..... 1101

Iodine value . . 11 Q 2

Adulterations ............. 1103

Oleoresin of parsley fruit .... 1103

Synonyms . . 1103

History .................... 1104

Drug used, its collection,

preservation, etc. ...... 1194

U. S. P. text and comments

thereon ............... 1105

Yield . . 1107

Chemistry of the oleoresin

and of the drug from

which prepared ....... 1108

Constituents of therapeutic

importance ............ 1110

Page

Physical properties ........ 1111

Color . . 1111

Odor ............. _ . 1111

Taste . . 1111

Consistence ............. 1111

Solubility ............... 1111

Specific gravity. .......... 1111

Refractive index . 1112

Chemical properties ........1113

Loss in weight on heating 1118

Ash content ............ 1118

Acid number . 1114

Saponification value ...... 1114

Iodine value ............ 1115

Adulterations .............. 1116

Oleoresin of pepper .......... 1116

Synonyms ......... i ...... . 1116

History ................. 1116

Drug used, its collection,

preservation, etc. ...... 1117

U. S. P. text and comments

thereon . 1118

Yield . . 1122

Chemistry of the oleoresin

and of the drug from

which prepared . . 1124

Constituents of therapeutic

importance . . 1128

Physical properties . 1128

Color .......... _ 1128

Odor . . 1128

Taste . . 1128

Consistence ............. 1128

Solubility . . 1128

Specific gravity ......... 1128

Refractive index ........ 1129

Chemical properties ....... 1130

Loss in weight on heating 1130

Ash content . 1131

Acid number ............ 1132

Saponification value ..... 1132

Iodine value . . 1183

Special quantitative tests . . 1134

Method for the estimation

of the piperine content 1134

Adulterations . . 1135

BIBLIOGRAPHY . . 1135

INDEX TO BIBLIOGRAPHY 1190

Du Mez — The Galenical Oleoresins.

911

Abbreviations Used for the Titles of Pharmacopoeias and

Treatises on Pharmacy.

Allg. P.-—S trump, Allgemeine Pharmakopde.

Argent. P. — Argentine Pharmacopoeia- — Farmacopoea Na¬

tional Argentina.

Aust. P. — Austrian Pharmacopoeia — Pharmacopoea Austriaca.

Bad. P. — Baden Pharmacopoeia Pharmacopoea Badensis.

Belg. P. — -Belgian Pharmacopoeia — Pharmacopoea Belgica.

Bern. P. — -Bernese Pharmacopoeia — Pharmacopoea Bernensis.

B. P. — British Pharmacopoea .

B. P. C. — British Pharmaceutical Codex.

Comp, to the U. S. P. — Companion to the United States Phar¬

macopoeia.

Dan. P. — Danish Pharmacopoeia — Pharmacopoea Danica.

Dan. Mil. P. — Danish Military Pharmacopoeia.

Diet, of Pharm. Sc. — Schweringer, Dictionary of Pharmaceu¬

tical Science.

Fin. P. — Finnish Pharmacopoeia — Pharmacopoea Fennica.

Fr. P. — French Pharmacopoeia — Pharmacopoee Francaise.

G. P. — German Pharmacopoeia — Pharmacopoea Germanica.

Geiger’s P. — Geiger’s Pharmacopde.

Han. P. — - Hannoverian Pharmacopoeia — Pharmakopde fur das

Koenigreich Hannover.

Hess. P. — Hessian Pharmacopoeia — Pharmakopde fur das

Kurfuerstenthum Hessen.

Hung. P. — Hungarian Pharmacopoeia — Pharmacopoea Hun-

garica.

Ital. P. — Italian Pharmacopoeia - — Farmacopoea Ufficiale del

Regno d’ It alia.

Jap. P. — Japanese Pharmacouceia — The Pharmacopoeia of

J apan.

King’s Am. Disp. — King’s American Dispensatory .

Mex. P. — Mexican Pharmacopoeia — Pharmacopoea Mexicana.

Nat. Stand. Disp. — National Standard Dispensatory.

Neth. P. — Netherlands Pharmacopoeia — Pharmacopoea Neder-

landica — N ederlandische Apotheek.

Nor. P. — Norwegian Pharmacopoeia — Pharmacopoea Nor-

vegica.

912 Wisconsin Academy of Sciences , Arts, and Letters.

Port. P. — ' Portuguese Pharmacopoeia — - Pharmacopoea Portu-

gueza.

Pruss. P. — Prussian Pharmacopoeia — Pharmacopoea Borus-

sica.

Roum. P. — Roumanian Pharmacopoeia — Pharmacopoea Ro-

mana.

Russ. P. — Russian Pharmacopoeia — Pharmacopoea Russica.

Schlesw. Holt. P. ■ — Schleswig-Holstein Pharmacopoeia — Phar -

makopoe fur Schleswig und Holstein.

Sp. P. — Spanish Pharmacopoeia — Farmacopoea Oficial Es-

pahola.

Swed. P. — Swedish Pharmacopoeia — Pharmacopoea Suecica.

Swiss P. — Swiss Pharmacopoeia — Pharmacopoea Helvetica.

U. S. Disp. — United States Dispensatory.

U. S. P. — United States Pharmacopoeia.

Univ. P. — Hirsch, Universal-Pharmacopde.

Yer. P. der Lond., Edinb. und Dub . Med. Coll. — Vereinigte

Pharmacopoeen der Londoner, Ediriburgher, und Dubliner

Medicince Collegien.

Du Mez — The Galenical Oleoresins.

913

PART I — GENERAL

Historical Introduction

The type of galenical preparation now known as an oleoresin

has been official in the United States Pharmacopoeia since 1850,

the oleoresins of cnbeb and pepper being the first members of

this class of preparations to receive recognition, however, under

the title of fluid extract.

The suggestion for the name oleoresin appears to have come

from Buchner though first applied as the name of a galenical

by Peschier. The latter, in 1825, had prepared an ethereal

extract of male fern which he designated Huile de Fong ere Male,

To this name, Buchner objected, suggesting the title Extractum

resinosum. In reporting Peschier ’s work, however, Buchner

speaks of the constituents of the ethereal extract as the oelharzige

Bestandtheile of male fern, and later in his account, he refers to

the finished preparation as the oelharziges Extract , i. e. an

oleoresinous extract. It would appear, therefore, that when

Peschier, in his second account (1828), speaks of an oleoresine,

our English oleoresin, he evidently took his suggestion from

Buchner’s use of the German attribute, oelharzig.

The suggestion of Buchner, that the above mentioned pre¬

paration of male fern be called an extract, appears to have met

with general favor throughout Europe as is indicated by its title

in the various European pharmacopoeias, past and present.

Likewise, such other members of this class of preparations as

have received recognition in the European countries are to be

found in the respective pharmacopoeias of these countries under

the heading, extracta. In the United States, a latinized form

of Peschier ’s title, oleoresine , has been adopted and these pre¬

parations are officially known as oleorsinae.

The following table of titles will give a fair idea of the early

development of the synonymy of these preparations :

914

Wisconsin Academy of Sciences , Arts , and Letters.

Table I. Early titles of oleoresms

1825. Huile de Fougere Mdle — Peschier.

1826. Extraction Filicis maris resinosum — Buchner.

1827. Extractum oleo-resinosum Filicis — Brandes.

Oleum Filicis Maris — Yan Dyk.

Oleo-Besina Filicis, Peschier — Ver. P. d. Lond., Edinb. and Dub.

Med. Coll.

1828. Oleoresine de Fougere Mdle - — Peschier.

Extrait oleoresineux de Cubebe — Dublanc.

1829. Extractum Filicis aethereum — App. to Pruss. P.

Aetherisches FarnTcraut extract — App. to Pruss. P.

1832. Extractum Filicis oleo-resinosum — Jourdan, Univ. P.

1834. Piperoide du Gingembre — B6ral.

1841. Extractum Badicis Filicis Maris aethereum — Bad. P.

Aetherisches Farrnkrautwurzel Extract — Bad. P.

Extractum Cub eb arum aethereum — Bad. P.

Aetherisches Cuhehen Extract — Bad. P.

1845. Extractum Filicis Maris aethereum — Geiger’s P.

Farrnwurzelextract — Geiger ’s P.

Extrait ethdre de Cuhebe — Geiger ’s P.

Oleoresinous Extract of Cubebs — Bell

Ethereal Extract of Cubebs — Procter.

1849. Oleoresinous Ethereal Extracts — Procter.

1852. Extractum Filicis Maris aethereum — Swiss P.

Extrait oleo-rdsineux de Fougere — Swiss P.

Huile de Fougere de Peschier — Swiss P.

1854. Extractum Stipitum Aspidii — Nor. P.

1857. OUo-Besineux de Cubebe — Garot and Schaeuffele.

1859. Oleoresina (ae) — Procter.

1863. Oleoresina Capsici — U. S. P.

Oleoresina Cubebae — U. S. P.

Oleoresina Lupulinae — U. S. P.

Oleoresina Piperis — U. S. P.

Oleoresina Zingiberis — U. S. P.

As becomes apparent from the preceding table, oleoresins be¬

came a recognized class of galenical preparations with their in¬

troduction into the United States Pharmacopoeia of 1860. The

name, as applied to a class of galenicals, appears to have been sug¬

gested by Procter in 1846. Although this term thereby ac¬

quired a dual meaning,1) it was not only shorter, but in other

respects more convenient than extracta aetherea, previously in

use in some of the European pharmacopoeias. The disadvan-

As a class of natural plant products and as a class of galenicals.

Du Mez- — The Galenical Oleoresins.

915

tage accruing from the substitution of oleoresina for extracta

aetherea lay in the fact that as a sub-class they were removed

from the other sub-classes of extracts:- e. g., the extracta (solida),

extracta fluida , etc. With the substitution of acetone for ether

as an extracting medium, in the eighth- revision of the United

States Pharmacopoeia , it is possibly fortunate that the designa¬

tion extracta aetherea never gained a footing in this country.

The preparation of this particular class of galenicals was de¬

pendent upon the use of ether. Although, a number of chem¬

ists before the eighteenth century had obtained some ether as an

ingredient of a mixture resulting from the action of sulphuric

acid upon alcohol, it appears that the first commercial ether

was prepared in 1730 by Frobenius,1) who, however, kept his

process a secret. The use of the distillation residues for the

preparation of more ether, known to Frobenius, was emphasized

by several German chemists, and caused a considerable reduc¬

tion in the price of this article. Thus Cadet, in 1774, pointed

out that he could sell an ounce of ether at 40 sous,2 3) whereas

Baume had sold it at 12 livres. But even with this reduction

in price, ether does not appear to have been a common phar¬

maceutical commodity at that time. Thus, e. g., Hermbstaedt8)

in 1792, mentions ether and enumerates its properties evidently

for the reason that it is of pharmaceutical interest primarily be¬

cause it is an ingredient of Liquor anodynus mineralis Hoff -

manni. However, it should be remarked that Baume mentioned

it in 1762 as a solvent in the preparation of resin of Jalap,4) and

in 1790, 5 ) he described its use in the preparation of ethereal

tinctures.

The first positive reference concerning - the use of ether as a

solvent in the preparation of a galenical of the type of our pres¬

ent oleoresins, that appears in the literature, is to be found in

Peschier’g report (in 1825) on the preparation of the Huile de

Fougere Male, the present oleoresin of aspidium. As a result

of the almost immediate popularity of this preparation, other

pharmacists were induced to experiment with ether in attempting

duplicate or modify Pesehier?s process. However, none of the

1 Kopp. Geschicht. d. Chem., vol. 4» p. 302.

2 Ibid.

3 Grundriss d. exp. Phar.ro., part 2, p. 161.

4 Elements de Pharm. (1872), p. 284.

5 Ibid. (1790), p. 262.

916 Wisconsin Academy of Sciences , Arts , and Letters.

early workers attempted to employ it in the extraction of other

plant drugs, and it was not until 1834, when Beral again called

attention to the use of ether as a solvent in his preparation of

Piperoide du Gingembre, our present oleoresin of ginger, that

its value in the extraction of oleoresinous drugs appears to have

been recognized. From then on, however, its use seems to have

widened rapidly as the French Pharmacopoeia of 1839 contained

no less than nineteen ethereal tinctures. The increase in the

number of oleoresins was not as rapid as might be expected in

view of the statement concerning the ethereal tinctures. Only

two other members of this class of preparations made their ap-

appearance before 1850, namely, the Extraction Cubebarum

aetkereum and the Extractum Seminis Cinae aethereum.

Some idea of the rate at which the Extracta aetherae , our pres¬

ent oleoresins, came into existence and were given official recog¬

nition will become evident from the following:

In the Prussian Pharmacopoeia of 1829, but one such prepara¬

tion was official, namely,

Extractum Filicis aethereum.

The Baden Pharmacopoeia of 1841 contained three prepara¬

tions of this class, viz:

1. ) Extractum Badicis Filicis Maris aethereum.

2. ) Extractum Cubebarum aethereum.

3. ) Extractum Seminis Cinae aethereum.

The Danish Pharmacopoeia of 1850 contained two prepara¬

tions of this class, viz:

1. ) Extractum Cubebarum aethereum.

2. ) Extractum Filicis Maris aethereum.

The third edition of the United States Pharmacopoeia , which

appeared in 1851, included two fluid extracts prepared with

ether as a menstrum, viz:

1. ) Extractum Cubebae fluidum.

2. ) Extractum Piperis fluidum.

Du Mez — The Galenical Oleoresins.

917

The Belgian Pharmacopoeia of 1854 recognized no less than

seven ethereal extracts, viz:

1) Extrait 4there de Fougere

2) Extrait Cthere de Cantharides

3) Extrait Cthere de Croton

4) Extrait ethere de Cubebe

5) Extrait ethere de d’Aunee

6) Extrait ethCre de Bois garu

7) Extrait ethere de Semen-eontra

It will be seen from the above array of ethereal extracts of¬

ficial in European pharmacopoeias that the introduction of

oleoresins into the fifth edition of the United States Pharmaco¬

poeia, which appeared in 1863, was well prepared.

Procter is commonly given credit for having introduced oleore¬

sins into American materia medica. That he was instrumental

in bringing them to the attention of the representatives of the

regular medical school, and that he obtained a place for them

in the United States Pharmacopoeia, possibly no one has reason

to doubt. A review of the early American literature on this

subject not only reveals this fact, but it also brings out the fact

that Procter appears to have been ignorant in large part of the

use of this class of preparations in Europe,1) for nowhere does

he mention it. It is note-worthy that it was a medical prac¬

titioner (Goddard) who first drew Procter’s attention (1846),

not to a typical representative of this class, but to the prepara¬

tion of Dublanc which was a representative of the extracta oleo-

resina made by a very cumbersome process, now long discarded

as being as unscientific as it is impractical. In the same year,

the English pharmacist, Bell, had his attention drawn to this

same preparation by Yore, thus showing that valuable prepara¬

tions not advertised were ignored, while a quasi scientific pre¬

paration heralded about apparently attracted general attention.

To what extent the Eclectic school of medical practioners

contributed to the popularization of this class of galenicals be¬

fore 1860 cannot be definitely stated from the scanty informa-

1 That Proctor did know of Mohr’s work on this class of preparations

becomes apparent when the fact is recalled that he adapted Redwood’s

translation of Mohr’s Pharmaceutische TechniJc to American pharmacy under

the title of Mohr, Redwood & Procter’s Pharmacy in 1849, and that he had

previously reviewed Redwood’s translation in the Am. Jour, of Pharm.

918 Wisconsin Academy of Sciences , Arts , and Letters.

tion at hand. However, it is interesting to note that the

American Dispensatory of 1854, gives the formula of Robinson

for preparing the ethereal oil of xanthoxylum , the present

Eclectic oleoresin of xanthoxylum. The same is directed to be

prepared by extracting the bark with ether and subsequently

removing the ether by evaporation — a process similar to the one

now employed in preparing the official oleoresins. Of but

slightly lesser interest is the advertisement of Wm. S. Merrel

which appeared in the Eclectic Medical Journal in 1855. Under

the heading, Class II. — Soft resinoids and oleo-resins, etc., the

following preparations were listed:

Apocynin

Ascelepedin

Aletrin

Eupurpurin

Iridin 1

Ptelein, or Oil of Ptelea

Oil of Lobelia

Oil of Xanthoxylum

Oil of Capsicum

Oil of S tilling ia

Oil of Male Fern

(from Dogsbane).

(from Pleurisy Root),

(from Star Root).

(from Queen of the Meadow),

(from Blue Flag).

(from Water Ash).

(from Lobelia Seed).

(from Prickley Ash).

(from African Cayenne).

In view of the fact that these preparations were already being

manufactured and advertised commercially in 1855, there can be

but little doubt that the Pharmacopoeial Revision Committee of

1860 must have been aware of their existence and have been in¬

fluenced to some extent thereby.

Definition

Oleoresins, as a class of galencials, are extracts prepared, as

a rule, with the aid of a highly selective solvent. Ether is the

solvent usually employed for this purpose at the present time,

whereas, acetone was directed to be used in the eighth revised

edition of the United States Pharmacopoeia. Other solvents of

this nature, namely: petroleum ether, benzene, chloroform, car¬

bon tetrachloride, et cetera, have been used, but have not been

officially recognized. The oleoresin of cubeb is an exception

1 Prof . John King- is said to have prepared and used Irisin (identical with

Iridin) in 1844. Letter from J. U. Lloyd to Edward Kremers (1906).

Du Mez—The Galenical Oleoresins. 919

to the rule as alcohol is the menstruum directed to be used

in its preparation.

These preparations derive their name from the fact that

the drugs from which they were originally prepared con¬

tained appreciable amounts of fatty or volatile oil and resin,

substances, for which ether and acetone were recognized to

be good solvents. They do not by any means necessarily cor¬

respond to the so-called natural oleoresins, which consist for

the main part of volatile oil and resin; but, in some cases,

are products relatively poor in one or both of these constit¬

uents. Thus, for example, the oleoresin of capsicum contains

little or no volatile oil and only a small amount of resin,

while the oleoresin of parsely is practically free from resin.

Furthermore, these preparations are not always liquid as is gen¬

erally stated. The oleoresin of lupulin, for instance, is of the

consistence of a soft extract when prepared according to phar-

macopoeial directions, and tends to become firmer with age

owing to the transformation of the so-called soft into hard resin.

The manner in which the oleoresins have been defined in the

various text books and treatises on pharmacy is brought out by

the following examples, which are representative of the periods

corresponding to the different decennial revisions of the United

States Pharmacopoeia:

“Oleoresinae — Their peculiarity is that they consist of principles which

when extracted by means of ether, retain a liquid or semi-liquid state

upon the evaporation of the menstruum, and at the same time have the

property of self-preservation, differing in this respect from the fluid ex¬

tracts which require the presence of alcohol to prevent decomposition.

They consist chiefly, as their name implies, of oil, whether fixed or volatile,

holding resin and sometimes other active matter in solution.” U. S. Disp.

(1870), p. 1315.

“Oleoresinae, Oleoresins — Mixtures of volatile oils with resins prepared

by exhausting certain drugs containing both together, the menstruum be¬

ing usually ether which extracts both. The menstruum or solvent is evap¬

orated off, and the usually semi-liquid extract which remains constitutes

the oleo-resin. ’ ’ Oldberg and Wall, Comp, to the TJ. S. P. (1884), p. 721.

“The oleoresins are official liquid preparations, consisting principally

of natural oils and resins extracted from vegetable substances by per¬

colation with ethylic ether. The oleoresins were formerly classed with

the fluid extracts, but they differ essentially from the latter:

1. They do not bear any uniform relation to the drug as fluid ex¬

tracts do, of gramme to cubic centimeter, — the yield of oleoresin obtained

920 Wisconsin Academy of Sciences, Arts, and Letters.

from the drug varying according to the proportion of oil and resin naturally

present :

2. The menstruum used, ethylic ether, extracts principles which are

often insoluble in alcohol or diluted alcohol, and vice versa. Oleoresin of

Cubeb, for instance, is not identical with Fluid Extract of Cubeb:

3. They are without exception the most concentrated liquid prepara¬

tions of the drugs that are produced. ’ ’ Bemington, Pract. of Pharm.

(1894), p. 433.

i ‘ Oleoresins are those substances obtained from vegetable medicines by

means of ether (sometimes alcohol, etc.,) which consist principally of a

fixed or volatile oil and a resin. In some cases the resin will be held in

solution by the oil, while in other cases, it will be precipitated upon stand¬

ing and will require agitation to diffuse and suspend it in the oil. A

third case occurs in which the oil and resin form a more or less perman¬

ent mixture, having the consistency of a very soft extract. ’ ’ King’s Am.

Disp. (1900), p. 1330.

‘ ‘ Oleoresins are ethereal extracts of an oleoresinous nature, obtained

from vegetable drugs by percolation with ether,” Coblenz’s Handbook of

Pharm. (1902), p. 290.

‘ ‘ Oleoresins, Oleore$mae (Oleoresins, L. oleum , oil and resina, resin) —

Natural solutions of resin in volatile oils, extracted by ether, acetone or

alcohol.” Culbreth, Mat. Med. (1906), p. 20.

“The pharmaceutical oleoresins are liquid preparations of drugs con¬

taining volatile oil and resin, obtained by percolation of such drug with

acetone, ether, or alcohol, and subsequent distillation of the solvent from

the dissolved oleoresins.” Arny, Prin. of Pharm. (1909), p. 259.

“Solutions of this class represent the medicinal virtues of the drugs

from which they are made, in a more concentrated form than is possible

in any other. They possess the power of self-preservation, and in this

respect are superior to fluidextracts. Oleoresins consist chiefly of fixed

or volatile oils associated with resin and other constituents; those of¬

ficially recognized, with one exception, are all prepared, ” et cetera.

Caspari, Treat, on Pharm. (1916). p. 354.

Drugs Used, Their Collection, Preservation, Etc.

Since the oleoresins are characterized chiefly by their content

of oil and resin (see definition above), it is evident that they

may be prepared from many of the numerous vegetable drugs)

of which these substances constitute an appreciable part. The

number of such drugs, however, which has actually been used

for this purpose, is comparatively small as is shown in the

table which follows. The table also reveals the fact that nearly

all of these drugs are derived from phenogamous plants and

that they consist, as a rule, of those organs in which oils and

resins are usually present in the greatest abundance.

Du Mez — The Galenical Oleoresins.

921

Table 2 — Drugs from which oleoresins have been prepared.

Phenogams

Capsicum (fruit)

Cardamon (seed)

Chenopodium (fruit)

Clove (unexp. flower)

Conium (leaf)

Croton (seed)

Cubeb (fruit)

Annatto (seed)

Asarum (root)

Anacardium (fruit)

Alkauet (root)

Cypripedium (rhizome)

Eucalyptus (leaf)

Galangal (rhizome)

Ginger (rhizome)

Helenium (flower)

Iris (rhizome)

Kousso (flower)

Lobelia (seed)

Lupulin (strobile)

Matico (leaf)

Mezereum (bark)

Parsley (fruit)

Pepo (seed)

Pepper (fruit)

Pomegranate (root)

Ptelea (bark)

Py rethrum (root)

Sabal (fruit)

Santonica (unexp. flower)

Savine (leaf)

Senecio (root &herb)

Spiraea (herb)

Taxus (leaves)

Xanthoxylum (bark)

Cryptogams

Aspidium (rhizome) Ergot (sclerotium of Claviceps purpurea)

Of the total number of drugs enumerated above, seven have

been utilized in the preparation of the oleoresins official in the

United States Pharmacopoeia, namely:

Parsley

Pepper

Aspidium

Capsicum

Cubeb

Ginger

Lupulin

With respect to the collection (harvesting) of the foregoing

and their preparation for use, there is little of a general nature

to be said as the plants from which these drugs are obtained

differ so widely in their habits. This subject will, therefore,

not be given consideration here, but will be discussed in Part II

under the treatment of the individual preparations.

Solvents Used.

At the present time, ether is the solvent directed to be em¬

ployed in the preparation of the official oleoresins with the ex¬

ception of the oleoresin of cubeb which is prepared with alcohol.

It will be recalled that the first of this class of preparations to

make its appearance, namely, the Huile de Fougere of Peschier,

was also prepared with ether. In fact, ether appears to have

been the only solvent2) given consideration in this connection

by the early European investigators.

1 One animal drug, cantharides, has been utilized for the preparation of

an ethereal extract. This preparation, which was official in the Belgian

Pharmacopoeia of 1854, cannot propterly be classed with the oleoresins since

it contained no resin — the animal organism being free from constituents of

this nature.

a Buchner in 1826 experimented with alcohol in preparing the Extr actum

Filicis resinosum, while Brandes, in 1827, made use of a menstrum con¬

taining both alcohol and ether, namely the Liquor anodynus, for the same

purpose. Later, 1828, Dublanc and Oberdoerffer employed alcohol in the

preparation of the oleoresinous extract of cubeb.

922 Wisconsin Academy of Sciences, Arts, and Letters,'

With the introduction of the oleoresins into the United States

Pharmacopoeia of 1860, and their extensive use in this country,

a number of American pharmacists were lead to the conducting

of experiments, which had for their main object the discovery of

a solvent less expensive and less dangerous to handle than ether.

We must, however, note that prior to this time (1860) an at¬

tempt was made by Berjot, a Frenchman, to use carbon disul¬

phide for the purpose of preparing the Extrait oleo-resineux de

Cubehe. Garot and Schaeuffele, in 1857, in a paper on Berjot ?s

preparation showed that nothing was gained by its use, as two

and one-half times as much carbon disulphide as ether was re¬

quired to extract the drug. Furthermore, the removal of the

last traces of this solvent was a matter of considerable difficulty.

The solvent which first appears to have suggested itself to

American investigators was benzin as is indicated in the publi¬

cations of Procter, Maish, Trimble and others. The first ac¬

count of its use in this connection appeared in 1866, when

Procter published his results on the preparation of the oleoresin

of cubeb. The following table shows the relative value of alco¬

hol, benzin and ether for the extraction of cubeb as found by

Procter.

Table 3. — Yield of oleoresin of cubeb.

While Procter could find no objection to the use of alcohol as

a solvent in the preparation of this oleoresin, he advised against

the use of benzin as he stated that it did not extract the cubebin

completely.

Simultaneously with the above publication of Procter, there

appeared an account of a general method for preparing the

oleoresins by Eittenhouse. The latter also worked with benzin,

but employed it as a “ follow up ’ ? solvent after percolation had

been partially completed with ether. He also experimented

with glycerin and fusel oil, employing them in a similar manner.

In 1872 Maish published a review of the experiments of A, H,

Du Mez~The Galenical Oleoresins.

923

Bolton and M. Roth. The latter of these two men conducted

an investigation on the extraction of ginger and cubebs with

benzin, the former also included capsicum in his series of ex¬

periments. These workers found that ether still extracted

some non-volatile matter after the drugs had presumably been

exhausted with benzin. Further, that, while the benzin oleore¬

sins were all soluble in ether, the ethereal oleoresins of cubeb

and ginger were only partially soluble in benzin, thus confirming

Procter’s work in 1866 on the oleoresin of cubeb.

Henry Trimble was the next investigator1) to experiment to

*any considerable extent with benzin as a solvent. In his re¬

port to the Pennsylvania Pharmaceutical Association, in 1888,

on commercial oleoresins, he stated that while benzin was in his

opinion preferable to concentrated ether for the extraction of

capsicum, it would not answer for the other official oleoresins.

Following is a table showing the comparative extractive powers

of ether and benzin as compiled by Trimble :

Table 4 — Relative extractive power of benzin and ether.

Results similar to the above with respect to the oleoresins of

ginger were reported by Samuel J. Riegel in 1891.

About this time George M. Beringer became interested in the

preparation of the oleoresins, and in 1892, he published an ac¬

count of his researches, in which he had employed not only

ether and benzin as extracting menstrua, but also the heretofore

little used solvent, acetone. With respect to benzin, he ar¬

rived at the same conclusions as did Trimble, viz: that its use

1 In 1877, L. Wolff in an article entitled: The use of Petroleum Benzvnd

in Pharmacy, stated that benzin extracted none of the pungent resin from

ginger, no cubebic acid from cubeb, no piperin from pepper and no san¬

tonin or resin from wormseed.

924 Wisconsin Academy of Sciences , Arts , and Letters.

is not permissable in the preparation of the official oleoresins1),

except, perhaps in the case of capsicum, and then only under

certain restrictions, namely: that percolation be terminated

after 2 cubic centimeters of percolate are obtained for every

gram of the drug, as upon further percolation, the oleoresin be¬

comes almost solid owing to the large increase of palmitin ex¬

tracted. In his experiments with acetone2) he found that, as

with ether, the first portion of the percolate contained nearly

all the medicinal ingredients of the drug. He, however,

continued percolation until the drug was exhausted. The

marc was then removed from the percolator, dried and re¬

percolated with stronger ether; but except in the case of

capsicum no further extractive matter was obtained. The

oleoresins were stated to be of excellent quality and the

yield and properties were nearly the same as when ether

was used. He especially recommended the use of acetone in

preparing the oleoresin of ginger, as he claimed that it was in

every way equal to the preparation made with ether. Follow¬

ing is a table showing Beringer’s results with acetone as com¬

pared with ether and benzin :

Table Relative extractive values of acetone , ether and benzin.

t

1 Two cubic centimeters of percolate were collected for each gram of drug.

8 Represents total extract from which 3 per cent, of wax precipitated, leaving

21.00 percent, of oleoresin.

a Represents total extract which yielded 5.93 per cent, of oleoresin.

1 Pile (1867) confirms this statement in so far as it concerns the oleoresin

of ginger. He states that neither benzin nor ether completely extract ginger,

but that alcohol is the best solvent for this purpose.

8 The acetone used by Beringer was procured from manufacturers of

chloroform as the product obtained from the distillation of wood was found

to consist largely of methyl alcohol and even higher boiling fractions.

Du Mez — The Galenical Oleoresins.

925

From a comparison of the above data with those obtained by

Trimble (See table 4), it would appear that acetone is equally

as serviceable as ether in the preparation of the official oleo¬

resins. Such appears, also, to have been the opinion of the Re¬

vision Committee of the United States Pharmacopoeia of 1900,

as the edition, which became official in 1905, directed that acetone

be employed in the manufacture of those oleoresins which were

formerly required to be prepared with ether.1 That this change

was unsatisfactory is evidenced by the numerous comments

on the subject occurring in the literature, and by the fact that

ether is again directed to be used for this purpose in the ninth

revised edition of the United States Pharmacopoeia.

To those unacquainted with the situation, the above action of

the Revision Committee of 1910, might be taken to indicate that

the matter of the proper solvent to be employed in the manu¬

facture of these preparations has been definitely settled and the

superiority of ether in this respect firmly established. A close

inspection of the preceding reports, along with other informa¬

tion of a similar nature occuring in the literature, would,, how¬

ever, appear to point out, that, as in the case of the oleoresin of

cubeb, other solvents might be advantageously employed in the

preparation of certain of these individuals. In this connection

the use of benzin,2) or better, petroleum ether,3) in the prepara¬

tion of the oleoresins of capsicum and parsley fruit might be

mentioned, or the employment of acetone in the preparation of

the oleoresin of ginger..4) As further evidence of the possibil¬

ities along this line, attention is also called to the experiments

of Wollenweber (1906) on the extraction of aspidium with ben¬

zene, and to the mention of chloroform5) and carbon tetra¬

chloride6) as solvents for the preparation of the oleoresins in

general.

The manner in which these solvents have been employed in

*The most important factor in determining this change was probably the

difference in cost of the two solvents at the time (1900), acetone being the

cheaper. This statement is confirmed in a measure by the fact that now,

since the price of ether has been reduced, owing to its preparation from

denatured alcohol, it is again the solvent officially recognized.

2 See preceding reports by Trimble, Beringer and others.

8 Hyers (1895) also made use of petroleum ether in extracting cubeb.

4 Idris (1898) stated that he found acetone, b. p. 65° C, to be the most

suitable solvent for extracting ginger.

• Dorvault, L’Officine (1898), p. 591.

•Lucas, Practical Pharmacy (1908), p. 149.

926 Wisconsin Academy of Sciences, Arts, and Letters .

the preparation of the various oleoresins will be discussed in

a general way under methods of preparation and in detail under

individual oleoresins.

Methods of Preparation

The methods of preparing the oleoresins as outlined in the

present edition of the United States Pharmacopoeia may he

stated in the following general way: extract the drug com¬

pletely1) by percolation, expose the percolate in a warm place

until the solvent has completely evaporated and separate the

remaining liquid portion from any deposited material. This is

essentially the method of procedure given in most of the late

editions of the foreign pharmacopoeias as well, notable excep¬

tions being the German and Japanese. In the two latter, the

drug is directed to be exhausted by maceration instead of per¬

colation. In detail, the methods described in the United States

Pharmacopoeia, as well as the foreign pharmacopoeias, differ

somewhat with the particular oleoresin as will be brought out to

some extent in the following discussion and more minutely

under the separate treatment of each individual. It is perhaps

needless to state that these methods are not of recent invention

but have been gradually evolved from the numerous experiments

conducted both in this country and abroad.

The first of these experiments dates back to the year 1825,

when Peschier prepared the Huile de Fongere Male, our pres¬

ent oleoresin of aspidium. In his description of the method of

preparation, he directs that the male fern rhizomes be extracted

with successive portions of ether, the decanted ethereal solu¬

tions mixed and evaporated at a gentle heat, and the remaining

oily residue collected and preserved as the finished product.

This is essentially the method which appeared in the early

European pharmacopoeias as is shown in the following typical

example taken from the Prussian Pharmacopoeia of 1830:

Agitate one ounce of powdered male fern root with successive portions

of eight ounces of ether until the ether decants clear. Then mix the

several portions and strain. Distill down to one-fourth of the volume

and evaporate the remainder on a water bath to a thin yellowish-brown

extract.

1 Percolation, in the extraction of capsicum is directed to be discontinued

when eight hundred mills of percolate have been obtained.

Du Mez — The Galenical Oleoresins .

927

An inspection of the above method brings out the fact that

the decanted menstruum was directed to be clarified by the

process of straining. Not only was a great deal of the solvent

lost by evaporation in this procedure, but a very considerable

amount remained adhering to the marc. While some of the

latter was, in actual practice, removed by pressing the drug

on the strainer with the hands, Mohr1) in commenting on the

method stated that, inasmuch as three-fourths of the ether were

often lost in these operations, it was useless to recover the re¬

mainder by evaporation. To overcome this loss to some extent,

he suggested making these preparations in the winter when the

low temperature would be less favorable for the volatilization of

the solvent. As ether, at this time and for many years later,

was a comparatively expensive solvent, it will become apparent

that a change in the method was to be desired.

The first decided departure2 from the above method of pro¬

cedure, which appears to have been given official recognition, is

to be noticed in the Baden Pharmacopoeia of 1841. The method

briefly stated is as follows :

Mix the powdered male fern root with a sufficient quantity of ether to

thoroughly moisten it. Then extract it in a Beal’sche Presse so connected

with a receiving flask that none of the menstruum will be lost by evap¬

oration.

A few years later, in 1846, there appeared a method in the

Swedish Pharmacopoeia which likewise included the process of

displacement, viz:

Macerate the male fern root, cut in small pieces, with ether and extract

in a displacement apparatus.3 Then distill the ethereal solution to one-

fourth of its volume and evaporate the remainder on a water bath to the

consistence of a thin extract.

Even with the use of a pressure percolator, so much ether

was still lost through spontaneous evaporation and through ab-

1 Mohr, Redwood and Procter’s Pharmacy (1849), p. 283.

3 Geiger, in 1827, employed the ReaVsche Presse in the preparation of the

Oleum Filicis Maris, our present oleoresin of aspidium.

8 The apparatus employed for this purpose was most probably the Filtre-

presse of Count Real or the Luft-presse of Dr. Romershausen, as both of

these so-called presses were in general use at that time. In fact, both are

mentioned in connection with the preparation of the extracta by the Prus¬

sian Pharmacopoeia as early as 1834.

928 Wisconsin Academy of Sciences , Arts, and Letters.

sorption by the bag,1) that, in operating with small quantities

of the drug, the recovery of the remainder was scarcely worth

the trouble. The recognition of these defects by Mohr lead

him to construct (in 1847) a special form of apparatus for con¬

tinuous extraction with volatile solvents. However, while

Mohr’s apparatus was a success from an economical standpoint,

there is no evidence to show that it was ever employed to any

extent by the American pharmacist, although, Procter, the

American editor of Redwood’s translation of Mohr’s treatise

on pharmacy, advocated its use in this connection in 1849.

About this time (1846) Procter caused the American pharma¬

cists to become interested in this class of preparations by call¬

ing attention to his improvement upon Soubeiran’s method (as

suggested by Dublanc)2 * * * * *) for preparing the Extrait oleo-resineux

de Cubebe , a preparation similar to our present oleoresin of

cubeb. The following is the method as devised by Procter.

“Take cubebs, in powder, one pound avoirdupois, and sulphuric ether

a sufficient quantity, which is two and one-half to three pounds; intro¬

duce the powder into a displacer, insert the lower end into a bottle that

fits it, add the ether carefully, and cover the top of the filter with a

piece of wet bladder through which several pin holes have been made.8 The

flow should be very gradual and if too rapid, the filter should be partially

closed with a cork. By attention to this point, much less ether will be

required. The ethereal tincture should be introduced into a large retort,

heated by a water bath, and the receiver well refrigerated. The dis¬

tillation should not be hurried toward the last. When five-sixths of the

ether have passed, it should be separated for use, and the evaporation be

continued in the retort, observing to keep the temperature below 120°F,

so as not to volatilize the volatile oil. ”

A few years later (1850), this method (in essential detail)

was given recognition by the United States Pharmacopoeia in

connection with the preparation of the fluid extracts of cubeb

and pepper, later known as the oleoresins of cubeb and pepper,

respectively. For the purpose of better bringing out this

1 Mohr, Redwood and Procter’s Pharmacy (1849), p. 268.

2Although Dublanc described a method for preparing the oleoresinous

extract of cubeb, similar to that of Soubeiran, in 1828, neither method is

given consideration here as both differed to such an extent from the usual

procedure that they had little or no influence on the development of the

present process.

8 From the above description, it appears that the form of displacer used

by Procter was the one described in Mohr, Redwood and Procter’s Phar¬

macy, (1849), p. 270.

Du Mez- — The Galenical Oleoresins.

929

similarity, the following general statement of the pharmacopoeial

methods is also given :

Take of the Drug, in powder, a pound;

Ether a sufficient quantity.

Put the drug into a percolator, and having packed it carefully, pour

the ether gradually upon it until two pints of filtered liquid are ob¬

tained, then distill off by means of a water-bath, at a gentle heat, a pint

and a half of the ether, and expose the residue in a shallow vessel, until

the whole of the ether has evaporated.

a

The methods in general as they were given in the United

States Pharmacopoeia of 1860 differ from the above only in the

quantity of drug and menstruum directed to be taken. Thus,

twelve troy ounces of drug were directed to be subjected to per¬

colation with ether until twenty-four fluidounces of filtered

liquid were obtained, when eighteen fluidounces of the ether

were to be removed by distillation. In the preparation of the

oleoresin of ginger, however, the following method of procedure

was given:

‘ ‘ Take of Ginger, in fine powder, twelve troy ounces ;

‘ 1 Stronger ether twelve fluidounces;

c 1 Alcohol a sufficient quantity.

“Put the ginger into a cylindrical percolator, press it firmly, and pour

upon it the stronger ether. When this has been absorbed by the powder,

add alcohol until twelve fluidounces of filtered liquid have passed. Re¬

cover from this, by distillation on a water-bath, nine fluid-ounces of ether,

and expose the residue in a capsule until the volatile part has evaporated. ’ 1

That the Pharmacopoeial Revision Committee was informed

of the work of Beral in this connection appears to be clearly

evident, as it was he, who first suggested this procedure (1834),

also, in the preparation of the ’oleoresin of ginger, then known

as the Piperoide du Gingemhre.

In 1866, Rittenhouse, commenting on the methods in gen¬

eral, which were given in the United States Pharmacopoeia of

1860, stated that about thirty-six fluid ounces of ether were re¬

quired to extract the drug when proceeding as officially directed.

He, however, conceived the idea of reducing the amount of ether

by a procedure similar to that employed in extracting the gin¬

ger rhizomes. Alcohol did not appeal to him as the proper

** follow upIJ solvent for this purpose and he, therefore, con¬

ducted a series of experiments, in which he made use of benzin,

59— -S. A. CL.

930 Wisconsin Academy of Sciences, Arts, and Letters.

glycerin and fusel oil. The following is the working formula

finally devised by him :

“Take any convenient quantity of the drug; for each ounce thus em¬

ployed, 1 y% fluid ounces of ether, and 1 fluid ounce or q. s. of benzin.

Pack the drug in a suitable apparatus, add the ether, and when it has ceased

to pass, pour on the benzin in the proportion of one fluid ounce for each

ounce of the drug employed or until as much percolate has been obtained

as equals the amount of ether employed. Eecover the ether by distilla¬

tion in the usual manner.”

The process of Rittenhouse does not appear to have received

much attention as there is no subsequent mention of it to be

found in the literature.

During the meantime Procter continued his work on the oleo-

resins and in the same year (1866), he pointed out that prac¬

tically all of the oleoresinous material was to be found in the first

portions of the percolate, and that a considerable quantity of

menstruum could be saved by discontinuing the operation be¬

fore the drug was completely exhausted. The following table

compiled by Procter clearly brings out this point :

Table 6 — Yield of oleoresin of cubeb to ether , alcohol and benzin.

The effect of Procter’s work is noticed in the 1870 and 1880

editions of the United States Pharmacopoeia. Thus, the Phar¬

macopoeia of 1870 directed that twenty instead of twenty-four

fluidounces (as formerly required) of percolate be collected for

every twelve troyounces of drug, while the Pharmacopoeia of

1880 required that only 150 parts of percolate be obtained for

every 100 parts of drug taken. It should also be noted, that

in the 1880 edition, the method of preparing the oleoresin of

ginger was made to conform with that given for the other oleo-

resins.

Du Mez — The Galenical Oleoresins.

931

The United States Pharmacopoeia of 1890, directed, that, in

the preparation of all of the official oleoresins, the drug be com¬

pletely exhausted by percolation with ether. The following

directions for the preparation of the oleoresin of cubeb are

typical of the methods given :

li Cubeb, in No. 30 powder, 500 Gm. ; ether a sufficient quantity.

1 1 Put the cubeb into a cylindrical glass percolator provided with a stop¬

cock, and arranged with a cover and receptacle suitable for volatile liquids.

Press the drug firmly and percolate slowly with ether, added in sue-

sive portions, until the drug is exhausted. Eecover the greater part

of the ether, etc. ”

The next edition of the United States Pharmacopoeia (1900)

contained a number of changes with respect to the methods of

preparing this class of galenicals. Two newT solvents were in¬

troduced, namely, acetone and alcohol ; the method of procedure

was modified in the case of the oleoresin of capsicum, and an

ordinary percolator was directed to be used in the preparation

of the oleoresin of cubeb. The following is a general state¬

ment of the manner in which the oleoresins of aspidium, ginger,

lupulin and pepper were directed to be extracted.

Introduce the powdered drug (degree of fineness specified) into a cylin¬

drical glass percolator, provided with a stop-cock, and arranged with a cover

and receptacle suitable for volatile liquids. Pack the powder firmly, and

percolate slowly with acetone, added in successive portions, until the drug

is exhausted.

The method of extracting the cubeb was stated as follows :

Introduce the powdered cubeb (degree of fineness specified) into a

cylindrical glass percolator, pack the powder firmly, and percolate slowly

with alcohol, added in successive portions, until the cubeb is exhausted.

The method described for the extraction of capsicum was

similar in all respects to the first of the methods given above,

except that percolation was directed to be discontinued when

eight hundred cubic centimeters of percolate had been obtained.

The above changes, except in the case of the oleoresin of

cubeb1) must be attributed to the work of Beringer, an account

of which was published in 1892. Not only did he advocate

the use of acetone in these preparations, but he also pointed out

1 It will be recalled that Procter in 1866 suggested the use of alcohol in

preparing the oleoresin of cubeb. See table 3, page 922.

932 Wisconsin Academy of Sciences , Arts, and Letters.

the advantage of discontinuing percolation short of exhaustion

in the case of capsicum.

The ninth revised edition of the United States Pharmacopoeia

shows but one change in the method of preparing the oleoresins,

viz: ether is directed to be used in those cases where acetone was

employed in the preceding edition.

From the foregoing discussion, it becomes apparent that the

United States Pharmacopoeia , even to the present edition, has

consistently adhered to the process of simple percolation in ex¬

tracting the oleoresinous drugs. This condition not only ap¬

pears strange, in view of the fact that modern methods of

operating with the volatile solvents, such as ether, make use of

some form of continuous extraction apparatus; but is thought

to show a lack of progress as well. Maish, in 1900, suggested

the use of Soxhlet’s apparatus for this purpose and pointed out

its advantage, especially when operating with small quantities

of drug. Reference is also made in this connection to similar

forms of apparatus in most of the present day text-books on

pharmacy.

With reference to the preparation of the oleoresins on a com¬

mercial scale, there is good reason to doubt the employment of

any of the heretofore mentioned methods. The method most

likely in use at the present time is one similar to that offi¬

cial in the British Pharmacopoeia of 1867. The latter, briefly

stated, is as follows:

Exhaust the powdered drug by percolation with alcohol, and distill the

percolate until a soft extract is obtained. Treat this extract with suc¬

cessive portions of ether, mix the ethereal solutions and again distill off

the solvent, when the residue will constitute the oleoresin.

The advantage of this method lies in the fact that it requires

the handling of comparatively small amounts of ether, and

thereby lessens the danger incurred in working with large quan¬

tities of this highly inflammable solvent. The disadvantage is

that alcohol may not extract all of the eother-soluble material

from the drug.

In the preceding survey, only the official oleoresins and their

methods of preparation have been considered. There is, how¬

ever, a number of preparations which have been classed as

oleoresin, in Parrish’s Treatise on Pharmacy , and King’s

American Dispensatory , although, they have never received of-

Du Mez — The Galenical Oleoresins.

933

ficial recognition. They are the so-called Eclectic oleoresins

and are in general directed to be prepared in the following man¬

ner :

Extract the drug by percolation with alcohol or ether and precipitate the

oil and resin by pouring the alcoholic or ethereal tincture into water. Lastly,

separate the product from the water by filtration.

Among the preparations which have been made in this way

are the following: oleoresin of iris (iridin), oleoresin of

xanthoxylum, oleoresin of cardamon (oil of cardamon), oleo¬

resin of ergot, (oil of ergot) and oleoresin of parsley,1) (oil of

parsley) .

In this connection, it should be pointed out that the fore¬

going are liquid preparations and do not constitute the so-called

resinoids, which are solids, although prepared in a similar way.

Apparatus Employed.

Under the two preceding headlines, the preparation of the

oleoresins has been discussed from the standpoint of the solvent

employed in extracting the drug, and with respect to the method

of procedure. There, is however, still another factor of inter¬

est which deserves consideration in this connection, namely:

the form of apparatus made use of.

It will be recalled that the first of this class of preparations

to make its appearance, the oleoresin of aspidium, as originally

prepared, required the use of nothing but a macerating jar,

a cloth strainer and some sort of container, in which the colated

liquid could be collected and exposed to the air to permit the

evaporation of the solvent. Likewise, these were the utensils

generally employed in the experimental stages of the prepara¬

tion of the other members of this class which became known at

an early date. As soon, however, as the oleoresins became

recognized as regular pharmaceutical commodities, the method

of preparation as outlined above was found to be impractical

owing to the complete loss of the solvent by evaporation. In

adapting the same to commercial use, steps were, therefore,

taken to recover as much of the latter as possible. For this

purpose, some form of distilling apparatus was employed, pre-

1 This preparation should not be confused with the oleoresin of parsley

as official in the present edition of the United States Pharmacopoeia.

934 Wisconsin Academy of Sciences, Arts, and Letters .

sumably, the retort and condenser. Even with this modifica¬

tion, however, a large part of the solvent was still lost in the

operation of straining.

About this time (1820 to 1840), the extraction of drugs by

the process of downward displacement was attracting consider¬

able attention, and, as the pharmacist saw in this procedure a

means of eliminating the operation of straining, it is not at all

surprising that it should have received early application in the

preparation of the oleoresins. In explanation of the method of

procedure as followed at the time, it should be stated that it was

in reality a process of percolation under pressure, and, as such,

required the use of a special form of apparatus. Two such

forms were already available at the time when the oleoresins

became a subject for investigation, namely : the Filtre-Presse of

Real and the Luft-Presse of Romershausen. In fact, Geiger

made use of the former in the preparation of the oleoresin of

male fern as early as 1827. While these forms of pressure

percolators eliminated the process of straining, their use, never¬

theless, appears to have been disadvantageous in certain other

respects. For instance, the method of operation was rather

cumbersome, and a considerable amount of solvent was absorbed

by the cloth bag containing the powdered drug, thus rendering

the apparatus of little value in working with small quantities

of the latter.

As a result of the early work with the pressure percolators,

experimentation along this line was stimulated and it was soon

shown that drugs could be completely extracted by simple per¬

colation under ordinary atmospheric pressures. The first evi¬

dence of the use of a simple percolator in the preparation of

the oleoresins appears in Beral’s account of his preparation of

the Piperoide du Gingembre in 1834. Fifteen years later

(1849), Procter, in an article on the oleoresinous ethereal ex¬

tracts, mentioned two forms of simple percolators, a conical

percolator made of tin, and Gilbertson’s displacement apparatus

constructed of glass. Both of these were similar in essential

detail to the percolators in general use at the present time. In

fact, the United States Pharmacopoeia still directs that these pre¬

parations be made by simple percolation, a modified form of

Gilbertson’s displacement apparatus being specified for use in

this connection. This condition seems strange, indeed, in view

of the fact that modern methods of operating with volatile

Du Mez — The Galenical Oleoresins.

935

solvents, such as ether, make use of some form of continuous ex¬

traction apparatus.

Such an apparatus was invented by Mohr in 1847 and its

advantages in the preparation of the oleoresins pointed out by

him at this time, and later, by Procter. An apparatus operat¬

ing on similar principles was described by Parrish in 1884 in his

Treatise on Pharmacy. More recently Maish (1900) has sug¬

gested the use of the Soxhlet apparatus for the preparation of

small quantities of oleoresins, while a number of other forms of

continuous extraction apparatus have been mentioned in this

connection in the various periodicals and text-books on phar¬

macy.

The different forms of apparatus, which have been mentioned

at various times in connection with the preparations of the oleo¬

resins, and the methods of operating with the same are described

in detail in the following chronological list:

Cadet, C. L.

Filtre-presse de M. Real.

Jour, de Pharm., 2, pp. 165 and 192 ; Repert. der Pharm. 2,

p. 356.

Fig. 1.) The body of the extraction apparatus A is made of

tin, the top of which, being screwed on, can be removed. It is

936 Wisconsin Academy of Sciences , Arts, and Letters.

supported on a tripod. At D and D are two false bottoms be¬

tween which the material to be extracted is packed. Into the

cover of the apparatus, the pipe B, which may be 50 to 60 feet

high, is fitted. The communication between B and A may be

stopped by means of the stop cock C. The dish E under the

tripod receives the percolate.

Fig. 2.) The second figure is a modification of the first do¬

ing away with the long tube. The solvent is admitted to the

space X by pouring it into the funnel E. The percolate is

collected in the container G-. The pressure is secured by filling

the cast iron container A with mercury. After the apparatus

C is charged with drug and solvent, the stop-cock H is closed

and the pipe B also filled with mercury which then forces the

menstruum through the firmly packed drug.

Buchner, J. A. 1819

Beschreibung und Abbildung der von Herrn Dr. Romers-

hausen erfundenen Luft-presse.

Repert. der Pharm., 6, p. 316.

V/

Z

Du Mez — The Galenical Oleoresins.

937

£ VI Ta&MI

The two twin cylinders B and C are mounted on the support A

and are provided with covers 1 and 10. On the support, the

diaphragm 3 is placed, covered with a straining cloth which is

held in position by the diaphragm 4 which in turn is fastened

by the clamp 5. A third diaphragm 6 is used to cover the sub¬

stance to be extracted. The two cylinders are united by the

tube 7 provided with a stop-cock. The lower part of B is also

provided with a stop-cock at S in order to allow the percolate to

flow out at 9. The lower section of C is converted into an air

tight compartment by the cover 11, which is provided with an

opening and stopper at 12. The parts indicated by 13, 14, 15,

16, and 17 belong to the suction pump necessary to create a va¬

cuum. The suction pump is outside the cylinder and the per¬

colate is not allowed to collect underneath the percolator B, but

is at once pumped in the reservoir C.

Beindorff 1826

Mag. f. d. Pharm., 9, p. 185. [Geiger, Hanbuch d. Pharm.

(1830), p. 142].

The cuts represent Beindorff Js modification of the Real

and Romershausen extraction apparatus. It will be noticed

that the apparatus in figure 6 is so mounted that it can be tipped

938 Wisconsin Academy of Sciences , Arts , and Letters.

at a convenient angle for filling and emptying. In figure 7, a

more compact form of the apparatus is shown. In the latter,

the long tube is replaced by an air pump.

These forms of pressure percolators were mentioned in con¬

nection with the preparation of the oleoresins by Mohr (1854)

in his Commentary on the Prussian Pharmacopoeia.

Du Mez — The Galenical Oleoresins .

939

Simonin

Journ. de Pharm. et de Chim., 20, p. 128.

1834

It is thought that one of the above represents the form of per¬

colator made use of by Beral (1834) in his preparation of the

Piperoide due Gingembre.

940 Wisconsin Academy of Sciences , Arts , and Letters.

Mohr

1847

Neuer Extractions Apparat fner Weingeist nnd Aether.

Arch, der Pharm., 100, p. 305. [Am. Jonrn. Pharm., 21,

P- 117].

The apparatus consists of a two-necked Woulf ’s bottle, figure

78 p, into the central mouth of which the metallic vessel R, figure

79, is fitted by means of a cork. The vessel R consists of a me¬

tallic cylinder a having a perforated strainer k near the bottom

and terminating with a funnel neck, to admit of its being fitted

into the Woulf ’s bottle. This cylinder is surrounded by a

second cylinder b, the space between them being intended to

contain either hot or cold water. In the top of the inner cylin¬

der a, a slightly conical vessel c is made to fit air tight, as shown

in the drawing. This vessel c is intended to be used as a con¬

densing apparatus, and for this purpose it is filled with cold

water. From the second or lateral opening of the Woulf ’s bot¬

tle, a glass or tin tube d, figure 78, is carried to the upper part of

the cylinder a, where it is inserted as shown in figure 80. The

cold water in the vessel c is renewed through the pipe e which

conducts it to the bottom, while the warm water runs off from

the top through the pipe /, figure 79. Hot or cold water is re¬

newed to the space between the two cylinders R by the tube

funnel h, figure 78, and the water from this space overflows into

g and is carried off together with that from /. The tube Ji is

inserted through a perforated cork at i so that by turning the

Du Mez — The Galenical Oleoresins.

941

tube downwards, the water from the space between the cylin¬

ders can be run off.

- 1849

Mohr, Redwood and Procter’s Pharmacy, p. 270.

This consists of a conical vessel A with a water joint rim at

the top into which the cover fits. A, tube D is ground to fit into

the opening in the bottom, and over the end of this tube is

placed a conical tube C, the lower end of which has several

notches cut in it, so that the liquid can pass under when placed

as shown in the drawing. The lower extremity of the vessel

A is ground to fit into the mouth of the receiver B.

The above apparatus was mentioned by Procter, in 1849, in

his article on “the preparation of the oleoresinous ethereal ex¬

tracts. ’ ’

- 1849

Mohr, Redwood and Procter’s Pharmacy , p. 272.

A is an ordinary tin displacer, except that the rim c is soldered

around the mouth, in such a manner as to form a water joint

when the rim of the cover d is placed in it ; a is a perforated

diaphragm, e a tin tube open below and above. The latter is

soldered to the lower diaphragm, through which it passes, while

the upper diaphragm slips over it loosely. In using the dis-

942 Wisconsin Academy of Sciences , Arts , and Letters .

placer, the ingredients are introduced around the tube to a

suitable height, the upper diaphragm put in its place, and

menstruum poured on, the joint half filled with water and the lid

inserted. The atmosphere of the bottle B communicates with

that of A through the tube e.

This form of percolator was mentioned by Procter (1849) in

his article on ‘ 4 The oleoresinous ethereal extracts. ? ’

— - — 1849

Mohr, Redwood and Procter’s Pharmacy, p. 270.

Figure A is a glass adapter, which is selected of suitable size.

The lower extremity of this is partially stopped with a cork cut

as represented in F, A layer of coarsely pounded glass is put

over the cork, and above this a layer of clean sand, thus form¬

ing a strainer for arresting the passage of the solid particles of

material to be acted upon. The end of the adapter is fitted,

by means of a perforated cork, into the mouth of a bottle. A

glass tube, one end of which is drawn to a capillary opening,

is also fixed in the cork as shown at C so as to allow the air to

escape out of the bottle as the liquid drops in. A piece of blad¬

der may be tied over the mouth of the vessel at A to prevent

the evaporation of the solvent, but a few pin holes must be made

in the bladder to admit of the ingress of air as the liquid passes

into the receiver below.

Du Mez — The Galenical Oleoresins.

943

The above form of percolator was mentioned by Procter

(1849) in his article entitled The Preparation of the Oleoresin-

ous Ethereal Extracts.

- 1873

Utensilien zur Bereitung der aetherischen nnd weingeistig-

aetherischen Extracte.

Hager’s Commentar zur Pharmakopcea Germanica, 1, p. 620.

This consists of a cylinder bb fitted into a cork / which is in¬

serted into the neck of a flask or bottle g, aa is a cover which

serves as a condenser. In the lower end of the cylinder bb is

a tin sieve plate ss in the center of which is a tin tube rr en¬

closed in a glass tube vv. The glass tube is held firmly in place

by a cork at each end pp. The condenser aa has a conical

shaped bottom N around the interior of which run two cor¬

rugated rings zz of tin. The space a , Fig. B, contains cold

water which enters from the openings cc and flows out through

944 Wisconsin Academy of Sciences , Arts, and Letters.

less, the top aa is taken off and D put on in its place. It is

also a condenser. The water flows in at a and off through b.

The conical bottom K is so arranged that the condensed solvent

the tubes ee. As soon as the menstruum drops through color-

drops from off the receiver i and is carried off into a flask

• through the outlet e. The space between vv and aa is filled

with either hot or cold water.

- 1873

Utensilien zur Bereitung der aetherischen und weingeistig-

aetherischen Extracte.

Hager’s Comment ar zur Pharmakopoea Geirmanica, 1, p. 622.

A displacement tube D with a wide mouth at its upper end is

closed with a cork through which runs a thistle tube T. The

lower end is pushed through a cork which fits tightly in a re¬

ceiving bottle R. The small glass tube l is for the purpose

of letting the air escape from the receiver R.

Du Mez — The Galenical Oleoresins. 945

1884

Parish’s Treatise on Pharmacy, p. 755.

A percolator of tinned copper is surrounded by a jacket of

the same material ; the receiver is a copper vessel with two necks

into one of which the percolator is secured, the other is connected

with a pipe leading to the closed head of the percolator which is

also jacketed; on the other side of the head is a perforated plate

60— S. A. L.

946 Wisconsin Academy of Sciences , Arts, and Letters.

of tinned copper, which distributes the ether over the surface of

the drug when it has been volatilized by placing the receiver

in hot water. After the exhaustion of the drug, the receiver is

removed, the lower orifice of the percolator closed, and the head

well refrigerated ; a stream of hot water is then passed into the

jacket ar‘ound the percolator, by which means the contained

ether may be recovered.

- 1886

Remington’s Practice of Pharmacy 1886, p. 366.

The apparatus consists of a cylindrical percolator fitted into

the mouth of a receiving bottle with the aid of a cork. The

upper part of the percolator being closed and a small opening

left in the cork to allow the escape of air from the receiving

bottle.

A continuous extraction apparatus can be made of this per¬

colator by enclosing the upper part in a suitable case and pass¬

ing cold water between, arranging the apparatus like a Liebig’s

condenser. A glass tube is connected with the top of the perco¬

lator and the mouth of the bottle by rubber tube connections,

Du Mez — The Galenical Oleoresins.

947

and if the receiving bottle be placed in a water bath and the water

gently heated, the ether will evaporate from the percolate, the

vapors rising in the tube and condensing in the upper part of

the percolator.

Lewin R. 1887

Ein neuer Extractions Apparat,

Arch, der Pharm., 215, p. 74. [Proc. A. Ph., 35, p. 12.]

This apparatus is adapted for 1) continuous extraction with

hot menstrua, 2) continuous extraction with cooled menstrua,

3) recovery of the menstrua from the finished extract by direct

distillation.

It is composed of three easily separable principle parts: C,

the tinned copper still, B, the copper percolator, which is pro¬

vided with three movable sieve bottoms for the reception of

1) For continuous extraction with hot solvents, the vapors

pass from the still C, in the tube 1, and enter through the tri-

948 Wisconsin Academy of Sciences , Arts , and Letters.

faucet I, when in position a , through tube 4, into the percolator,

the substance to be extracted. A is the condenser.

B, penetrate the substance to be extracted, and condense. The

percolate passes into the receiver and from this flows through

the tri-faucet III in its position a, through the tube 7, again

into the still, to repeat this course as long as it may be desir¬

able. To prevent pressure in the apparatus, the tube 2, is

removed during this operation, and the tri-faucet II is placed

in position a . This admits the vapor into the cooling worm, A,

which thus forms a safety valve.

2) For the continuous extraction with cooled solvents, the

vapors pass from the still C, into tube 1, and enter through the

tri-faucet I, in its position h, through tube 2, into the cooling

worm A, from this as a liquid through the tri-faucet II, in its

position a, into the percolator, and so through the substance to

be extracted into the still as before.

3) For the recovery of the solvent from the extract by direct

distillation, the vapors pass from the still C, through tube 1,

through the tri-faucet I, in its position &, through tube 2, into

the cooler, A, through the tri-faucet II in its position b, into the

exit tube 3, which latter may be lengthened at pleasure.

Portions of the percolator may be removed from the receiver

at pleasure through the tri-faucet III, in its position c, by the

tubes 2 and 3. All of the tubes are connected or disconnected

by good screw joints.

Flueckiger, F. A. 1889

Ein zweckmaessiger Extraktionsapparat.

Arch. d. Pharm., 227, p. 162. [Proc. Am. Pharm. Assoc., 37,

p. 338.]

The extraction tube A is provided at C with a diaphgram

from the center of which a small tube or neck extends into the

funnel D. The tube B F attached to the side, passes into

a tubulure G, which is provided with an ordinary cork K

by means of which communication through the tube B F,

between the upper, and the lower portions of the apparatus

may be cut off or established. Thus causing the condensed

liquid to return through the drug when the communication is

closed or allowing the liquid to be distilled off when it is open.

Du Mez — The Galenical Oleoresins.

949

Caspari in his Treatise on Pharmacy (1916) describes the use

of this apparatus in connection with the preparation of the oleo¬

resins.

- - - 1890

Szombazi Soxhlet’s Extraction Apparatus.

Dingier ’s Pol. Journ., 256, p. 461. [Zeitschrift f Anal. Chem.,

19, p. 365.]

Maish (1900) first suggested the use of this apparatus in the

preparation of the oleoresins.

950 Wisconsin Academy of Sciences , Arts , and Letters.

Alpers, William C. 1896

Oleoresinae.

Merck’s Rep., 5, p. 593. [Proc. Am. Pharm. Assoc., 45, p. 435.]

The apparatus consists of a cylindrical percolator a. The

upper end of the percolator is closed with a large cork b through

which two holes have been bored — the one for receiving a bent

glass tube c, the other for a small glass funnel d. The lower

narrow end of the percolator is closed by a cork e through which

a straight connecting glass cock / passes into another perforated

cork g that closes the receiving bottle Ji. This cork contains

a second perforation with a small bent glass tube i. The glass

tubes c and i are joined by means of a small piece of rubber

tubing at k.

Coblentz’s Handbook of Pharmacy , p. 290.

1902

A is a percolator with a stop cock C. It is inserted into a

receiver B. The receiver B and percolator A are connected

Du Mez—The Galenical Oleoresins.

951

with a tube as shown in the figure for the purpose of equalizing

the pressure as the apparatus is closed throughout.

- - - - 1908

Brandel and Kremers, Percolation, p. 52.

A is an ordinary conical percolator of such a size that it will

not be more than two-thirds filled with the drug to be extracted.

B is a round-bottom flask, containing a twice perforated stop¬

per, through one hole of which a glass tube connects the flask

to the percolator. Through the second hole is inserted the

glass tube C which also passes through the cork stopper in the

top of the percolator. The end of the condenser D is also in¬

serted through this cork. All cork connections should be tightly

sealed with gelatine.

The above is the form of apparatus which was used in the

laboratory in the preparation of the oleoresins when 500 grams

or more of the drug were extracted.

952 Wisconsin Academy of Sciences , Arts , and Letters.

Yield

The yield of oleoresin is a variable quantity depending, first

of all, upon the oleoresin content of the particular drug from

which it is prepared. Thus, the oleoresin content of ginger

is only about one-half that of the aspidium and one-fourth that

of cubeb. Not, only, however, does the oleoresin content vary

with the different drugs, but the drug, when of the same genus

and species, may show a variation due to a number of in¬

fluences, such as the climate in which grown, time of harvest¬

ing, conditions under which stored, et cetera. As an illustra¬

tion of these influences, aspidium may be taken. The maxi¬

mum yield of oleoresin, in this case, is obtained from the freshly

dried Russian rhizomes collected in the month of September.1)

Or, the case of ginger may be cited. In this instance, the

African rhizomes harvested at maturity (usually in Feb¬

ruary)1) give the largest amount of oleoresin. This character¬

istic will be taken up in detail under the treatment of the

individual oleoresins. The other important factors in deter¬

mining the amount of oleoresin obtained, in general, are two

in number, viz: the solvent employed in extracting the drug,

and the method employed in operating with the same. Both

of these factors have been dealt with in a general way under

the two preceding headings. They will also be discussed more

fully in connection with the individual preparations.

Chemistry

The Chemistry of the oleoresins per se has apparently re¬

ceived but little attention, except in the case of the

oleoresin of aspidum. The latter has been the subject

of numerous investigations and its chemistry is now under¬

stood fairly well. Some work has also been done toward de¬

termining the composition of the oleoresins of cubeb and

lupulin, but our present knowledge of the chemistry of these

preparations is still very indefinite.

A very considerable amount of work has been done toward

clearing up the chemistry of the drugs from which the oleo¬

resins are prepared, and it is from this source that we are

1 See tables of yield under the oleoresins of aspidium and ginger, re¬

spectively.

Du Mez — The Galenical Oleoresins.

953

obliged to obtain what information we have concerning the

composition of most of these preparations. It is for this rea¬

son that the chemistry of the drags from which the oleoresins

are prepared is given consideration in this monograph. See

i 1 Chemistry of the drag and its oleoresin ’ ’ under the treatment

of each individual oleoresin.

Physical and Chemical Properties

The determination of the physical and chemical properties

of the galenical oleoresins in general does not appear to have

been undertaken systematically in the past. While there are

numerous references in the literature concerning color, odor,

taste and consistence, there is no mention, except in connection

with the oleoresins of aspidium and cubeb, of the properties

which we should naturally expect to find under a description

of a class of preparations of this nature, viz: specific gravity,

refractive index, acid number, saponification value, et cetera.

This condition is surprising in view of the work which has

been done along this line in connection with the natural pro¬

ducts of the same name. That cognizance is, however, being

taken of the subject at the present time is evidenced in the

comparatively recent work which has been done abroad on the

oleoresin of aspidium. In the latter case, the methods usually

employed in fixing the standards of similar natural products

were applied, and with considerable success. A brief general dis¬

cussion of these properties as well as other characteristics, which

have been mentioned in this connection, follows.

Physical Properties

Color:

The color is a characteristic property of the individual mem¬

bers of this class of preparations. Considered with respect

to a single member, it serves in some cases as a measure whereby

the quality of the product may be roughly determined. Thus,

a brown color in the oleoresin of aspidium indicates an inferior

preparation, in the making of which old deteriorated rhizomes

have been used, whereas, a deep green color is said to indicate

adulteration with salts of copper. Likewise, a brown color

in the oleoresin of cubeb warrants the opinion that ripe in¬

stead of unripe fruits have entered into its preparation. How-

954 Wisconsin Academy of Sciences , Arts , and Letters.

ever, as the color of the individual preparations, when properly

made, varies to a considerable extent, and as the description of

exact shades is a difficult matter, this property as described in

the literature is naturally somewhat indefinite. This subject

will receive further consideration of the treatment of the in¬

dividual oleoresins.

Odor:

The oleoresins without exception possess distinct odors re¬

sembling in an intensified degree those of the drugs from which

they are prepared. In general, this property offers a ready

means of identifying these preparations. In specific instances,

it may also serve as an indication of the quality of the product.

For example, a rancid odor in the case of the oleoresin of as-

pidium is evidence of the use of old deteriorated rhizomes in

its preparation or of undue exposure to the air while kept in

storage. For similar reasons, the oleoresin of lupulin may

have a disagreeable cheesy odor. Furthermore, unevaporated

solvent, even when present in comparatively small amounts,

may be most easily detected by this means. This property will be

discussed in greater detail under the individual oleoresins.

Taste :

The taste of the individual oleoresins, like the odor, is a

property acquired in an intensified degree from the drugs from

which they are prepared. Likewise, this property also serves

as an aid in the identification of these preparations. In addi¬

tion, however, it has been made the basis of a quantitative

physiological testC1) for the determination of the quality of

the oleoresins of capsicum and ginger. For a further discus¬

sion of this property, see the individual oleoresins.

Consistence:

The U. S. P. oleoresins, with the exception of the one pre¬

pared from lupulin, are liquids. The degree of fluidity, how¬

ever, varies with the individual under consideration, with the

temperature and with certain other conditions, which will be dis¬

cussed in detail under the separate treatment of each indi¬

vidual. The oleoresin of lupulin is usually of the consistence

of a very soft extract.

1 See under the oleoresins of capsicum and giner respectively.

Du Mez—The Galenical Oleoresins.

955

Solubility:

The solubility of the different oleoresins naturally depends

to a large extent on the solvent which was employed in their

preparation. It does not, however, follow from this statement

that, because an oleoresin was prepared with ether, it will al¬

ways be completely soluble in the same. Some of these pre¬

parations on standing undergo chemical changes with a result¬

ing change in solubility. For example, the oleoresin of aspi-

dium forms a deposit on ageing, and the deposited material is

practically insoluble in ether. As a rule, the oleoresins, when

prepared with ether, form clear or slightly cloudy solutions

with absolute alcohol, acetone and chloroform, whereas, they

are only partially soluble in petroleum ether and carbon tetra¬

chloride.

In the case of certain members of this class of preparations,

this property has been of considerable value in detecting adul¬

terations or in the identification of the solvent which was em¬

ployed in their manufacture. For specific instances of the

application in this connection, see under the oleoresins of aspi-

dium and ginger.

Specific gravity:

The value of determining the specific gravity as an aid to

standardizing the oleoresins appears to have been first noted by

Procter. In 1866, he published data showing how this constant,

in the case of the oleoresin of cubeb, varied with the solvent

employed in its preparation, and further pointed out that a low

specific gravity observed in the commercial product was, in one

instance at least, an indication of the incomplete removal of

the solvent, ether. Procter's observations were as follows:

Table 7. — The specific gravity of the oleoresin of cubeb.

This work, however, appears to have received but little atten¬

tion as there is no further mention of the determination of this

956 Wisconsin Academy of Sciences . Arts , and Letters.

constant in this connection in the literature until 1903. In that

year, the English firm of Southall Brothers and Barclay pub¬

lished a statement in their Laboratory Reports , in which a stan¬

dard range for the specific gravity of the oleoresin of aspidum

was given. Interest in the matter again seems to have waned

and it was not until 1911, when Parry showed that the last

named preparation was being extensively adulterated with castor

oil, that the necessity for standardizing this preparation be¬

came apparent. The subject was then taken up in earnest,

however, and in 1913, no less than four articles on the deter¬

mination of the physical and chemical constants of the oleo¬

resin of aspidium made their appearance. In each of these,

the determination of the specific gravity was given some con¬

sideration.

From the foregoing brief resume of the literature on this sub¬

ject, it becomes apparent that the determination of the specific

gravity as a factor in evaluating the oleoresins has received

consideration in connection with but two of the official prepara¬

tions. Furthermore, that practical use has been made of this

constant only in the case of the oleoresin of aspidium. The

results obtained with respect to these two preparations, how¬

ever, are deemed to be of sufficient importance to warrant the

determination of this constant in the case of the other members

of this class of preparations.

The manner in which this constant was determined by the

above mentionel investigators does not become apparent from

their work as reported in the literature. It is thought, how¬

ever, that an ordinary glass pycnometer and chemical balance

were employed for this purpose. In the determinations made

in the laboratory, a 10 cubic centimeter pycnometer was used,

except in the case of the oleoresin of lupulin which was usually

too thick to handle in this manner. For the determination of

the specific gravity of the latter, a Nicholson’s hydrometer was

employed. All determinations were made at 25° C.

The results as obtained in the laboratory and those reported

elsewhere will be discussed in detail under the treatment of the

individual oleoresins.

Refractive index:

The determination of the refractive index has received con¬

sideration only in connection with the standardization of the

Du Mez — The Galenical Oleoresins. 957

oleoresin of aspidium. In this case, it has proven to be of par¬

ticular value in detecting adulteration with castor oil as was

first pointed out by Parry in 1911. Subsequent work by other

investigators has not only confirmed Parry’s observations, but

has shown that in some instances a low refractive index may be

an indication of a low filicin content due to natural causes1)

as well.

Since most of the other official oleoresins are sufficiently trans¬

parent to permit of the direct determination of this constant,

it was thought that such determination might likewise prove to

be of some aid in standardizing these preparations. That such

an opinion has proven to be correct will be shown in connection

with the discussion of this topic under the individual cases.

For the determination of this constant in the laboratory, the

Abbe refractometer was employed, all observations being made

at 25° C. In those cases (the oleoresins of ginger and lupulin)

where the color was too intense to permit of a direct determina¬

tion being made, the oleoresin was dissolved in an equal volume

of castor oil and the refractive index computed from the follow¬

ing formula :

nD (b) = 2nD (a + b) — nD (a)

a = refractive index of castor oil.

b — 1 6 il “ oleoresin.

Chemical Properties

Loss on Heating:

The oleoresins without exception lose weight on drying. This

loss is usually referred to in the literature as the moisture con¬

tent. It has been determined by heating the preparation at

100 to 105° C. for a definite period of time, or until of con¬

stant weight. The falacy of designating the loss of weight

thus obtained as the moisture content becomes evident when we

take into consideration the fact that these preparations con¬

tain volatile substances other than water, which would also be

removed by heating to a temperature of 100° C. Indeed, the oily

1 The male fern rhizomes have been shown to vary in filicin content due

to the climatic conditions under which they were grown, time of harvesting,

et cetera. See under “Drug used,, its collection, preservation, etc.”

958 Wisconsin Academy of Sciences , Arts , and Letters.

nature of these preparations exclude the presence of any great

quantity of moisture. This statement has been borne out by

laboratory experiments. Attempts to determine the moisture

by means of the xylene1) method failed to reveal the presence

of a measurable amount of water in any of the samples examined.

The loss in weight is, therefore, due, ordinarily, to the removal

of volatile oil and in exceptional cases to the removal of un¬

evaporated solvent. Such being the case, the determination of

this constant serves as a means of measuring the amount of

volatile oil naturally occurring in these preparations and as a

means of detecting the presence of unevaporated solvent.

The amount of weight lost by the oleoresins when deter¬

mined as stated above varies greatly with the individual

members comprising this class of preparations. The oleoresin

of cubeb which contains a comparatively large amount

of volatile oil naturally sustains a comparatively great

loss, while the oleoresin of capsicum which contains

a small amount of volatile matter shows but a slight loss.

There is noted a further variation in the case of each individual

due to a variation in the amount of volatile matter naturally

occurring in the drug from which the oleoresin was obtained,

or to a variation in the conditions under which the individual

was prepared. As an illustration, the oleoresin of cubeb may

be cited. The volatile oil content of cubeb is stated to be 10 to

18 per cent. A much greater variation is, therefore, to be ex¬

pected in the oleoresin which represents only the alcohol soluble

portion of the drug. With respect to the conditions under

which the oleoresin of cubeb is prepared, observations in the

laboratory have shown that the preparation will contain a larger

amount of volatile oil when the solvent is allowed to evaporate

spontaneously at room temperature, than when the same is re¬

moved by evaporation on a water bath. In most cases, the

variation, due to the difference in solvent used in extracting

the oleoresins, appears to be so slight as to be almost negligible.

In the case of the oleoresin of pepper, however, there is a very no¬

ticeable difference. This is very likley due to the nature of the

preparation, its viscosity making it difficult to remove the last

traces of the less volatile solvents without the application of

heat.

1IJ. S. Dept. Agric., Forest Service, Circ. 134.

Du Mez—Tfoe Galenical Oleoresins.

959

In the determinations of this nature made in the laboratory,

a weighed amount of the oleoresin (about 2 grams) was heated

in an electric oven at 100° C for 3 hours, cooled in a desiccator

and weighed, the difference in the two weights being taken as

the loss.

A more detailed consideration of this subject will be found

under the treatment of the individual oleoresins.

Ash Content:

The determination of the ash content of the oleoresins is

of special value in identifying the solvents which have been used

in their preparation. Such determinations, made in this

laboratory, also by the firm of Dieterich1) in Helfenberg, have

shown that, while there is as a rule comparatively little dif¬

ference in the ash content of these preparations, when prepared

with the same solvent, there is a marked variation in the case

of each individual when different solvents are employed. The

oleoresin of lupulin is an exception to this rule. It's ash con¬

tent varies to a considerable extent even when prepared with

the same solvent.

In addition to the above, the qualitative examination of the

ash of commercial samples has revealed the fact that nearly all

of them contain copper, due in most cases to the action of the

free fatty acids on the utensils employed in their preparation.

In some instances, the presence of the metal must be attributed

to the addition of copper salts for the purpose of imparting

the desired green color to preparations of inferior quality. See

under the adulteration of the oleoresins of aspidium and cubeb,

respectively.

The ash content of the oleoresins examined in the laboratory

was determined as directed by the last edition of the United

States Pharmacopoeia under ^Determination of Ash or Non¬

volatile Matter,” p. 589.

Copper, when present, was identified by the blue color of the

solution formed when the ash was dissolved in a few drops of

hydrochloric acid, diluted with water, and ammonium hy¬

droxide solution added.

1 The firm of Dieterich has for a number of years determined the ash

content of the oleoresins of aspidium and cubeb. A tabulation of the re¬

sults as obtained by this firm will be found under the separate treatment

of these oleoresins.

960 Wisconsin Academy of Sciences, Arts, and Letters.

For a more detailed discussion of this subject, see under in¬

dividual oleoresins.

Acid Number:

Kremel in 1887 determined the acid numbers of the oleo¬

resins of aspidium and cubeb. Inasmuch, however, as he made

but one determination in each case, no conclusions can be drawn

from his work. Similar determinations made in this laboratory

on all of the official oleoresins show that this property varies

greatly depending on the particular individual under considera¬

tion. Furthermore, that no general statement can be made as

to its value in fixing the standards of these preparations, but

that it is of importance when considered in connection with

individual cases as will be brought out later.

For the manner in which this constant was determined in

the laboratory, see the United States Pharmacopoeia, ninth re¬

vision, (1916), p. 591.

Saponification Value:

The saponification values of the official oleoresins, as deter¬

mined in this laboratory and elsewhere,1) indicate that this

property may be an important factor in fixing standards for

these preparations. The results obtained by Parry, Harrison

and Self, and others show that in the case of the oleoresin of

aspidium, the saponification value varies directly as the filicin

content, and is, therefore, useful as a check on the determina¬

tion of the latter. Considered in connection with such of these

preparations as contain easily oxidizable substances, an abnor¬

mally high saponification value is very likely caused by an in¬

crease in the acid content due to the action of the oxygen of the

air, and is thus an indication of an old product2) or of improper

care in storing. As an example, the oleoresin of lupulin may

be cited. In this case, a high saponification value signifies an

old preparation or one that has been prepared from deteriorated

drug.3) These factors, together with the influence of the solvent

employed and the method of preparation on this property, will

1 Saponification values have only been determined in the past in the case

of the oleoresin of aspidium and in one instance in the case of the oleoresin

of cubeb.

2 See oleoresin of aspidium.

3 See oleoresin of lupulin.

Du Mez — The Galenical Oleoresins.

961

be considered in greater detail under the treatment of the in¬

dividual members.

The manner in which this constant was determined in the

laboratory is described on p. 590 of the United States Phar¬

macopoeia, ninth revision.

Iodine value:

The determination of the iodine value as an aid to the

standardization of the oleoresins appears to have been first em¬

ployed by the firm of Dieterich in Helfenberg in 1904, however,

only in the case of the oleoresin of aspidium. It has since re¬

ceived further practical application, in connection with the same

preparation, by the English firm of Evans Sons, Lescher and

Webb, while a number of similar determinations have been made

by the author. The results1) obtained with respect to this

preparation show that the iodine value varies directly as the

filicin content, and, therefore, serves as another check on the

determination of the latter constituent.

With respect to the other official oleoresins, it may be stated

that, as a general rule, the iodine value is high in the case of

those preparations which contain a large amount of unsaturated

constituents of ether fatty or volatile oil.2) Further than this,

it may be influenced largely by the pature of the other consti¬

tuents of these preparations and will be considered in detail in

connection with the treatment of each individual.

For the method employed in the laboratory in the determina¬

tion of this constant, see the United States Pharmacopoeia, ninth

revision, p. 590.

Special Tests

While the different official oleoresins can, as a rule, be identi¬

fied without difficulty, the use of various adulterants in their

preparation, through ignorance in some cases, or with willful

intent on the part of unscrupulous manufacturers, has made

it necessary to guard against this practice by making use of

certain qualitative and quantitative tests. As will be brought

out later, such tests have been applied principally to the pre¬

parations official in foreign countries, namely : the oleoresins

1 See under oleoresin of aspidium. *

2 See under oleoresin of eufoeb.

61— S. A. L.

962 Wisconsin Academy of Sciences , Arts, and Letters .

of aspidium and cnbeb. No tests of this, or, as a matter of fact,

of any kind have been included in the United States Phar¬

macopoeia. It is thought, however, that if interest in these prep¬

arations could be awakened in this country, the need of sim¬

ilar precautions with respect to all of the official oleoresins would

become apparent.

Qualitative Tests:

Inasmuch as the common physical properties, such as odor,

taste and appearance, are very characteristic of the oleoresins,

it is hardly necessary to resort to other means for their identi¬

fication. It appears, however, that the use of the so-called

false cubebs in the preparation of the oleoresin of cubeb has

made necessary a more certain method of identification. Such

a method, based on the red color produced when concentrated

sulphuric acid is added to the oleoresin prepared from the gen¬

uine fruit,1) has, therefore, been given in most of the late Eur¬

opean pharmacopoeias. Likewise, the use of other species of

fern in the preparation of the oleoresin of aspidium caused a

qualitative test for this preparation to be included in the late

editions of the Austrian, Hungarian and Netherlands phar¬

macopoeias. For the details of these methods, see qualitative

tests under the respective oleoresins.

Quantitative Tests:

On the whole, very little has been done in the past toward

developing quantitative methods for the evaluation of the oleo¬

resins. This condition is perhaps due, for the main part, to an

imperfect knowledge of the chemistry of most of these prepara¬

tions, as well as to the lack of exact information concerning the

constituents of therapeutic value. In the case of the oleoresin

of aspidium, however, the therapeutic value of the preparation

has been shown to depend upon a number of acid constituents,

the quantity present varying through natural and artificial causes.

As a result, various methods2) for the determination of the total

acid content have been devised and are in use at the present

time, a modification of the original method of Fromme being

officially recognized in the late edition of the British and Swiss

1 Dekker states that the so-called false cubebs give a yellow color with

concentrated sulphuric acid. Pharm. Ztg. (1912), 84, p. 845.

2 See under oleoresin of aspidium.

Du Mez — The Galenical Oleoresins.

963

pharmacopoeias. The only other work of this nature appears

to have been done quite recently (1914) by the H. K. Mulford

Co. in the standardization of the oleoresins of capsicum and

ginger. This firm has devised a physiological method for this

purpose based on the extreme pungency of these preparations,

the highest dilutions in which these preparations (on the aver¬

age) are still perceptable to the taste being taken as standards.

Experiments conducted in the laboratory in preparation for

this monograph have shown, not only that there is an oppor¬

tunity for improving on some of the above mentioned methods,

but that there is need for the development of quantitative meth¬

ods which may be applied to the other individuals of this class

as well. With respect to the forepart of thiss tatement, it is

thought that a gravimetric method for the estimation of the

pungent principles (gingerol) in ginger would be an improve¬

ment over the physiological method of the Mulford Co. as per¬

sonal idiosyncrasy would thus be eliminated. Trials with the

method of Garnett and Grier1) (for the estimation of gingerol

in ginger) adapted to the oleoresin appear to indicate the cor¬

rectness of this opinion. In the case of the oleoresin of capsi¬

cum, however, the physiological method apparently offers the

only practical course at the present time, in view of the fact

that the active constituent, capsaicin, is present in such minute

quantities that an accurate gravimetric determination would be

a difficult matter.

In considering the application of new methods, the work done

in this laboratory on the oleoresin of pepper may be cited.

Since the therapeutical value of this preparation is apparently

due to its piperine content, a method for the quantitative de¬

termination of this constituent appeared to be desirable. With

this object in view, the nitrogen present was determined by the

Kjeldahl method and the piperine content computed therefrom.

Some very interesting results were obtained.2) As to further

possibilities along this line the determination of the apiol con¬

tent of the oleoresin of parsley, or the estimation of the quantity

of total acid resins present in the oleoresin of cubeb may be

mentioned.

1 See under oleoresin of ginger.

3 See under oleoresin of pepper.

964 Wisconsin Academy of Sciences, Arts, and Letters.

Adulterations

The examination of commercial samples of the oleoresins has

shown that they are all adulterated at times. With respect to

most of these preparations, adulteration is thought to be acci¬

dental, e. g. the presence of copper in nearly all samples due to

the use of copper utensils in the manufacture of the same, or

the use of ripe instead of unripe fruits in the preparation of

the oleoresin of cubeb. In some cases, however, adulteration

has been practiced with willful intention to defraud, as for

example, the addition of fatty oils to the oleoresins of aspidium

and cubeb. Other instances of this kind will be given con¬

sideration under the treatment of the individual oleoresins.

Du Mez — The Galenical Oleoresins.

965

PART II— INDIVIDUAL OLEORESINS

OLEO RESIN OF ASPIDIUM

Synonyms

Aceite de Helecho Macho , Sp. P. 1905.

Aether es pafran-kivonat, Hung. P. 1880.

Aetherhaltig es Farr enter aut extract, Aust. P. 1844.

Aetherisches Farrnkraut extract, Pruss. P. 1830.

Aetherisches Farrnhrautwurzel Extract, Bad. P. 1841.

A Ivejuuriekstrakti, Finn. P. 1914.

Balsamo de Helecho, Dorvault, L’Officine, Sp. Trans. 1879.

Balsamum Filicis, Pareira, Mat. Med. 1854.

Baume de Fougere, Dorvault, L ’Oleine, 1898.

Braegne-Extract, Dan. Mil. P. 844.

Bregnerod Extract, Nor. P. 1870.

Bregnerodekstrakt, Nor. P. 1895.

Bregnerotekstrakt, Nor. P. 1913.

Estratto di Felce Maschio, Swiss. P. 1907.

Estrato di Felce Maschio Etereo, Ital. P. 1902.

Ethereal Extract of Male Fern, Journals.

Extract of Male Fern, Jap. P. 1907.

Extract van Mannetjes-Varen, Nethl. P. 1871.

Extracto de Feto Macho, Port. P. 1876.

Extracto de Feto Macho Ethereo, Port. P. 1876.

Extracto Etereo Helecho, Sp. P. 1884.

Extracto Ethereo de Helecho Macho, Sp. P. 1905.

Extracto oleo-resinoso de Helecho, Dorvault, L’Officine, Sp. Trans. 1879.

Extractu de Filice Mascule, Roum. P. 1874.

Extractu di Felce Machio, Swiss. P. 1865.

Extractum Aethereum Filicis, Sp. P. 1884.

Extr actum Aethericum Filicis, Fr. P. 1866.

Extractum Aethericum Filicis Maris, Fr. P. 1866.

Extractum Aspidii, Nor. P. 1854.

Extractum di Felce Machio Etereo, Port. P. 1876.

Extractum Filicis, G. P. 1900.

Extractum Filicis aethereum, Pruss. P. 1861.

Extractum Filicis liquidum, B. P. 1914.

Extractum Filicis Maris aethereum, Ital. P. 1902.

Extractum Filicis oleoso-resinosum, Jourdan, Univ. P. 1832.

Extractum Badicis Filicis Maris athereum, Bad. P. 1841.

966 Wisconsin Academy of Sciences, Arts, and Letters .

Extraction Stipitum Aspidii , Nor. P. 1854.

Extrait de Fougere, Belg. P. 1906.

Extrait de Fougere Mdle, F. P. 1908.

Extrait Etherd de Fougere, Belg. P. 1854.

Extrait Ether e de Fougdre Mdle , Fr. P. 1866.

Extrait oleo-resineux de Fougere, Bern. P. 1852.

Extrait ol&o-resineux de Foug&re Mdle, Fr. P. 1908.

Farnextrakt, Ger. P. 1900.

Farrenkrautextrakt, Bern. P. 1852.

Farrnwurzel Extract, Swiss. P. 1865.

Filicis Extr actum, Belg. P. 1906.

Filixextrakt, Journals.

Huil.e de Fougere Mdle, Belg. P. 1854.

Huile de Fougere de Peschier, Bern. P. 1852.

Liquid Extract of Fern Root, Br. P. 1864.

Liquid Extract of Male Fern, Br. P. 1885.

Oil of Filix mas, Parrish, Treat, on Pharm. 1867.

Oil of Male Fern, Journals.

Oleoresin of Fern, U. S. P. 1870.

Oleoresin of Male Fern, U. S. P. 1910.

Oleoresina Aspidii, U. S. P. 1910.

Oleo-resina de Helecho, Dorvault, L’Oflicine, Sp. Trans. 1879.

Oleoresina Filicis, U. S. P. 1860.

Oleo-Resina Filicis, Peschier, Yer. P. der Lond., Edinb., and Dub. Med.

Coll. 1827.

Oleo-resine de Foug&re, Dorvault, L’Officine, 1898.

Oleum Filicis, Hung. P. 1861.

Oleum Filicis Maris, Sp. P. 1905.

Oleum Filicis Maris aether eum, Swiss. P. 1865.

Oleum Filicis Peschiei'i, Pareira, Mat. Med. 1854.

Oleum Filicis pingue resinosum, Geiger’s P. 1835.

Oleum Radicis filicis, Strump. Allg. P. 1861.

Orhunksrot Extrakt, Swred. P. 1901.

Pafran-Kivonat, Hung. P. 1871.

Varenextract, Neth. P. 1905.

Wurmf arnextrakt , Swiss. P. 1893.

Wurmfarnoel, U. S. Disp. 1907.

Du Mez — The Galenical Oleoresins.

967

History

The oleoresin of aspidium, or Huile de Fougere Male as it

was originally known, was first prepared by Peschier in 1825.1

The advantages of Peschier ’s preparation over the forms in

which male fern was being administered at the time were quickly

noted and it received almost immediate recognition throughout

Europe. The rapidity with which it was taken up by the

medical profession is evidenced in the fact that it was mentioned

in the Vereinigte Pharmacopoeen der Londoner , Edingurgher

und Dubliner Medicines Collegien, a German translation of the

pharmacopoeias of London* Edinburgh and Dublin, which ap¬

peared in 1827, and, that two years later (1829), it became of¬

ficial in the Prussian Pharmacopoeia. Its introduction into

other European pharmacopoeias followed, as a general rule, in

the chronological order of their appearance or revision, whereas,

it was the last of this class of preparations to be admitted to the

United States Pharmacopoeia previous to the ninth revision,

having been recognized for the first time in the edition of 1870.

At the present time, it is the only preparation of this kind

which is official in all of the national pharmacopoeias. How¬

ever, it is only in the United States where it is officially recog¬

nized under the title oleoresin, it being classed as an extract

in all of the foreign pharmacopoeias. For a better apprecia¬

tion of this fact, see the preceding table of synonyms.

A better idea of the popularity of this preparation and the

rate at which it came into prominence will be obtained from

the following table in which are chronologically enumerated the

names of the pharmacopoeias of the countries, states and muni¬

cipalities where it first received official recognition, also, the

dates of appearance of the succeeding editions in which it occurs.

Prussian Pharmacopoeia — 1829, 1846, 1862.

Pharmacopoeia of Baden - — 1841.

Austrian Pharmacopoeia — 1844, 1869, 1889, 1906.

Pharmacopoeia of Schleswig-Holstein — 1844.

1 Gebhardt in 1821, and Morin in 1824, in their analyses of male fern,

extracted the rhizomes with ether and obtained what they termed a thick,

green, fatty oil. This was, of course, the Huile de Foug&re of Peschier.

Neither of these investigators, however, pointed out its value as a galenical

preparation, although, the latter stated that he considered it to be the ther¬

apeutically active principle of the rhizomes.

968 Wisconsin Academy of Sciences , Arts , and Letters .

Swedish Pharmacopoeia —1846, 1869, 1879, 1888, 1901, 1908.

Pharmacopoeia of Berne — 1852.

Belgian Pharmacopoeia — 1854, 1885, 1906.

Norwegian Pharmacopoeia — 1854, 1870, 1879, 1895, 1913.

Pharmacopoeia of Hannover — 1861.

Pharmacopoeia of Hessia — 1862.

British Pharmacopoeia — 1864, 1867, 1885, 1898, 1814.

Swiss Pharmacopoeia — 1865, 1 872, 1893, 1907.

French Pharmacopoeia — 1866, 1884, 1908.

Austrian Pharmacopoeia — 1869, 1889, 1906.

Hungarian Pharmacopoeia — 1871, 1888, 1909.

Netherlands Pharmacopoeia — 1871, 1889, 1905.

German Pharmacopoeia — 1873, 1882, 1890, 1900, ]910.

United States Pharmacopoeia — 1870, 1880, 1890, 1900, 1910.

Roumanian Pharmacopoeia — 1874.

Portuguese Pharmacopoeia — 1876.

Spanish Pharmacopoeia — -1884.

Italian Pharmacopoeia — 1892, 1902, 1909.

Danish Pharmacopoeia — 1893, 1907.

Japanese Pharmacopoeia — 1907.

Russian Pharmacopoeia — 1910.

Finnish Pharmacopoeia — 1914.

Drug Used, Its Collection, Preservation, Etc.

The rhizomes directed by all of the present day pharma¬

copoeias to be used in the preparation of the oleoresin of as-

pidium are those of the male fern1 now referred by botanists

to the genus Dryopteris as Dryopteris Filix-mas (Linne) Schott.

As male fern, especially in the older works on pharmacy, has been

referred to genera other than Dryopteris, the following table of

botanical synonyms is given:

1 The rhizomes of ferns other than those which have been officially recog¬

nized are said to yield oleoresins which are active in the expulsion of the

tapeworm.

Kuersten states that the rhizomes of Aspidium athamanticum Kunze yield

a preparation which is as active as that obtained from male fern. Arch,

d. Pharm. (1891), 229, p. 258.

Lauren reports the use of an extract in Finland prepared from Aspidium

spinulosum Sw. which he states is very active as a teniafuge. Finska

Laegaresaellck. Handl. (1897), p. 9; Pharm. Centralh, (1897), 39, p. 775.

Rosendahl suggests that the rhizomes of Dropteris dilata replace those

of Dryopteris Filix-mas in the preparation of the official oleoresin as he has

found them to be four times as active as the latter in the expulsion of

Bothryocephalus latus. Hygienic Lab. Bull. No. 87, p. 250.

Du Mez—The Galenical Oleoresins.

969

Aspidium Filix-mas Swartz.

Aspidium mildeanum Goeppert.

Lastrea Filix-mas Presl.

Nephrodium Filix-mas Michaux.

Polyp odium Filix-mas Linne.

Polystichum Filix-mas Roth.

Tectarea Filix-mas Cavan.

Polypodium-nemorale Salisbury.

Polystichum durum et induratum Schui.

Polystichum abbreviatnm I)e Candolle.

In addition to the rhizomes of Dryopteris Filix-mas (Linne)

Schott, the United States Pharmacopoeia also permits the use of

the rhizomes of Dryopteris marginalise Linne formerly referred

to the genius Aspidium as Aspidium margindle Schwartz. It

should be noted in this connection that the official recognition

of Dryopteris marginalis Linne appears to have been based on

the somewhat doubtful statements of but three persons made

hack in the seventies. These men, Patterson,1 Cressler,2 and

Kennedy,3 respectively, reported that they had prepared oleo¬

resins from the rhizomes of this fern. Two of them, Cressler

and Kennedy, also stated that their preparations were found to

be active in the expulsion of tape worm, while Patterson merely

reported that his preparation resembled the German oleoresin

of male fern in appearance and taste. There does not appear

to be any evidence in the literature to show that an oleoresin

authentically prepared from this rhizome was ever given a trial

by a reputable physician. Furthermore, there is no evidence

to the effect that the rhizome is ever used in preparing the

oleoresin at the present time, a statement which has also been

made by Rushy.4

The definition of Aspidium as given in the ninth revision of

the United States Pharmacopoeia is as follows: ^The rhizome

and stipes of Dryopteris Filix-mas (Linne) Schott, or of

Dryopteris marginalis (Linne) Asa Gray (Fam. Polypodiaceae ) ,

collected in the autumn, freed from the roots and dead portions

of rhizomes and stipes and dried at a temperature not exceed¬

ing 70° C. Preserve aspidium in tightly closed containers and

protect from light. ’ 5

1 Am. Journ. Pharm. (1875), 47, p. 292.

2 Cressler states that he prepared an oleoresin from what he thought to

be male fern, but which later proved to be Aspidium marginale. Ibid.,

(1878), 5, p. 290.

8 Ibid. (1879), 51, p. 382.

4 Drugg. Circ. (1910), 54, p. 616.

970 Wisconsin Academy of Sciences , Arts, and Letters.

With further reference to the species of drug specified by the

Pharmacopoeia, it should be stated that the male fern of com¬

merce, obtained from Europe, is frequently contaminated with

the rhizomes of other species of fern, principally those of

Vryopteris spinulosa Kunze. Pendorff (1903), who examined 20

samples of the commercial drug, reported that 12 of them con¬

tained over 50 per cent, of rhizomes of this species.

The pharmacopceial directions concerning the collection of the

rhizomes in autumn are in keeping with specifications given in

most of the foreign pharmacopoeias1 and are based on the re¬

sults of extensive investigations carried out in continental

Europe and England. Analyses of the drug harvested at dif¬

ferent periods of the year have shown autumn to be the sea¬

son in which the therapeutically active constituents are pres¬

ent in greatest amount. Thus, the firm of Caesar and Loretz,

in their Berichte for 1898, state that the amount of active con¬

stituents present does not begin to approach the maximum until

the month of August and that it again begins to diminish in

October. They, therefore, conclude that the rhizomes should

be harvested only in the months of August, September and

October. Similar conclusions were drawn by Ed. Schmidt2

from a series of observations made in France in 1903. The fol¬

lowing table compiled by the latter shows the variation in crude

filicin content of the ethereal extracts (oleoresins) prepared

from the rhizomes harvested during six consecutive months of

the year.

Table 8. — ■ Variation of crude filicin content due to season.

1 The Spanish Pharmacopoeia (1905) directs thae the rhizomes be collected

at the end of spring or in the autumn,

2 These pour Vobtention du Diplome de Docteur de VUnwersite de Parte

(1903), p. 116.

Du Mez—The Galenical Oleoresins.

971

The table not only shows a variation in the crude filicin

content due to season, but also points out the fact that there is

a very considerable variation due to the locality1 in which the

rhizomes are grown. This factor, while evidently overlooked

by the United States Pharmacopceial Revision Committee, ap¬

pears to be of considerable importance in influencing the qual¬

ity of the oleoresin. Further proof of this is to ibe found in

the reports of Van Aubel,2 Madsen,3 Matzdorff,3 and Caesar

and Loretz.4

Further inspection of the pharmacopoeial definition shows

that the official drug is intended to be represented by the whole

rhizome - and stipe deprived only of the roots and dead portions,

which is also in conformity with the description generally found

in foreign pharmacopoeias. This is a wise provision in that the

rhizomes not only contain less of the active constituents when

peeled5 but deteriorate much more rapidly. On the other hand,

compliance with this specification would appear to be a difficult

problem for. the pharmacist as practically all of the drug on the

American market is peeled. The latter statement is based on

the examination of a number of samples in the laboratory6 and

on the reports of pharmaceutical manufacturers7 and others8.

In the drying of the rhizomes, the United States Pharmaco¬

poeia specifies that the temperature shall not exceed 70° C.

This temperature is thought to be too high, as filmaron, the

most active constituent therapeutically, melts at 60 °C and is

very prone to undergo decomposition.9 The directions as given

1 A variation due principally to soil and climate.

2 Van Aubel (1896) states that the rhizomes growing in Wolmar on the

shores of the Aa and those growing in the Jura and Vosges mountains yield

an oleoresin which is more active therapeutically than that prepared from

the rhizomes growing in Italy.

3 Madsen (1897) and Matzdorff (1901) report the oleoresin prepared from

Russian rhizomes to be the most active.

4 Caesar and Loretz attribute the uniform activity of the oleoresin pre¬

pared by them to the fact that they obtain their supply of rhizomes from

the same locality each year.

5 See preceding table by Schmidt.

® Of the sixteen samples of male fern rhizomes purchased from various

sources in the United States and examined in the laboratory all but three

were in the peeled condition.

7 Letters received from a number of pharmaceutical manufacturers in this

country indicate that the drug as usually received from Europe is peeled.

8Flaut (1914) states that though the 77. 8. Pharmacooepia requires the

use of unpeeled aspidium, none such is to be found on the market.

8 Kraft (1902).

972 Wisconsin Academy of Sciences, Arts , and Letters .

in the Belgian Pharmacopoeia (1906), “dry at a temperature

below 40°C,” or the Norwegian Pharmacopoeia (1914), “dry

at a temperature not exceeding 60° C,” appear to be more

rational.

In connection with the pharmacopoeial provision concerning

the preservation of the drug, attention is called to the fact that

the late edition of the German Pharmacopoeia (1910) requires

that the dried rhizomes be kept over freshly calcined lime.

Such a procedure was shown by Hager, as early as 1871, to

render the oleoresin prepared therefrom less liable to form a

deposit.

The fact that the United States Pharmacopoeia does not

specify a time limit for the consumption of the drug is unfor¬

tunate in view of the rapidity with which it is known to de¬

teriorate.1 So important is this factor, that the French Phar¬

macopoeia (1908) directs that only the recently collected and

freshly dried rhizomes be employed and the other European

pharmacopoeias commonly specify that they be renewed an¬

nually. That there is need of similar restrictions in this

country will become evident from the following table showing

the results obtained in the examination of fourteen samples

of commercial rhizomes. Six of these samples were purchased

from importers and drug millers in the United States during

the winter and spring of 1909 and 1910, respectively. The other

specimens were received in January of 1913 and represent

samples obtained from abroad as well as in this country. In

each case, the rhizomes were sorted, those shoAving a green frac¬

ture having been separated from those showing an internal

brown color.

1 Peschier as early as 1825 noted that the therapeutic activity of the

rhizomes diminished on ageing and recommended that they should he con¬

sumed within a period of less than two years after harvesting.

Caesar and Loretz state that they prepare the year’s supply of oleoresin

immediately after harvesting and drying the rhizomes to insure the maxi¬

mum activity of the preparation.

Du Mez — The Galenical Oleoresins.

973

Table 9. — Percentage of green rhizomes in samples of male fern purchased

from drug millers and jobbers.

1 Composed entirely of Osmunda rhizomes.

It will be noticed that even the rhizomes purchased in Ger¬

many were not in good condition. As these rhizomes were ob¬

tained in January, they should have shown an internal green

coloration had they consisted of the fresh stock harvested in

the preceding autumn. From this, it appears that the German

supply for exportation, at least, is not renewed yearly as it

should be, but is allowed to accumulate and deteriorate.

U. S. P. Text and Comments Thereon.

Oleoresin of aspidium was admitted to the United States

Pharmacopoeia in 1870 and has been official in all subsequent

editions.

1870

Oleoresina Filicis

Oleoresin of Fern

Take of Male Fern,1 in fine powder,3 pour ether upon it, until twenty-four

twelve troyounces; Ether 4 a suf- fluidounces of liquid have slowly

ficient quantity. passed.6 Becover7 the greater part of

Put the male fern into a cylindri- the ether by distillation on a water-

cal glass percolator, provided with a bath, and expose the residue, in a

stop-cock, and arranged with cover capsule, until the remaining ether has

and receptacle suitable for volatile evaporated.8 Lastly, keep the oleo-

liquids,6 press it firmly, and gradually resin in a well-stopped bottle.®

974 Wisconsin Academy of Sciences , Arts, and Letters.

1880

Oleoresina Aspidii

Oleoresin of Aspidium

[Oleoresina Filieis, Pharm., 1870]

Aspidium,1 in No. 60 powder,3 one

hundred parts . 100.

Stronger Ether,4 a sufficient quantity.

Put the aspidium into a cylindrical

glass percolator, provided with a

cover and receptacle suitable for vola¬

tile liquids,6 press it firmly, and

gradually pour stronger ether upon it,

until one hundred and fifty (150)

parts of liquid have slowly passed.6

Recover7 the greater part of the

ether by distillation on a water-bath,

and expose the residue, in a capsule,

until the remaining ether has evap¬

orated.8

Keep the oleoresin in a well stopped

bottle9.

Note. Oleoresin of aspidium us¬

ually deposits, on standing, a granu¬

lar crystalline substance.10 This should

be thoroughly mixed with the liquid

portion, before use.11

1890

Oleoresina Aspidii

Oleoresin of Aspidium

Aspidium,1 recently2 reduced to No. 60

powder,3 five hundred grams

. 500 Gm.

Ether4 a sufficient quantity.

Put the aspidium into a cylindrical

glass percolator, provided with a stop¬

cock, and arranged with cover and

receptacle suitable for volatile liquids.6

Press the drug firmly, and percolate

slowly with ether, added in succes¬

sive portions, until the drug is ex¬

hausted.6 Recover the greater part

of the ether from the percolate

by distillation on a water-bath, and,

having transferred the residue to a

capsule, allow the remaining ether to

evaporate spontaneously.8

Keep the oleoresin in a well-stop¬

pered bottle.9

NOTE. Oleoresin of Aspidium

usually deposits, on standing, a gran¬

ular-crystalline substance.10 This

should be thoroughly mixed with the

liquid portion before use.11

Du Mez — The Galenical Oleoresins.

975

1900

Oleoresina Aspidii

Oleoresin of Aspidium

Aspidium,1 recently 2 reduced to No.

40 powder,3 five hundred grammes

. 500 Gm.

Acetone,4 a sufficient quantity.

Introduce the Aspidium into a cy¬

lindrical glass percolator, provided

with a stop -cock, and arranged with a

cover and a receptacle suitable for

volatile liquids.5 Pack the powder

firmly and percolate slowly with ace¬

tone, added in successive portions,

until the Aspidium is exhausted.*

Recover7 the greater part of the ace¬

tone from the percolate by distilla¬

tion on a water-bath, and, having

transferred the residue to a dish, al¬

low the remaining acetone to evap¬

orate spontaneously in a warm place.8

Keep the oleoresin in a well-stoppered

bottle.9

NOTE. Oleoresin of aspidium us¬

ually deposits, on standing, a granu¬

lar crystalline substance.10 This

should be thoroughly mixed with the

liquid portion before use.11

Average dose . . . 2 Gm.

(30 grains).

1910

Oleoresina Aspidii

Oleoresin of Aspidium

Oleores. Aspid.— -Oleoresin of Male Fern

Aspidium,1 recently 2 reduced to

No. 40 powder,3 five hundred

grammes . 500 Gm.

Ether,4 a sufficient quantity.

Place the aspidium in a cylindrical

glass percolator, provided with a

stop-cock, and arranged with a cover

and a receptacle suitable for volatile

liquids.5 Pack the powder firmly, and

percolate slowly with ether, added in

successive portions, until the drug is

exhausted.* Recover 7 the greater

part of the ether from the percolate

by distilling on a water bath, and,

having transferred the residue to a

dish, allow the remaining ether to

evaporate spontaneously in a warm

place.8 Keep the oleoresin in a well-

stoppered bottle.8

NOTE. — Oleoresin of Aspidium, on

standing, usually deposits a granular

crystalline substance.10 This should

be thoroughly mixed with the liquid

portion before use.11

Average Dose— Caution ! Single

dose, once a day, Metric, 2 Gm.—

Apothecaries, 30 grains.

976 Wisconsin Academy of Sciences , Arts , and Letters.

1. ) The Pharmacopoeia of 1870 recognized but one species

of fern (Aspidium Filix-mas) as the source of the official drug,

hence, the directions : 1 ‘ Take of Male Fern, etc. ’ ’ In the sub¬

sequent editions, Aspidium marginale was also recognized as a

cource of supply. In these editions, the drug is, therefore,

referred to by the generic name, Aspidium. The species from

which the official drug is obtained are now referred by botanists

to the genus Dryopteris. See page 969 under “Drug used, its

collection, preservation, etc.”

2. ) Owing to the fact that the drug deteriorates rapidly

when in the powdered condition, the last three editions of the

Pharmacopoeia have specified that the rhizomes be preserved

whole and that they may be reduced to a powder shortly before

using. For factors causing the deterioration of the drug, see

under “Drug used, its collection, preservation, etc.”

3. ) In the last two editions of the Pharmacopoeia, it is di¬

rected that the drug be employed in the form of a moderately

coarse powder (No. 40). In the previous editions, a fine pow¬

der (No. 60) was specified. The coarser powder posesses dis¬

tinct advantage in that it is better adapted to percolation and

can be produced with a greater degree of uniformity.

4. ) It will be observed that the pharmacopoeias of 1870, 1880

and 1890 directed that the drug be extracted with ether; that

acetone was the menstruum specified in the Pharmacopoeia of

1900 ; and that ether is again directed to be used for this pur¬

pose by the present Pharmacopoeia.

These changes appear to have been made for economic rea¬

sons as is evidenced in the following statement by Beringer

(1916) : “In the Eighth Revision, acetone was directed in place

of ether, because at that time the former was cheaper. As it

is now permissable to use denatured alcohol in the manufacture

of ether, that solvent is made so cheaply that it is again advan¬

tageous to use it in place of acetone.” If the comparative cost

of the two solvents was the factor which induced the Revision

Committee to make the last change, it is indeed fortunate that

ether was the cheaper inasmuch as it has proven to be the more

desirable from a scientific standpoint as well.

Acetone, although the official menstruum for the preparation

of this oleoresin for more than a decade, does not appear to

have been employed for this purpose to any considerable ex-

Du Mez — The Galenical Oleoresins.

977

tent by the manufacturer. This statement is based upon the

examination of a number of commercial samples purchased at

various times during the past ten years. While the reason for

the above condition does not become apparent from the litera¬

ture, it is thought that it is to be attributed to the fact that

acetone yields a product of inferior quality, rather than to the

relatively low cost of ether. In support of this supposition, at¬

tention is called to the statement of Dunn (1909), who reports

that it is necessary to purify the oleoresin made with acetone

by dissolving the same in ether, also, to the observations made in

the laboratory.

Experiments conducted in the laboratory have shown that

the oleoresin, when prepared with acetone, is brown in color and

always contains considerable deposited matter. While the greater

bulk of the deposited material has the appearance of extractive

matter and is very likely of no consequence from a therapeutical

standpoint, portions of it answer to the descriptions of filixnigrin

and filix acid, decomposition products of the therapeutically

active constituents. The latter observation is in keeping with

that of Kraft (1902), who found that filmaron, the most im¬

portant of the therapeutically active constituents, decomposes

in acetone solution yielding the above mentioned decomposition

products. It was also noted that the amount of deposited

material increases much more rapidly in the preparations made

with acetone than in those in which ether was used as the men¬

struum for extracting the drug.

As previously stated, ether has proven to be the more sat¬

isfactory solvent for scientific as well as economic reasons. In

fact it has been found to be superior to any of the solvents

which have been experimented with in this connection, namely :

benzin, benzene, chloroform and carbon disulphide. See Part I,

page 921, under ‘ ‘ Solvents. ’ ’ At the present time, it is the sol¬

vent universally employed in the manufacture of the oleoresin,

which is in itself a good reason for its adoption by the Pharma¬

copoeia. Furthermore, the product obtained with ether is

perfectly homogenous and forms a deposit only after long

standing, the constituents of therapeutic value evidently under¬

going no decomposition in ethereal solution. However, the

quality of the preparation, even when ether is employed in ex^

tracting the drug, is influenced to a certain extent by the purity

of the solvent.

62— S. A. L.

978 Wisconsin Academy of Sciences , Arts , and Letters.

Alcohol and water appear to be the impurities which tend

to exert a deleterious influence upon the finished product. Thus,

Daccomo and Scoccianti (1896) observed that ether containing

a considerable amount of alcohol did not completely extract the

therapeutically active constituents from the drug and that the

oleoresin obtained was more prone to form a deposit than when

ether of a greater degree of purity was used. See also page 984

under “Yield of oleoresin.” Similar effects were observed

by the firm of Caesar and Loretz (1899.) The presence of

water is so great a factor in promoting decomposition

(hydrolysis?) that the German Pharmacopoeia (1910) directs

that the rhizomes be preserved over freshly burned lime, a

procedure which was recommended by Hager as early as 1871.

Further evidence of the undesirability of the presence of water

is to be found in the Norwegian (1913) and Finnish (1914)

pharmacopoeias, which direct that the ethereal tincture be dried

with anhydrous sodium sulphate or fused calcium chloride pre¬

vious to the removal of the solvent by distillation.

5. ) For a description of the various forms of percolators

designed for extraction with volatile solvents, see Part I under

‘ ‘ Apparatus used. ’ ’

6. ) All editions of the Pharmacopoeia, including the present,

direct that the drug be extracted by the process of simple per¬

colation even though the advantages of a continuous extraction

apparatus in the handling of a volatile solvent like ether have

been repeatedly pointed out. See Part 1 under “Solvents”

and under “Apparatus used.”

Of special interest in this connection is the work of Matzdorff

(1901), the results of which show that the therapeutically ac¬

tive constituents are not completely extracted by simple perco¬

lation as ordinarily carried out, but that complete extraction

is effected in a comparatively short time with the use of a Soxh-

let’s apparatus.

7. ) In connection with the recovery of the solvent by dis¬

tillation, attention is again directed to the deleterious effect of

the presence of moisture and to the manner in which the same

is directed to be removed by the Norwegian and Finnish phar¬

macopoeias. See above.

Attention is also invited to the pharmacopoeial directions re¬

garding distillation, namely that it be conducted on a water

Du Mez—TJie Galenical Oleoresins.

979

bath. Inasmuch as Kraft (1902) states that filmaron melts

at 60 °C and undergoes decomposition at higher temperatures,

it is thought that the pharmacopoeial directions should contain

a warning against exceeding this temperature during distilla¬

tion.

8. ) The removal of a part of the solvent by spontaneous

evaporation as directed by the Pharmacopoeia tends to operate

against obtaining a uniform product as the time required to

accomplish the same varies with the temperature. If evapora¬

tion is allowed to proceed at a low temperature (winter tem¬

perature), the preparation will be exposed to the action of the

air for a very considerable length of time and partial oxida¬

tion of some of the constituents will very likely result.

The complete removal of the solvent can be accomplished

much more rapidly by heating the preparation on a water bath,

and without injury, if the temperature is kept below 60 °C. By

such a procedure, the above conditions are eliminated and a more

uniform product will be obtained.

9. ) The oleoresin should be kept in well-stoppered bottles

as it becomes rancid on prolonged exposure to the air due to

the hydrolysis and partial oxidation of the glycerides composing

the fatty oil.

10. ) For a discussion of the nature of the deposit which

forms in the oleoresin on standing, see pages 992 and 1004 under

“Constituents of therapeutic importance,” and under “Other

properties. ’ ’

11. ) As to the propriety of the pharmacopoeial directions

concerning the mixing of the deposit with the liquid portion

before dispensing, there is some doubt. The question, however,

is one which should be decided by the pharmacologist rather

than the pharmacist and will, therefore, not be considered here.

The use of an alkali, ammonia as suggested by Beringer

(1892), for the purpose of facilitating the admixture of the pre¬

cipitate with the liquid portion should be condemned as a dan¬

gerous practice. The danger lies in the fact that the slightly

soluble toxic constituents are converted into soluble compounds

by union with the alkali and are thereby rendered readily ab¬

sorbable.

Of further interest in this connection is the procedure recom¬

mended by Seifert (1881) and Kraemer (1884) for avoiding

980 Wisconsin Academy of Sciences, Arts, and Letters.

the formation of a deposit, namely: that the ethereal tincture

be kept on hand and that the oleoresin be prepared therefrom

just previous to dispensing.

Yield

The yield of oleoresin, when ether is the solvent employed

in extracting the drug, is commonly stated to be 10 to 15 per

cent, in the various dispensatories and American text-books on

pharmacy. As a matter of fact, the amount of oleoresin actually

obtained is about 7 to 10 per cent. (See the tables which fol¬

low.) When petroleum ether or benzene is used, the yield is

slightly lower, as a rule, whereas, it is much higher (about 18

per cent.) when acetone is employed. These statements refer

to the yield as found for the air dried drug. When the latter

is dried at a temperature of 100 to 110° C, the percentage of

oleoresin obtained will naturally be somewhat higher as is shown

in the table immediately following.

Du Mez — The Galenical Oleoresins,

981

Table 10. — Yield of oleoresin as reported in the literature.

Date

1827

1828

1829

1844

1851

1852

1876

1888

1891

1892

Remarks

Rhizomes harvested

August.

Rhizomes harvested in

September.

Rhizomes harvested in

February.

Peeled rhizomes dried at

100° c.

Portion of rhizomes having

borne fronds the previous

year.

Portion of rhizome bearing

fronds.

Portion of rhizome to de¬

velop fronds the next year.

Rhizomes harvested in

April. Dried at 110° C.

Rhizomes harvested in July

Dried at 110° C.

Rhizomes harvested in Oc¬

tober. Dried at 110° C.

Rhizomes harvested in

July, 1889.

Rhizomes harvested in

September, 1889 .

Rhizomes harvested in

October, 1889

Rhizomes harvested in

December.

Rhizomes harvested in

February, 1890 .

Rhizomes harvested in

April. 1890.

Whole Rhizomes.

Peeled

Rhizomes from “Rheinische

Tiefebene (Calcar).”

Rhizomes from “Rheinische

Tiefebene (Dinslaken).”

Rhizomes from “Yoreifel

(Aachen.)”

Rhizomes from “Hocheifel

(Gterolstein.)”

Rhizomes from “Taunus

(Braubach.)”

Rhizomes from “Wester-

wald auf Thonschiefer

(Daaden.)”

de Paris, 1903, p. 78.

du Diplome du Docteur 1’ University

982 Wisconsin Academy of Sciences , Arts , and Letters.

Table 10. — Continued.

Date

1902

1903

1905

1906

Observer

Bellingrodt-

Con.

Hausmann

Buttin .

Schmidt, E. (l)

Dietrich

Roder

Wollenweber.

Yield of oleoresin to

Per ct.

9.95

8.90

8.50

10.00

8.00

9.30

8.00

6.60

9.60

9.10

6.40

6.90

9.80

9.30

7.00

9.94 to

10.60

Up to

11.20

9.22 to

10.1

10.30

10.00

s

Per ct.

Benzene

9.81

10.10

Petrol.

Ether

9.8

9.5

Remarks

Rhizomes from “Wester-

wald auf Basalt boden

(Daaden.)”

Rhizomes from “Hansruck

(Simmern) ’

Rhizomes from “St.Gallen,

Switzerland.”

Rhizomes ircm “Bludenz

(Vorarlberg).”

Rhizomes from “Appenzell,

Switzerland.”

Rhizomes from “Bierber-

wier, Tyrol.”

Rhizomes harvested in

spring.

Whole rhizomes from near

Paris harvested in Sep¬

tember.

Whole rhizomes from the

Vosges Mts. harvested in

September.

Whole rhizomes from the

Jura Mts. harvested in

September.

Peeled rhizomes from the

Vosges Mts. harvestsd in

September.

Whole rhizomes from near

Paris harvested in Oc¬

tober.

Whole rhizomes from the

Vosges Mts. harvested in

October.

Whole rhizomes from the

Jura Mts. harvested in

October.

Peeled rhizomes from the

Vosges Mts. harvested in

October.

From air dried rhizomes.

From rhizomes dried at

100° C.

Yield obtained when the

product was heated at

95° O for 2 hours, cooled

in a desiccator & weighed.

Air dried rhizomes extract¬

ed in a Soxhlet’s appar¬

atus.

Exiccated rhizomes ex¬

tracted in a Soxhlet’s

apparatus.

Air dried rhizomes extract¬

ed in a Soxhlet’s appar¬

atus.

Exiccated rhizomes ex¬

tracted in a Soxhlet’s

apparatus,

1. c., p. 110.

Du Mez — The Galenical Oleoresins.

983

Table 10. —Continued.

Date

1999

1911

1913

914

Observer

VanderkleedO)

Vanderkleed

Rosendahl...

Harrison&Self

Riedel .

Vanderkleed

Yield of oleoresin to

Perct.

Perct. Perct.

10.00

12.50

11.50

9.50

11.60

8.80

7.90

8.80

7.70

9.70

8.60

7.50

7.00

10.90

9.40 to

9.70

o “

Per ct.

\ Solvent ?

< 6.85 to

( 10.12

Remarks

Reported as yield of oleo¬

resin.

Rhizomes harvested in

May.

Rhizomes harvested in

August.

Rhizomes harvested in

October.

Rhizomes from “Harz.”

‘Bay<

( “ Schwarz -

-n wald, Wuert-

( emberg.”

I “Mosel,

< Rhein-

( Preussen.”

Average yield of oleoresin

is reported as 8. 23 per cent.

1 The high yield (1.79 per cent.) obtained in this instance is suggestive of

the use of acetone as the menstruum for exhausting the drug. It may, how¬

ever, have been due to the extensive adulteration of the latter with the

rhizomes of Dryopteris spinulosa. Rosendahl (1911) obtained 17.0 per cent,

of oleoresin from the rhizomes of this species by extraction with ether.

Table 11 .—Yield of oleoresin obtained in the laboratory.

0) The alcoholic extract was obtained by simple percolation.

984 Wiscorisin Academy of Sciences, Arts , and Letters.

An examination of the first of the foregoing tables reveals

the fact that the yield is influenced to a very considerable extent

by the condition of the drug from which the oleoresin is pre¬

pared. Thus, for instance, the amount obtained is less when the

powdered whole rhizomes are used than when peeled rhizomes

are employed. This is to be expected in view of the fact that

the outer layers contain little that is soluble in the solvent

(ether) usually made use of. It will also be noticed that na¬

tural causes, such as, locality in which the rhizomes are grown,

and time of harvesting are important factors in this connec¬

tion. These influences will be brought out more clearly on an

inspection of the following table which shows the results of this

nature obtained by Ed. Schmidt.

Table 12. — Effect of locality in which the rhizomes are grown and the time

of harvesting on the yield of oleoresin.

In addition to the comments already made with regard to the

influence of the solvent on the yield, the observations of Dac-

como and Sccocianti (1896) are of importance in this connec¬

tion. These investigators found that the amount of oleoresin

obtained, when ether was employed for extracting the drug, de¬

pended to some extent on the purity of the former. Thus,

ether, specific gravity 0.720 gave 10 per cent, of oleoresin,

whereas, ether, specific gravity 0.756 yielded 17 per cent. It

was further pointed out, however, that the greater yield was

not desirable as in this case the preparation did not contain

all of the therapeutically active constituents and in addition

was more prone to form a deposit on standing.

Du Mez — The Galenical Oleoresins.

985

Chemistry of the Drug and Oleoresin.

Tabulation of Constituents .

A survey of the voluminous literature1 pertaining to the

chemistry of the male fern rhizome shows the constituents of

pharmaceutical interest to be as follows: volatile oil, fatty oil,

filix acid, albaspidin, flavaspidic acid, aspidinol, flavaspidinin

(phloraspin), filmaron, filixnigrin, chlorophyll, filix tannic acid,

wax, sugar, starch and inorganic constituents. Of these sub¬

stances, the following have been identified in the oleoresin ob¬

tained by extracting the drug with ether:

Volatile oil 2

Fatty oil3 .

Filix acid 4

Albaspidin 5

Flavaspidic acid

Aspidinol 6 ....

Flavaspidinin 5 .

Filmaron 5 .

1 The following have reported more or less complete analyses of the male

fern rhizome or of the ethereal extract : Gebhardt, cited by Geiger, Mag. f.

Pharm. (1824), 7, p. 38; Morin, Journ. de Pharm. et de Chim. (1824), 10,

p. 223; Buchner, Rep. f. d. Pharm. (1827), 27, p. 337; Batso, Trommsdorff’s

n. Journ. d. Pharm. (1827), 14, p. 294; Peschier, Ibid. (1828), 17, p. 9;

Luck, Jahrb. f. prakt. Pharm. (1851), 14, p. 129; Bock, Arch. d. Pharm.

(1851), 115, p. 257; Kruse, Ibid (1876), 209, p. 24; Daccomo, Annali di

Chim et Farmak. (1887), 87, p. 69; Boehm, Arch. f. Exp. Path. u. Pharmak.

(1896), 38, p. 35; Kraft, Schweiz. Wochenschr. f. Chem. u. Pharm. (1902),

40, p. 322.

2 The percentage of volatile oil as given above has been computed on the

basis of an average yield of 10 pr cent, of oleoresin.

3 The quantity of fatty oil present in the oleoresin has been shown to vary

with the strength of the ether employed in extracting the drug and with

the degree to which the latter has been exhausted. These factors, however,

are not sufficient to explain the large variation in oil content as found by

various investigators. The variation is more probably due to the different

methods employed in its estimation. Thus, Bock reports the presence of

42 per cent of fatty oil. Arch. d. Pharm. (1851), 115, p. 266; Kremel esti¬

mates it at 40 to 45 per cent, Pharm. Post d. Pharm. (1887), 20, p. 525;

Wollenweber at 70 to 75 per cent, Arch. d. Pharm. (1906), 244. p. 467.

4 There is a very considerable difference in the filix acid content of the

oleoresin as reported in the literature. This is due, principally, to the nat¬

ural variation in the filix acid content of the drug and to the different

methods employed in its estimation. The limits as given above are those

obtained by the method of Fromme and represent the percentage occuring

in the oleoresin prepared from the better rhizomes. Under these conditiops,

Madsen found 5.8 to 12.1 per cent. Arch. f. Pharm. og. Chem. (1897), 54,

p. 269; Gehe & Co., 5.78 to 11.32 per cent, Handels-Ber. (1897), p. 60;

Bellingrodt, 5.75 to 10.75 per cent, Apoth. Ztg. (1898), 13, p. 869; Caesar

and Loretz, 8.65 to 12.48 per cent, Geschaefts-Ber. (1901), p. 68.

986 Wisconsin Academy of Sciences, Arts, and Letters.

Filixnigrin 5 . . “ “ 6.00 “ “

Chlorophyll6 . . “ “

Wax 7 . . . . “ “

Ash . 1 ‘ 3.50 to 5.00 “ “

Occurrence and Description of Individual Constituents.

Volatile oil.8 The volatile oil as described by Ehrenberg is

a clear yellow liquid having a specific gravity of 0.85 to 0.86

at 15° C, and is stated by him to be composed principally of

fatty acid esters of hexyl and octyl alcohol, the acids ranging

from propionic to caproic.

The quantity of essential oil present in the rhizomes is stated

• to vary with the seasons of the year, 0.04 to 0.045 per cent, being

contained therein at the time of the year when the drug is

usually collected.9

Fatty oil.10 The fatty oil as obtained from the male fern

rhizomes by extraction with ether and subsequent purification

is stated by Katz11 to be composed of the glyceryl esters of oleic,

palmitic, cerotic and butyric acids.12

Filix acid 13 ( Filicin )14 Filix acid (C35H38012) crystalizes

5 Kraft, Schweiz. Wochenschr. f. Chem. u. Pharm. (1902), 40. p. 323.

6 Bock, Arch. d. Pharm. (1851), 115, p. 266.

7 Kraft, 1. c.

8 The volatile oil as described above is that obtained from the rhizomes

by steam distillation and in all probabilities differs somewhat from the same

as it exists in the galenical oleoresin.

9 Ehrenberg reports the presence of volatile oil as follows : rhizomes

gathered in April, 0.008 per cent; in June .025 per cent; in September, Octo¬

ber and November, 0.04 and 0.045 per cent. Arch. d. Pharm. (1893), 231,

p. 345.

10 The fatty oil of male fern was probably first isolated by Luck. In

1851, he reported that the oily portion ( filixolme ) of the ethereal extract

was a glyceride yielding filomy silsaeure and filixolinsaeure upon saponifi¬

cation. Jahrb. f. prakt. Pharm. (1851), 22. p. 130.

From Luck’s description it is considered that these acids were in all

probability butyric and oleic, respectively.

n Arch. d. Pharm. (1898), 236, p. 655.

12 Butyric and oleic acids have also been identified by Farup in the fatty

oil obtained from Aspidium Spinulosum. In addition a phytosterol, lino-

linic, and probably isolinolinic acid are stated to have been detected. Arch,

d. Pharm. (1904), 242, p. 17.

13 The term filixsaeure was first used by Luck to designate this constituent.

Filix acid is the translation given above rather than the usual English

form, filicic acid, to avoid confusion with the filicmsa&ure of Boehm, a re¬

duction product of the former, Ann .d. Chem. (1899J, 307, p. 249, or the

Acidum filiceum of Batso, a supposedly volatile acid which the latter isolated

from the ethereal extract. Tromsdorff’s n. Joura. d. Pharm. (1827), 14,

p. 249.

14 Filicin is the term introduced by Poulsson to designate the crystalline

form of filix acid as he was of the opinion that it also existed in the amor-

Du Mez—The Galenical Oleoresins.

987

in small yellow plates melting at 184 to 185° C. It is difficulty

soluble in water, alcohol, and ether, quite readily soluble in

ethyl acetate. According to Boehm,15 its constitution16 is prob¬

ably represented by the following structural formula:

hsc ch,

Filix acid has been found to be present in the male fern

rhizome17 in quantities varying from 0.268 to 2.159 per cent,

the variation in content depending principally upon the loca¬

tion in which the rhizomes are grown and on the time of har¬

vesting.18

phous state. Arch. f. Exp. Path. u. Pharm. (1895), p. 357. The term is now

usually employed to designate the mixture of acid substances obtained in

the quantitative evaluation of the oleoresin. It should not be confused

with the Filicina of Batso, supposedly an alkaloid isolated from the ethereal

extract. 1. c.

15 Ann. d. Chem. (1901), 318, p. 256.

16 The following investigators have contributed work on the constitution

of filix acid: Luck, Ann. d. Chem. (1845), 54, p 119; Jahrb. f. prakt.

Pharm. (1851), 22, p. 129; Grabowski, Ann. d. Chem. (1867), 143, p. 279;

Daccomo, Ber. d. deutsch. Chem. Gesell. (1888), 21, p. 2962; Gaz. Chim.

Ital. (1895), 24, 1, p. 511 ; Ibid. (1896), 26, 2, p. 441 ; Paterno, Ber. d. deutsch.

Chem. Gesell. (1889), 22, p. 463; Schiff, Ann. d. Chem. (1889), 253, p. 236;

Poulsson, Arch. f. Exp. Path. u. Pharm. (1895), 35, p. 97; Boehm, Ibid.

(1897), 38. p. 35; Ann. d. Chem. (1898, 302, p. 171.

17 Filix acid has also been isolated by Hausmann from Athyrium Filix

femina Roth. Arch. d. Pharm. (1899), 237. p. 556, and has been identified

by Bowman in Aspidium rigidum Swartz. Am. J. Pharm. (1881), 53, p. 389.

18 Matzdorff, Apoth. Ztg. (1901), 16, p. 274.

988 Wisconsin Academy of Sciences, Arts, and Letters.

Albaspidin.19 Albaspidin crystallizes in fine colorless needles

melting at 147 to 148° C. It is readily soluble in ether, chloro¬

form and benzol, difficultly soluble in alcohol, acetone and

glacial acetic acid. Its constitution is stated to be represented

by one of the three following formulae :20

I

Flavaspidic acid. Flavaspidic acid (C24H2808) was first

isolated from the ethereal extract by Boehm. It is stated to

exist in two forms (a and /?) which differ in their melting points,

the a-flavaspidic acid melting at 92 °C and the ^-modification at

156 °C. The a-acid on heating is converted into the j3- acid

19 Albaspidin should not be confused with aspidin. Hausmann has shown

the latter to be a constituent of Dryopteris spinulosa O. Ku.ntze, but that

it is not present in Dryopteris filix mas Schott. Arch. d. Pharm. (1899),

237, p. 544.

30 Boehm, Arch. f. Exp. Path. u. Pharm. (1897), 38, p. 35; Ann. d. Chem.

(1901), 318, p. 268.

Du Mez — The Galenical Oleoresins.

989

which may be crystallized from hot benzol or glacial acetic acid.

The /?-form is converted into the a-modification on crystallizing

the former from alcohol. The a-acid is thought to be the enol-,

the /?-acid the keto-form. The structure is shown in the fol¬

lowing formulae:21

Flavaspidic acid has been isolated from the male fern rhi¬

zome in quantities varying from 0.10 to 0.15 per cent.22

Aspidinol. Aspidinol (C12H1604) crystallizes in small yel¬

lowish-white needles melting at 156 to 161 °C. It is difficultly

soluble in petroleum ether and benzol, readily soluble in ether,

alcohol, chloroform, carbon disulphide and acetone. The fol¬

lowing two formulae have been suggested by Boehm as repre¬

senting the structure of this compound :23

CH,

I

C

CH,

I

C

HOC

HC

V

COCH. HOC

OV

COCC,H» HjCjCOC

CH

COH COH

Flavaspidinin.24: Flavaspidinin closely resembles flavaspidic

21 Boehm, Ann. d. Chem. (1901), 318, p. 253 ; Ibid. (1903, 329, p. 310.

21 In addition to establishing the presence of flavaspidic acid in the male

fern rhizome, Hausmann has also isolated this compound from Athyrium

Filix femina Roth, and Aspidium spinulo'sum Swartz. Arch. d. Fharm. (1899),

237, p. 556.

23 Arch. f. Exp. Path. u. Pharm. (1893), 33, p. 35; Ann. d. Chem. (1901),

318, p. 245; Ibid. (1903), 329, p. 286.

24 Kraft. Schweiz. Wochenschr. f. Chem. u. Pharm. (1902), 40, p. 323.

The “phloraspin” (C23H2808) of Boehm is probably identical with flavas¬

pidinin. The pale yellow crystals obtained from the alcoholic solution melt

at 211 °C, and are stated to be almost insoluble in ether, petroleum ether,

benzene and carbon disulphide, but more readily soluble in acetone, chloro¬

form, hot absolute alcohol, ethyl acetate, glacial acetic acid and boiling

xylene. Ann. d. Chem. (1903), 329, p. 338.

990 Wisconsin Academy of Sciences , Arts , and Letters.

acid. It crystallizes from ethyl acetate in nearly colorless

prisms melting at 199 °C. It is soluble in methyl alcohol, dif¬

ficultly soluble in ether, carbon disulphide and alcohol, readily

soluble in warm benzene, chloroform, ethyl acetate, acetone and

amyl alcohol.

Filmaron.25 Filmaron (C47H52016) is a light yellow, amor¬

phous powder melting at about 60° C. It is insoluble in water,

difficultly soluble in alcohol, methyl alcohol and petroleum ether,

readily soluble in acetone, chloroform, ether, ethyl, acetate,

benzene, carbon disulphide, carbon tetrachloride, amyl alcohol

and glacial acetic acid. In acetone solution, at ordinary tem¬

peratures. or upon warming with alcohol, it gradually decom¬

poses into filix acid and filixnigrin. The following structural

formula has been suggested by Kraft:

II, Cn. .xh3

<r

Filixnigrin ,26 Filixnigrin is the term used by Kraft to desig¬

nate the mixture of brown to black amorphous decomposition

products of the foregoing constituents. These decomposition

products differ from the mother substances in that they are in¬

soluble in petroleum ether. They have been isolated from the

ether al extract. To what extent they occur in the plant, if at

all, has not been determined.

Chlorophyll. The green coloring matter of the male fern

rhizome and of the oleoresin prepared therefrom is generally

conceded by the various investigators to be chlorophyll, al-

25 Kraft, 1. c.

28 Kraft, l. c.

Du Mez — The Galenical Oleoresins,

991

though, no attempt appears to have been made to determine its

composition. Work upon the pigments present in a closely

related species of fern, Aspidium Filix femina Roth, has re¬

sulted in the isolation of carrotin (C16H320) and three aspi-

diophylls, C208H347O32N, C240H320O31N2 and C210H34e048N2?.27

The amount of chlorophyll present in the rhizome varies

with its age and with the season of the year.28

Wax. The wax occurring in the male fern rhizome has not

been studied from a chemical standpoint, although its presence

in the ethereal extract was observed at a very early date.29

Filix Tannic Acid.30 Filix tannic acid (C41H48N024) is a

glucoside breaking down upon hydrolysis into hexose and a

mixture of reddish-brown compounds.31 It is readily soluble

in water and dilute alcohol.

Filix tannic acid usually constitutes about 7 per cent, of

the rhizome, as much as 7.8 per cent, having been isolated there¬

from.32

Ash. Analyses33 of the male fern rhizome have shown the

ash to contain the basic elements, K, Na, Ca, Mg, A1 and Fe

combined with the acid radicles CF, S04", P04"', Si03" and

^Ebard, Ann. Inst. Pasteur (1899), 13, p. 456. The more recent work

of Willstaetter and his pupils on the chlorophylls isolated from more than

200 different plants belonging to numerous families indicates that mag¬

nesium is a constant consituent of the molecule, which is considered by

them to be a methyl phytyl ester of the tricarboxylic acid, chlorophyllin,

C31H29N4Mg ( COOH ) 3. Viewed in this light, the above formulae for the

aspidiophylls are erroneous in that they contain no magnesium and express

molecular weights which are much too high. Ann. d. Chem. (1908), 358,

p. 267 ; Ibid. (1910), 378, p. 1.

28 Kruse has observed that the rhizomes collected in April and October

have a more intense green color than those gathered in July. Arch. d.

Pharm. (1876), 209, p. 24.

29 Batso, Trommsdorff’s n. Journ. d. Pharm. (1827), 14, p. 294; Peschier

Ibid. (1828), 17, p. 5 and Bock, Arch. d. Pharm. (1851), 115, p. 266, report

the presence of a stearin-like substance in the ethereal extract.

Caesar and Loretz have observed that rhizomes rich in wax yield an

ethereal extract which is not fluid at the ordinary temperature. Gechaefts

Ber. (1897), p. 62.

30 In the light of our present knowledge concerning the chemistry of male

fern, filix tannic acid is not considered to be a constituent of the oleoresin

when prepared with ether. As its presence in the latter has been reported

by early investigators, the above description has been included here. See

analysis by Bock, Arch. d. Pharm. 1851, 115, p. 266.

31 Malin, Ann. d. Chem. (1867), 115, p. 276; Wollenweber, Arch. d. Pharm.

(1906), 244, p. 480.

33 Wollenweber, 1. c.

33Bock, Arch. d. Pharm. (1851), 115, p. 257; Spies, Jahresb. d. Pharm.

(1860), 20, p. 15.

992 Wisconsin Academy of Sciences , Arts , and Letters.

C03". Hell and Company34 report the presence of 0.0144 per

cent, of copper. Spies, however, was unable to detect the presence

of either copper or manganese.

The ash content of the dried rhizomes varies, about 2.0 to

3.0 per cent being the usual amount obtained.35

Constituents of Therapeutic Importance

The value of the oleoresin of aspidium as a teniafuge has

at various times been attributed to either its filix acid* 1 or vola¬

tile oil2 content. Comparatively recent pharmacological in¬

vestigation, 3 however, has shown that the property of expell¬

ing the tape worm is not due to a single constituent, but is

shared by a number of the acid-like components, namely: filix

acid, flavaspidic acid, albaspidin, aspidinol, flavaspidinin and

filmaron. Of these substances, filmaron is the most active and

is stated by Jaequet4 and others to be the constituent of most

importance therapeutically.

The diminution in the therapeutic activity of the oleoresin

on ageing has been found to be due to the breaking down of

some of these constituents into compounds which are inert or

less active as teniafuges. Of the decomposition products tested

by Straub, phloroglucin, filicin acid and butyric acid were

found to be non-toxic when administered to frogs.5 Filix acid

on the other hand was found to be toxic. Its value as a

teniafuge is, however, doubtful.6

Physical Properties

Color: The color of the oleoresin varies to a considerable

extent depending principally on the condition of the drug from

which it is prepared. It is described by various writers as

being yellowish-green, green, dark green or greenish-brown.

34 Pharm. Post (1894), 27, p. 168; Journ. de Pharm. et de Chim., 139,

p. 493.

36 Bock gives the ash content of the air dried rhizomes as 2.13 per cent.,

Kruse as 1.90 to 2.2 and Spies as 2.74. For the exsicated rhizomes, the latter

obtained 3.19 per cent.

1 Poulsson, Arch. f. Exp. Path. u. Pharmak. (1891), 29, p. 9.

3 Robert, Therap. Monatsch. (1893), p. 136.

3 Straub, Arch. f. Exp. Path. u. Pharmak. (1902), 48, pp. 1-47.

4 Therap. Monatsh. (1904), 18, p. 391.

5 l c.

6 Boehm, Arch. f. Exp. Path. u. Pharmak. (1897), 38, p. 35.

Du Mez — The Galenical Oleoresins.

993

When prepared from the freshly dried and powdered rhizomes

gathered in the autumn,1 it usually has an olive-green color

when spread out in a thin layer on a white porcelain surface.

A brownish-green color is an indication of the use of old de¬

teriorated drug2 in its preparation, whereas, a deep green color

suggests adulteration with salts of copper or Chlorophyll.3

The nature of the solvent employed in extracting the drug is

also stated to have an influence on the color of the prepara¬

tion, the use of ether (specific gravity 0.720) yielding an oleo-

resin of a green color, whereas, the color is brownish-green

when ether (specific gravity 0.728) is employed.4

Odor : The odor of the oleoresin is peculiar, like that of

male fern.

Taste: The preparation has a bitter, nauseous, subacrid

taste.

Consistence: The oleoresin when freshly prepared is homo¬

geneous and is of about the same degree of fluidity as castor

oil. It is variously stated as being of the consistence of syrup,

fresh honey or an oily extract.

Solubility: The oleoresin when prepared with ether forms

clear or slightly cloudy solutions with acetone, ether, chloro¬

form and carbon disulphide.5 It is partially soluble in carbon

tetrachloride, benzene, methyl alcohol, ethyl alcohol (95 per

cent.), glacial acetic acid and petroleum ether. The degree to

which it is soluble in the last three solvents mentioned has

been made the basis of tests for the detection of adulteration

with castor oil.

According to Hill (1913), not less than 8 volumes of the

oleoresin should be soluble in 10 volumes of petroleum ether,

a lesser degree of solubility indicating adulteration. Jehn and

1 The oleoresin prepared from rhizomes gathered in October is stated by-

Kruse (1876) to have a more intense green color than that prepared from

rhizomes gathered in July.

Caesar and Loretz in their Berichte for 1913 state the condition of the

season in which the rhizomes are harvested has an influence on their color

which becomes evident in the oleoresin, e. g. the oleoresin, when prepared

from the rhizomes gathered in a dry season, is often very dark green in color.

2 Buchner (1826) found that when the drug was kept in an open container

for more than a year a brown instead of a green colored oleoresin was ob¬

tained.

3 Wepen and Lueders (1892), Beckurts and Peters (1893) and others.

4 Bellingrodt. (1898).

6 This statement holds good only for the freshly prepared oleoresin and

does not apply when the same contains deposited material.

03— S. A. L.

994 Wisconsin Academy of Sciences, Arts , and Letters.

Crato1 state that the presence of castor oil is indicated when

more than 50 per cent, of the oleoresin is soluble in 95 per cent,

alcohol. Solubility tests made in the laboratory with glacial

acetic acid have shown that not over 10 per cent, by volume

of the oleoresin is soluble in the latter, a greater degree of

solubility indicating adulteration with castor oil.

Specific gravity: Observations made in the laboratory show

that the specific gravity should be above 1.000 when determined

at 25° C. This is in keeping with the findings of Parry (1911)

and Hill (1913), respectively, even though their determinations

were made at 15° C. It is also the standard given in the late*

edition of the British Pharmacopoeia. A specific gravity of

less than 1.000 usually indicates adulteration with castor oil

or a preparation naturally low in filiein content. It may, how¬

ever, be due to the addition of chlorophyll as pointed out by

Hill, or to the presence of un evaporated solvent. These de¬

tails, together with the effect produced by the use of different

solvents in the extraction of the drug are brought out in the

following tables:

Table 13 — Specific gravities of oleoresins prepared in the laboratory.

1 Kommentar zum Arzneibuch fuer das deutsche Reich (1901), p. 258.

2 Same as 2 and 3 after having stood in the laboratory for 6 years. Both

contained a heavy deposit which was not mixed with the liquid portion when

the specific gravity was redetermined.

Du Mez ■ — The Galenical Oleoresins.

995

Table 14. — Specific gravities of commercial samples.

1 Adulterated with castor oil.

2 Contained added chorophyll.

3 Low in crude filicin content.

4 Referred to as suspicious.

B Contained ether.

996 Wisconsin Academy of Sciences , Arts , and Letters.

Refractive index: A refractive index of not less than 1.490

at 40 °C is required for this oleoresin by the late edition of the

British Pharmacopoeia. This is in accordance with the observa¬

tions of Hill (1913). The statement by Parry (1911), that

the refractive index should not be below 1.500 when deter¬

mined at 20 °C is confirmed by the results which were obtained

by Harrison and Self (1913), and is more in conformity with

the observations made in this laboratory at 25° C. When the

oleoresin is properly prepared, ether being the menstruum used,

the refractive index appears to vary directly as the crude filicin

content. A low refractive index, therefore, indicates a pre¬

paration naturally low in filicin content. With respect to the

commercial oleoresins, however, a low refractive index may also

result from adulteration with castor oil or chlorophyll, or may

be due to the presence of unevaporated solvent as is shown in

the tables which follow:

Table 15.— Refractive indices of laboratory preparations .

1 These figures represent the refractive indices of oleoresins which had

stood in the laboratory for six years.

Du Mez — The Galenical Oleoresins.

997

Table 16 — Refractive indices of commercial oleoresins.

Sample

No.

1-16.

1-7.

Date

1911

1912

1913

Observer

Evans 8ons,Lescher &Webb

Parry .

Evans Sons, Lescher& Webb

Southall Bros. & Barclay

DuMez.

Harrison & Self.

Hill.

1915

1916

Evans Sons.Lescher &Webb

Southall Bros. & Barclay

Source

Not stated

England.

Manila, P. I . .

United States.

Germany.

England..

Germany.

Europe.

England.

Europe...

England.

Europe..

Not stated.

DuMez.

Stearns & Co . .

Lilly & Co .

Sctuibb & Sons .

Parke, Davis & Co.

Refractive

index

At 15° C

1.484 (2)

1.485 0)

1.501

At 20° C

1.484(0

1.487 (i)

1.488 (2)

1.4885 (0

1 493(0

At 15° C

1.507 to

1.509

At 20° C

1.4880 (i)

1.4840 (i)

1.5040

1.5055

1.5065

1.5210(?)

At 25° C

1.484(D

1.485 (i)

1.489

1.490

1.492

1.493

1.494

At 20° C

1.4910(8)

1.4944

1.4984

1.5055

1.5080

1.5084

At 40° C

l,4823 (i)

1.4869 (i)

1.4874 (0

1.4880

1.4909

1.4915 (2)

1.4920

1.4922

1.4925

1.4935

1.4940

1.4945

1.4960

1.4965

1.4980

1.4985

1.4988

1.4990

1.5006

1.5025

1.5036

At 15° C

1.500 to 1.51C

1.495 (3)

1.497 (3)

1.499 (3)

At 25s C

1.4975

1.5115

1.4976

1.4983

1.5000

1.5001

1.5020

At 25 0 C

1.4953 (*)

1.4988 (4)

1.4993 (5)

1.4998

1 Samples adulterated with castor oil.

2 Samples contained added chlorophyll.

3 Samples are referred to as being suspicious.

4 Low in crude filicin content.

6 Contained unevaporated solvent.

998 Wisconsin Academy of Sciences , Arts , and Letters.

Chemical Properties.

Loss in weight on heating: Hill (1913) stated that the oleo-

resin when heated at 100 °C should not lose more than 6 per

cent, of its weight, a greater loss indicating the presence of

unevaporated solvent. The statement is confirmed by other

data of this nature reported in the literature as well as by

the results obtained in the laboratory as is shown in the tables

which follow:

Table 17 — Laboratory preparations — Loss in weight on heating.

Du Mez — The Galenical Oleoresins.

999

Table 18 — Commercial oleoresins — Loss in weight on heating.

(0 Unevaporated solvent (ether) was present.

Ash Content: The results of this nature reported in the lit¬

erature, as well as those obtained in the laboratory, indicate

that the ash content of the oleoresin, when prepared with ether,

seldom exceeds 0.50 per cent, which is the standard given in the

Belgian and Spanish pharmacopoeias. With respect to the

commercial samples examined in the laboratory, the high ash

content obtained was due to the presence of copper, evidently

a result of the use of copper utensils in the manufacture of these

preparations. The results of the determinations made in the

1000 Wisconsin Academy of Sciences , Arts , and Letters.

laboratory and those reported in the literature are given in the

tables which follow :

Table 19. — Ash contents of laboratory preparations.

Table 20 — Ash contents of commercial oleoresins.

O) Contained unevaporated solvent— ether.

Acid number: The acid numbers 82.2 and 82.7 were ob¬

tained for the oleoresins prepared in the laboratory. Inas¬

much, however, as these preparations were made six years

previous to the time when the determinations were made, it is

thought that the value of this constant would be somewhat

lower for the oleoresin when freshly prepared. This state¬

ment is based on the assumption that the acidity of the prep¬

aration will increase on standing due to the partial hydrolysis

of the glycerides of the fatty acids and to the breaking down

of the complex substances constituting the so-called crude filiein.

Du Mez — The Galenical Oleoresins.

1001

In the case of the commercial samples, the acid numbers were

found to vary as a rule in the same direction as the filicin

content. It would appear, therefore, that the value obtained

for this constant might serve as a check on the latter determina¬

tion. The results obtained in the determination of the acid

numbers of the preparations examined in the laboratory and

those reported by Kremel follow:

Table 21 .—Acid number s of laboratory preparations.

P) These preparations were 6 years old when the acid number was de¬

termined.

Table 22. — Acid numbers of commercial oleoresins.

P) Contained ether.

Saponification value: Determinations made by Parry in 1911

lead him to state that the saponification value of this prepara¬

tion should not be lower than 230, corresponding to a crude

filicin content of not less than 22 per cent. The values obtained

for this constant in the laboratory and those reported by Har¬

rison and Self agree, as a rule with this statement, when the

minimum filicin content is taken as 20 per cent. A value of

less than 230 in the case of commercial samples has been shown

to be due in general to adulteration with castor oil. In a few

instances, however; it is to be attributed to the presence of

unevaporated solvent, or to a low filicin content due to the use

of a poor quality of drug in the manufacture of the oleoresin.

1002 Wisconsin Academy of Sciences, Arts , and Letters.

The relatively high values obtained in the laboratory for the

old preparations low in filicin content (16.0 and 16.27 per cent,

respectively) is very likely due to the effect caused by the

hydrolysis of the constituents of high molecular weight with

the formation of acids of comparatively low molecular weight.1

The saponification values found for the preparations examined

in the laboratory as well as those reported in the literature are

given in the tables which follow:

Table 23 — Saponification values of laboratory preparations.

(x) Old preparations low in filicin content.

1 See under “Chemistry of the drug and oleroesin.”

Du Mez — The Galenical Oleoresins.

1003

Table 24 — Saponification values of commercial oleoresins.

1 Adulterated with castor oil.

2 Low in crude fllicin content.

3 Referred to as suspicious.

4 Contained ether.

Iodine value: Observations made in the laboratory indicate

that the oleoresin should have an iodine value of not less than

99, corresponding to at least 20 per cent, of crude filicin. Pre¬

parations giving a lower value than this were found to be low

in crude filicin content due to adulteration with castor oil or

to the presence of unevaporated solvent. On the other hand,

it was observed that a high iodine value does not always signify

a high filicin content, e. g. iodine values of 106.3 and 108.1

were obtained for preparations containing only 16.0 and 16.27

per cent, of crude filicin, respectively. As the latter were

1004 Wisconsin Academy of Sciences, Arts, and Letters.

old and contained deposited material equal to nearly one-half

of their bulk, the high iodine values obtained for the super-

natent liquid portions were very likely due to the concentra¬

tion of the compounds of a lesser degree of saturation (glycer¬

ides of the unsaturated fatty acids) as a result of the decom¬

position and deposition of the more highly saturated com¬

pounds (crude filicin). The results obtained in the determina¬

tion of this constant are shown in the following tables :

Table 25. — Iodine values of laboratory preparations.

1 These preparations were six years old when examined.

Table 26. — Iodine values of commercial oleoresins.

1

2

1

2

B

4

1

2

3

4

5

6

7

8

1

2

3

4

Sample

No.

Date

Observer

Source

Iodine

value

1804

im

Dieterich .

Evans Sons, Lescher & W ebb

Germany.

Not given

100.6

84.2

89.2 (!)

92. SC1)

95.9

1913

DuMez

1916

England .

Manila. P. I .

England .

United States. .......

Germany .

England. .

Germany . . .

United States .

Squibb & Sons. .

Stearns & Co .

Lilly & Co .

Parke, Davis & Co.. .

85.80

87.2 O

89.4 P)

94.4

97.1

98.3 C1)

100.2

101.5

95. 30

97. 70

98.20

103.2

1 Adulterated with castor oil.

2 Low in crude filicin content.

5 Contained ether.

Other Properties

The oleoresin, when freshly prepared, is homogeneous, but

upon standing, a deposit is formed therein as a result of the

breaking down of some of its constituents. The precipitated

Du Mez — The Galenical Oleoresins.

1005

material has been identified by Boehm1 as crystalline filix acid

and a wax-like substance. Kraft,2 in a later investigation, con¬

firmed the findings of Boehm insofar as they concerned the

presence of filix acid. The wax-like material, however, he

found to be composed of a number of substances, decomposi¬

tion products of the therapeutically active constitutents, which

he designated as filixnigrin. As the deposit has been found to

be active3 in the expulsion of tapeworm, although in a much

lesser degree than the oleoresin proper, the United States Phar¬

macopoeia directs that it be mixed with the liquid portion be¬

fore dispensing.

Special Qualitative Tests

A number of the European pharmacopoeias prescribe tests

for the determination of the quality of this preparation. These

tests are of two kinds, namely, those which have for their object

the establishment of the presence of the constituents of thera¬

peutic value, i. e. the substances of an acid character known

collectively as crude filicin, and those which serve to identify

starch when present. The former are based on the fact that

the above mentioned constituents of an acid character may be

precipitated directly by means of certain solvents, or from

alkaline solutions by means of acids. The following are the

official tests of this nature:

Tests for Filicin.

Austrian Pharmacopoeia (1906): Upon adding an excess of petroleum

ether to the oleoresin dissolved in a small quantity of ethyl ether, a white

precipitate should be produced.

1 Netherlands Pharmacopoeia (1905): If 0.025 gram of the oleoresin dis¬

solved in 2 cubic centimeters of ether be shaken with 5 cubic centimeters

of a saturated barium hydroxide solution and 5 cubic centimeters of water,

the aqueous portion, when separated and filtered, should give a floccu-

lent precipitate on being acidified with hydrochloric acid.

Hungarian Pharmacopoeia (1909): If 0.25 gram of the extract be dis¬

solved in 2 cubic centimeters of ether and shaken with 10 cubic centi¬

meters of lime water, the aqueous portion filtered and acidified with hydro¬

chloric acid, a copious white precipitate should be formed.

JArch. f. exp. Path. u. Fharmak:. (1897), 38, p. 35.

3 Kraft (1902).

3 Reuter, Pharm. Ztg\ (1891), 36, p. 245; Straub, Arch. f. exp. Path. u.

Pharmak. (1902), 48, p. 1.

1006 Wisconsin Academy of Sciences , Arts , and Letters.

The application of these tests in the laboratory has shown

that they are of practically no value as an indication of the

quality of the oleoresin, as preparations very low in crude

filicin content give comparatively heavy precipitates when

treated as described above. Furthermore, they do not serve

as a means of identification as oleoresins prepared from the

rhizomes of certain other species of fern1 behave in a similar

manner when subjected to these conditions.

Tests for Starch

A test for the presence of starch has been included in those

pharmacopoeias in which the oleoresin is directed to be pre¬

pared by the process of maceration, namely, the German and

Japanese. In these instances, it serves as a means of distin¬

guishing between preparations which have been filtered as of¬

ficially directed and those which have been merely strained

through cloth as is often the case. A similar test is also found

in the pharmacopoeias of those countries (Hungary, Spain and

Switzerland) in which this preparation is frequently made by

maceration, although the official process is that of percolation.

The test as officially recognized in the different countries is

identical with that described in the German Pharmacopoeia.

It is as follows:

The oleoresin, when diluted by shaking with glycerin, should not

show the presence of starch grains under the microscope.

Experience in the application of this test to the preparations

examined in the laboratory has shown that it is unsatisfac¬

tory when carried out as described above. The fault lies in

the fact that the glycerin cannot be thoroughly mixed with

the oleoresin by shaking. If mixing is effected by trituration

in a mortar, the results are better, although there is consider¬

able danger in rupturing the starch grains by this procedure.

In addition to the foregoing, special tests have been pro¬

posed for the detection of adulterants when present. They

are as follows:

1 See under “Drug used, its collection, preservation, etc.”

Du Mez—The Galenical Oleoresins.

1007

Tests for the Presence of the Oleoresin of Dryopteris Spinulosa.

Hausmann found that the male fern of commerce frequently

contained large quantities of the rhizomes of Dryopteris spinu¬

losa Kunze. He therefore devised a test for the detection of the

use of the latter in the preparation of the oleoresin. It is based

on the fact that the rhizomes of Dryopteris spinulosa Kunze

contain aspidin, whereas those of the official species, Dryopteris

Filixmas Schott do not.

Hausmann ’s Method (1899): Dissolve a small amount of crude filicin 1

in as small a quantity of absolute ether as possible and set the solution

aside in a desiccator. If aspidin is present, the thick solution will form

a crystalline brine in a few hours, when the needle-like crystals of the

former can easily be identified under the microscope. If aspidin is not

present, the solution undergoes no change even on long standing except

to deposit a granular substance.

Tests for the Presence of Castor Oil

The tests for the presence of castor oil are based on the

solubility of the oleoresin in various solvents and are discussed

under the heading, ‘ ‘ Solubility .’ ’

Tests for the Presence of Salts of Copper

The tests for the presence of salts of copper involve an ex¬

amination of the ash of the oleoresin and are discussed under

the general treatment of the subject, 4 ‘Ash content.’ ’

Special Quantitative Tests.

A great deal of work has been done with reference to the

evaluation of this preparation, and as a result, a number of

methods for the quantitative estimation of the constituents of

therapeutic importance has been devised. The chemical meth¬

ods may be conveniently divided into two groups, the one includ¬

ing those methods which have for their object the quantitative

determination of the filix acid; and the other comprising the

methods in which the quantity of the total constituents of an

acid character is determined.

1 See under “Special quantitative methods”.

1008 Wisconsin Academy of Sciences, Arts, and Letters.

Methods for the Determination of Filix Acid.

As the oleoresin was originally thought to owe its teniafuge

properties to its filix acid content, the determination of this

constituent naturally received consideration first. The nature

of the methods devised for its estimation and their subsequent

development is illustrated in the descriptions which follow :

Method of Kremel (1887): Place a weighed quantity (about 10 grams)

of the oleoresin in a flask and macerate it successively with several portions

of petroleum ether when the greater part will be dissolved leaving the

filix acid as an insoluble residue. Collect the latter on a fiilter and wash

with more petroleum ether. Then dissolve it while on the filter in hot

alcohol, remove the latter by evaporation and again wash with petroleum

ether to remove the last traces of fat. Finally dry and weigh.

Method of Bocchi (1896) :* Dissolve 1 to 2 grams of the oleoresin in a

small quantity of ether, place the solution iu a separatory funnel and

shake it with successive portions of lime water until the shakings become

colorless and remain clear on the addition of acetic or hydrochloric acids.

Filter the united lime water solutions into a separatory funnel and acidify

with hydrochloric acid when a dirty yellow precipitate will form. Dis¬

solve / the latter by shaking with carbon disulphide added in successive

portions, unite the shakings, filter and remove the solvent by evaporation

on a water bath. Dry and weigh the residue which is pure filijx acid.

Method of Kraft (1896): Add a solution composed of 2 grams of

potassium carbonate, 40 grams of water and 60 grams of alcohol (95 per

cent.) to 5 grams of the oleoresin in a suitable flask and shake for 15

minutes. Filter 83 grams of this liquid into a separatory tunnel, add 9

grams of dilute hydrochloric acid, 50 grams of ether and 35 grams of

water and shake vigorously. After the mixture has separated draw off

the lower hydro-alcoholic liquid and repeat the shaking, using 35 grams

more of water. Separate the latter and run the remaining ethereal so¬

lution into a tared Erlenmeyer flask of 100 cubic centimeters capacity.

Distill off the greater part of the ether and evaporate the remainder down

to about 2 grams. Dissolve the dried mass in 1.5 grams of amyl alcohol

and precipitate the filix acid by the addition of 30 cubic centimeters of

methyl alcohol (5 cubic centimeters added at once and the remainder drop

by drop.) Allow the precipitate and supernatant liquid to stand over

night in a cool place, then collect the former on a tared filter and wash

it with 15 cubic centimeters of methyl alcohol (use 3 portions of 5 cubic

centimeters.) Finally, dry the precipitate at a temperature between 60°

and 70 °C and weigh. The weight obtained will represent the filix acid

contained in 4 grams of the oleoresin.

1 The procedure as outlined above really gives the amount of total acid

substances (crude filicin) present, but is described here as it was proposed

by its originator as a method for the determination of the filix acid content.

Du Mez~The Galenical Oleoresins.

1009

Original Method of Fromme (1896): Dissolve 1.5 to 2 grams of the

oleoresin in 2 grams of ether, and thoroughly mix the solution in a porce¬

lain dish (diameter 8 to 10 centimeters) with 3 grams of calcined mag¬

nesia (or 8 grams of burned lime.) Allow the ether to evaporate com¬

pletely and triturate the remaining dry pulverent mass with water, added

gradually until a thin brine is formed. Set the mixture aside until the

magnesia has settled, then decant the supernatant aqueous portion on a

dry filter. Continue to repeat this operation, using fresh portions of

water, until the filtrate no longer gives a precipitate when acidified with

hydrochloric acid. Place the combined filtrates (usual weight 200 to 250

grams) in a separatory funnel, acidify with hydrochloric acid and shake

out the precipitate with carbon disulphide added in successive portions

(20, 10 and 10 cubic centimeters.) Filter the united carbon disulphide

shakings into a round-bottom flask of 100 cubic centimeters capacity and

evaporate to dryness on a water bath. Dissolve the crude filix acid ob¬

tained in this manner in 10 drops of amyl alcohol, using a gentle heat

if necessary, then add 10 cubic centimeters of methyl alcohol (added drop

by drop at the beginning and later rapidly.) Set the liquid containing

the crystals aside in a cool place for 12 hours, then collect the latter on a

tared filter, and, after washing with several 5 cubic centimener portions

of methyl alcohol, dry at a temperature between 60° and 70 °C and weigh.

Improved Method of Fromme (1897): Place 5 grams of the oleoresin,

30 grams of ether and 100 grams of a solution of barium hydroxide (1 peT

cent.) in a 200 cubic centimeter flask and shake for 5 minutes. Then run

the mixture into a separatory funnel, and, after allowing it to stand for 10

to 15 minutes, run off into another separatory funnel 86 grams (cor¬

responding to 4 grams of the oleoresin) of the lower aqueous layer.

Acidify by the addition of hydrochloric acid (25 to 30 drops) and shake

out with ether (in 25, 15, 10 and 10 cubic centimeter portions.) Filter

the combined ether washings into a 100 cubic centimeter flask and evapor¬

ate to dryness on a water bath. Dissolve the residue in 1 cubic centimeter

of amyl alcohol by heating over a free flame and precipitate the pure filix

acid with 30 cubic centimeters of methyl alcohol (added drop by drop

until a permanent precipitate is produced, and the remainder at once.)

After the liquid has stood quietly in a cool place for 10 to 12 hours,

collect the precipitate on a tared filter, wash with methyl alcohol (two 5

cubic centimeter portions,) press the filter between porous plates, dry at

an initial temperature of 40 °C and finally at 80° C, and weigh.

Stoder’s Method (1901): Dissolve 5 grams of the oleoresin in 20 cubic

centimeters of ether, add 100 cubic centimeters of a freshly prepared so¬

lution of barium hydroxide (2 per cent.) and shake the mixture fre¬

quently during 1 hour. After allowing the mixture to stand quietly for

a short time, separate the lower aqueous layer by filtration. Collect

86 cubic centimeters of this portion (corresponding to 4 grams of the

oleoresin) in a separatory funnel and acidify with 10 cubic centimeters of

dilute hydrochloric acid. Shake out the resulting precipitate with three

portions of ether (40, 30 and 20 cubic centimeters) added successively,

unite the shakings and remove the solvent by distillation. Dissolve the

64-— S. A. L.

1010 Wisconsin Academy of Sciences , Arts , and Letters.

residue in 1 cubic centimeter of amyl alcohol, and, after the solution has

stood in a cool place for 48 hours, add 15 cubic centimeters of methyl

alcohol. After standing for 24 hours more, collect the precipitated filix

acid on a filter, wash with 5 cubic centimeters of methyl alcohol, dry on

a water bath and weigh.

It will be noticed that the preceding methods, with the ex¬

ception of the one devised by Kremel, are very similar in gen¬

eral outline, practically the only difference being found in the

procedure by which the crude filix acid is directed to be purified.

This difference is of special importance, however, as the weight

of the product finally obtained will naturally vary with the de¬

gree to which purification has been effected, and this in turn

will cause the computed percentage to vary, as is shown in the

following table :

Table 27. — Variation in filix acid content due to the difference in the meth¬

ods employed in its determination.

The above table shows further that the filix acid is obtained

in the state of greatest purity when the improved method of

Fromme is employed. And this method was usually given

preference in the valuation of the oleoresin until it was dis¬

covered that the teniafuge properties were not due to the filix

acid, alone, but were to be attributed in part to the presence of

a number of other substances as well, compounds resembling

acids to a certain extent in their chemical behavior.

Methods for the determination of the Crude Filicin.

With the above mentioned advance in our knowledge con¬

cerning the therapeutic constituents of -this preparation, the

methods for the determination of the filix acid lost their value

and have since been superceded by those which have for their

Du Mez — The Galenical Oleoresins.

1011

object the determination of the quantity of total active constit-

uents (crude filicin) present. The methods which have been

proposed for this purpose are as follows:

Method of Bulle (1867) :* Add a liberal amount of water to a weighed

portion of the oleoresin contained in a suitable flask and heat on a water

bath at 40° to 50°C. Add sufficient ammonia water to produce a strong

odor of the same after vigorously shaking. Allow the mixture to stand

in cold water for 3 or 4 hours and add 1/5 to ^4 of its volume of a sat¬

urated solution of salt, then filter. Wash the flask and filter with the

salt solution, diluted with 6 parts water, until the filtrate no longer gives

a precipitate with hydrochloric acid. Add dilute hydrochloric acid to the

filtrate until precipitation is complete, collect the precipitate on a filter,

wash and dry over sulphuric acid until of constant weight.

Method of Baccomo and Sccocianti (1896): 3 Dissolve 1 to 3 grams of

the oleoresin in a small quantity of ether and shake the solution for %

hour with an equal volume of an aqueous copper acetate solution. Allow

the mixture to stand and separate, decant the ethereal liquid and collect

the precipitate on a tared filter. Wash it successively with water, alco¬

hol and ether, then heat at 100°C until of constant weight. When dry

111.55 parts of the precipitate represent 100 parts of filix acid.

Method of Schmidt (1903) : 3 Place 5 grams of the oleoresin in a mortar

and convert it to a coarse powder by triturating it with a sufficient quantity

of calcined magnesia. Then add 250 cubic centimeters of water and thor¬

oughly mix. After the magnesia has settled, decant the aqueous portion

on a filter. Repeat this operation twice using 150 eubic centimeters of

water each time. Transfer the combined filtrate to a separatory funnel

and add hydrochloric acid in sufficient quantity to produce complete pre¬

cipitation. Shake out the precipitate with ether, specific gravity 0.720 to

0.722, added in successive portions (100, 50 and 30 cubic centimeters.)

After filtering the ethereal shakings, remove the solvent by distillation

and dry the residue at 100° C.

Method of From/me (1905):* Dissolve 5 grams of the extract in 30

grams of ether, add 100 grams of a saturated solution (3 per cent.) of

barium hydroxide, and shake the mixture vigorously during several minutes.

Transfer to a separator, and run 86 grams (4 grams of the extract) of the

lower equeous layer into a flask of 200 eubic centimeters capacity. Add

2 grams of hydrochloric acid (25 per cent.) and shake out with 3 portions

of ether, 25, 15, and 10 cubic centimeters. Separate the ether, and filter

each portion successively through the same plain double filter into an

1 Cited by Doesterbehn (1898).

2 This procedure was proposed as a method for the estimation of the

filix acid. As its nature and the results obtained in its application show that

it is in reality a method for determining the total constituents of an acid

character, it has been included here.

3 The method proposed by Goris and Voisin (1913) is almost identical

with the above, the only difference being- that 2 to 3 grams of the oleoresin

are taken instead of 5 grams as directed by Schmidt.

4 This is the method (but slightly modified) which is official in the British,

Finnish and Swiss pharmacopoeias.

1012 Wisconsin Academy of Sciences, Arts , and Letters.

Erlenmeyer flask of 200 cubic centimeters capacity which has been pre¬

viously weighed. Wash the filter with 10 cubic centimeters more of ether,

and finally distill off the ether and dry the residue at 100°C. Weigh after

allowing it to stand in a desiccator for half an hour. The weight multi¬

plied by 25 will give the percentage of crude filicin in the sample.

The striking similarity in the above methods is quite ap¬

parent and needs no special mention. Attention, however, is

invited to the principal point of difference, namely, the reagent

employed for the purpose of rendering the constituents to be

determined soluble in water. In the methods under considera¬

tion, ammonia water, magnesium oxide and barium hydroxide

have been made use of. As the amount of crude filicin ob¬

tained has been shown to depend to a considerable extent upon

which one of these reagents is employed, the difference in the

results reported in the literature in this connection is readily

accounted for. The importance of this factor is clearly brought

out in the following data obtained by Hill :

Table 28 — Influence of different alkalies on the percentage of crude

filicin obtained.

These results would appear to indicate that potassium hy¬

droxide is the most efficient reagent for effecting a soluble com¬

bination of the constituents comprising the so-called crude

filicin. The data, however, are misleading in that the strong

alkali combines with other material therapeutically inert, and

thereby causes the results to be high. While there is no in¬

formation of a physiological nature at hand to substantiate the

statement that barium hydroxide is the best reagent for this

purpose, it is nevertheless, thought to be the most satisfactory

from a chemical stand point at least. The method of Fromme,

in which the latter is directed to be used, was, therefore, em¬

ployed in the evaluation of the oleoresins examined in the

laboratory. The results obtained in these analyses, together

with those reported by other workers are given in the table

which follows:

Du Mez — The Galenical Oleoresins.

1013

Table 29. — Crude filicin content of laboratory samples of the oleoresin

determined by Fromme's method.

3 Ether, specific gravity 0.720.

2 Ether, specific gravity 0.728.

3 Oleoresins which were prepared in 1910 and had deteriorated. Exam¬

ined shortly after being prepared, the ethereal oleoresin showed a crude

filicin content of 26.35 per cent.

From the foregoing, it is apparent that the crued filicin

content is influenced1 by the age of the oleoresin as well as by

the solvent which has been employed in its preparation. In the

case of acetone, the low results obtained are not due to the in¬

complete extraction of the constituents to be determined, as

might be inferred, but rather to the relatively large amount of

total extractive matter obtained. It will be noticed that when

the oleoresin is fresh and ether is the solvent which has been

used in its preparation, the crude filicin content (is usually

above 20 per cent. This is in accordance with the require¬

ments of the British Pharmacopoeia and is thought to be a more

reasonable standard than that adpoted by the Swiss, or the

Finnish pharmacopoeias. The former requires a filicin content

of 26 to 28 per cent, while the latter specifies a minimum con¬

tent of 26 per cent. This statement is further supported by

the results obtained in the examination of commercial samples

as is shown in the following compilation of such data :

1 For the effect of the condition of the rhizomes used on the crude filicin

content, see under “Drug used, its collection, preservation, etc.”

1014 Wisconsin Academy of Sciences , Arts , and Letters,

Table 30. — Crude filicin content of commercial samples of the oleoresin

determined by Fromme's method.

Sample

No.

2 .

1 .

2 .

3 .

4 .

5 .

6 .

1 to 16.

Date!

1901

1903

1911

Observer

Caesar & Loretz .

Source

1....

2 .

3 .

4 .

1 .

2 .

3. .

4 .

5......

6 .....

1 to 7

1912

191

Prepared by the firm.

Evans Sons, Lescher &

Webb.

Parry .. . . . . .

Evans Sons, Lescher &

Webb.

Southall Bros. & Barclay

1913

9.

10.

11

12..

13..

Bohrisch

England

Germany

DuMez.

Evans Sons, Lescher &

Webb.

Goris & Voisin.,

Harrison & Self

Hill

England .

United States

Germany ... .

England .

Germany .

United States

Not given .

Germany . . .

Switzerland

France .

Germany . . .

England

Not given.

Crude filicin

Per cent.

21.40

26.15

27.37

28.17

30.00

30.12

30.80

30.92

27.08

28.22

28.78

29.39

30.05

36.60

26.30

28.00

8.40 (*)

8.60 (x)

8.80 l1)

9.00 (»>

9.20 (»)

10.80 (*)

22.90 to 26.30

6.09 (»)

7.16 (»)

26.04

28.76

14.85

15.42

16.00

24.00

8.79

14.36

16.55

17.51 (l)

20.32

20.77

21.3 to 25.30

15.60 (H

19.60 (')

19.70 (*)

13.61 to 19.00

7.13 to 24.00

20.60 to 22.13

13.70

19.10

21.20

24.80

25.80

28.10

11.60

13.20

14.10

18.10

18.92

19.30

20.22

20.67

21.57

21.60

22.00

22.65

23.10

(*)

Du Mez — The Galenical Oleoresins.

1015

Table 30. —Continued.

1 These samples were adulterated with castor oil.

2 Apparently an oleoresin from some species of fern other than Dry-

opteris Mix mas.

In addition to the information given in table No. 29, table

No. 30 reveals the fact that a low filicin content in the com¬

mercial oleoresins is frequently due to adulteration with castor

oil.

Physiological Tests.

In view of the difference in toxicity of the various constit¬

uents of the oleoresin with respect to the tapeworm, a physio¬

logical method for the evaluation of this preparation would ap¬

pear to be desirable. The method proposed for this purpose

by Yagi indicates the possibilities along this line. However,

as there is no available information regarding its application,

aside from that given by the originator, no statement can be

made concerning its practical value. A description of the

method for conducting the test follows :

Method of Yagi ( 191 4) : After thoroughly drying in a desiccator, ac¬

curately weigh 1 gram of the oleoresin and dissolve it in 25 cubic centi¬

meters of ether. Bring the therapeutically active constituents into

aqueous solution by shaking the ethereal liquid with a saturated solution

of magnesium hydroxide, using 50 cubic centimeters of the latter for every

1016 Wisconsin Academy of Sciences, Arts , and Letters.

cubic centimeter of the former. Filter and divide the filtrate into several parts.

Prepare solutions of different dilution from these parts by adding a

measured amount of water to each. Then immerse 5 earthworms in each

of these solutions and note the maximum dilution in which all 5 are killed.

For computing the relative value of the preparation compare these re¬

sults with those obtained when using a standard solution prepared by dis¬

solving a weighed amount of filix acid, filmaron or albaspidin in water in

the same manner as described above for the oleoresin. In the case of these

standard solutions the limit of toxicity is given as follows: filmaron, 3

parts in 1,000,000; filix acid 4 parts in 1,000,000; albaspidin 1 part in

100,000.

Adulterations

The efforts which have been made in recent year& to stand¬

ardize this preparation have resulted in the discovery that the

commercial article is very frequently adulterated, the latter

being accomplished in a variety of ways.

The method usually resorted to by unscrupulous manufac¬

turers in order to increase their profits consists of diluting the

finished product with some comparatively cheap material.

Castor oil1 has generally been used for this purpose. In some

cases, the oleoresin is prepared from deteriorated brown rhi¬

zomes and made to assume the green color of the official pre¬

paration by the addition of chlorophyll or salts of copper.2

Adulteration, however, is not limited to the addition of for¬

eign materials to the finished product, but may take place in

the drug from which the oleoresin is prepared. The forms in

which the drug may be contaminated are conveniently classed

under three heads, viz.: (a) the substitution of old deteriorated

rhizomes for the fresh material, (b) the admixture of chaff

and dead stipe bases with the rhizomes, and (c) the admixture

of rhizomes of unofficial species of fern with those of the

official species. For a discussion of these conditions, see under

“Drug used, its collection, preservation, etc.”

1 Parry (1911) ; Evans Sons, Lescher and Webb (1911) ; and others.

2 Weppen and Lueders (1892); Beckurts and Peters (1893); Fendorff

(1913) ; and others.

A trace of copper is usually present in the commercial product as a result

of the use of copper utensils in the manufacture of the preparation. (See

under “Ash”).

Du Mez — The Galenical Oleoresins.

1017

OLEORESIN OF CAPSICUM

Synonyms

Aetherische Spanishpfeffer extrakt, Nat. Disp. 1884.

Capsicum,1 Ohem. & Drugg. (1913), 82, p. 470.

Capsicol, Vierteljahrschr. f. prakt. Pharm. (1873), 22, p. 507.

Ethereal Extract of Capsicum, Am. Journ. Pharm. (1849), 21, p. 114.

Extractum Capsici aethereum, Hirch, Univ. P. 1902, No. 1905.

Oleoresin of Bed Pepper, Stevens, Pharm. and Disp. (1909), p. 255.

Oleoresina Capsici, U. S. P. 1910.

OleorCsine de Capsique, U. S. Disp. 1907.

Spanishpfeffer extract, Nat. Disp. 1884.

Spanishpfeffer-Oelharz, Nat. Disp. 1884.

History

The oleoresin of capsicum appears to have been first prepared

by Procter in 1849, and it was through his efforts that it was

introduced into the United States Pharmacopoeia of 1860. Up

to the present time, no such preparation appears in any of the

foreign pharmacopoeias. A similar preparation known as capsi-

cin has, however, been in use in Europe since 1873.2

Drug Used , Its Collection , Preservation , Etc.

The drug directed to be used by the present edition of the

United States Pharmacopoeia is “the dried ripe fruits of Capsi¬

cum fructescens Linne3 (Fam. Solanaceae), without the presence

or admixture of more than 2 per cent, of stems, calyxes or other

foreign matter.” The preceding editions of the Pharmacopoeia

since 1880 have specified the use of the species known as Capsi¬

cum fastigiatum Blume. The change is evidently due to the

fact that the leading commercial varieties of Cayenne pepper

are at the present time being received from Africa and Japan and

1 For other uses of the term capsicin, see under “Chemistry of capsicum

and its oleoresin.”

2 Buchheim states that capsicin (the ethereal extract of capsicum) was

being prepared and sold by Merck of Darmstadt in 1873. Vierteljahrschr.

f. prakt. Pharm. (1873), 22, p. 507.

Capsicin, as found on the market in England, is stated to be indefinite in

that it may be an alcoholic, a chloroformic, an ethereal or an acetone prep¬

aration. Chem. and Drugg. (1913), 82, p. 470.

3 This is also the species recognized by the French Pharmacopoeia. In the

other European pharmacopoeias, in which this drug occurs, it is usually the

the larger fruited variety, Capsicum annum, which is designated.

1018 Wisconsin Academy of Sciences , Arts , and Letters.

belong to the first mentioned species4 which has also been

known as Capsicum baccatum Yell.

The fruit is plucked when ripe, exposed to the sun until dried,

and then usually packed in suitable shape for market. It should

be preserved in the whole condition in a cool place,5 and prefer¬

ably in a closed container as it is prone to become rancid owing

to the large amount of fatty oil which it contains.

U. S. P. Texts and Comments Thereon .

The oleoresin has been official in the United States Phar¬

macopoeia for the past half century having been recognized for

the first time in the edition of 1860.

1860

Oleoresina Capsici

Oleoresin of Capsicum

Take of Capsicum,1 in fine powder,2 distillation on a water-bath, eighteen

twelve troy-ounces; fluid-ounces of ether,8 and expose the

Ether3 a sufficient quantity. residue, in a capsule, until the re-

Put the capsicum into a cylindrical maining ether has evaporated. f

percolator,4 press it firmly, and gradu Lastly, remove, by straining, the fatty

ually pour ether upon it until twenty matter which separates on standing,*

four fluid ounces of filtered liquid and keep the Oleoresin in a well-stop-

have passed.® Recover from this, by pered bottle.1®

1870

Oleoresina Capsici

Oleoresin of Capsicum

Take of Capsicum,1 in fine powder,2 ounces of liquid have slowly passed.*

twelve troyounees; Recover the greater part of the ether

Ether3 a sufficient quantity. by distillation on a water-bath,8 and

Put the capsicum into a cylindrical expose the residue in a capsule, until

percolator, provided with a etop-coek, the remaining ether has evaporated/

and arranged with cover and recep- Lastly, remove, by straining, the fatty

tacle suitable for volatile liquids,4 matter which separates on standing,®

press it firmly, and gradually pour and keep the Oleoresin in a well-stop-

ether upon it, until twenty-four fluid pered bottle.1®.

4 Tolman and Mitchell, Bull. 183, Bur. of Chem. (1913), p. 9.

6 Brown, Bull. 150, Kentucky Agric. Exp. Sta. (1910), p. 131.

Du Mez—TJie Galenical Oleoresins.

1019

1880

Oleoresina Capsici

Oleoresin of Capsicum

Capsicum,1 in No. 60 powder,2 one residue, in a capsule, until the remain-

Hundred parts . 100 ing ether has evaporated.7 Lastly,

Stronger Ether,8 a sufficient quantity, pour off the liquid portion,8 transfer

Put the capsicum into a cylindrical the remainder to a strainer, and, when

percolator, provided with a cover and the separated fatty matter (which is

receptacle suitable for volatile liquids,4 to be rejected) has been completely

press it firmly, and gradually pour drained, mix all the liquid portions to-

stronger ether upon it, until one hun- gether.®

dred and fifty (150) parts of liquid Keep the oleoresin in a well stop-

have slowly passed.8 Recover the ped bottle.1*

greater part of the ether by distilla- Preparation. Emplastrum Capsici.

tion on a water-bath,® and expose the

1890

Oleoresina Capsici

Oleoresin of Capsicum

Capsicum,1 in No. 60 powder,2 five

hundred grammes . 500 Gm.

Ether,3 a sufficient quantity.

Put the capsicum into a cylindrical

glass percolator, provided with a stop¬

cock, and arranged with cover and

receptacle suitable for volatile liquids,4

Press the drug firmly, and percolate

slowly with ether, added in successive

portions, until the drug is exhausted.6

Recover the greater part of the ether

from the percolate by distillation on

a water-bath,® and, having transferred

the residue to a capsule, allow the re¬

maining ether to evaporate spontan¬

eously.7 Then pour off the liquid por¬

tion, transfer the remainder to a

strainer, and, when the separated fatty

matter (which is to be rejected) has

been completely drained, mix the li¬

quid portions together.*

Keep the oleoresin in a well-stop¬

pered bottle.1*.

Preparation : Emplastrum Capsici.

1020 Wisconsin Academy of Sciences , Arts, and Letters.

1900

Oleoresina Capsici

Oleoresin of Capsicum

Capsicum,1 in No, 40 powder,3 five

hundred grammes ..... .500 Gm.

Acetone,8 a sufficient quantity .

Introduce the capsicum into a cylin¬

drical glass percolator, provided with

'a stop-cock, and arranged with a

cover and a receptacle suitable for

volatile liquids.4 Pack the powder

firmly, and percolate slowly with ace¬

tone, added in successive portions,

until eight hundred cubic centimeters

of percolate have been obtained.®

Recover the greater part of the ace¬

tone from the percolate by distilla¬

tion on a water-bath/ and, having

transferred the residue to a dish, al¬

low the remaining acetone to evapor¬

ate spontaneously in a warm place.1

Then pour off the liquid portion,®

transfer the remainder to a glass fun¬

nel provided with a pledget of cotton,

and when the separated fatty matter

(which is to be rejected) has been

completely drained, mix the liquid

portions together.9 Keep the oleo¬

resin in a well-stoppered bottle.1®

Average dose.- — -0.030 Gm. = 30

milligrammes (% grain).

1910

Oleoresina Capsici

Oleoresin of Capsicum

Oleores. Capsic.

Capsicum,1 in No. 40 powder3 five

hundred grammes ...... 500 Gm.

Ether,3 a sufficient quantity.

Place the capsicum in a cylindrical

glass percolator, provided with a stop¬

cock, and arranged with a cover and

a receptacle suitable for volatile li¬

quids.4 Pack the powder firmly and

percolate slowly with ether, added in

successive portions, until the perco¬

late measures eight hundred mils.6

Recover the greater part of the ether

from the percolate by distillation on

a water-bath,6 and, having transferred

the residue to a dish, allow the re¬

maining ether to evaporate spontan¬

eously in a warm place.1 Then pour

off the liquid portion,8 transfer the

remainder to a glass funnel provided

with a pledget ’ of cotton, and, when

the separated fatty matter (which is

to be rejected) has been completely

drained, mix the liquid portions to¬

gether.9 Keep the oleoresin in a well-

stoppered bottle.10

Preparation — - Eplastrum Capsici.

Average Dose.— -Metric, 0.03 Gm. —

Apothecaries, % grain.

Du Mez — The Galenical Oleoresins.

1021

1) For a description of the drug, see pag 1017 under “Drug

used, its collection, preservation, etc.”

2) The editions of the Pharmacopoeia previous to that of 1900

directed that the drug be reduced to a fine powder (No. 60)

for percolation. As a No. 40 powder has been found to be

equally satisfactory for this purpose, the last two editions

of the Pharmacopoeia have specified the use of the coarser

powder.

3) Ether is the solvent which is directed to be used in the ex¬

traction of the drug at the present time. Previous editions of

the Pharmacopoeia, with the exception of that 1900, also, speci¬

fied the use of ether for this purpose. The use of acetone as di¬

rected by the Pharmacopoeia of 1900 was unsatisfactory as the

large amount of extractive matter obtained caused the residue

which remained upon the evaporation of the solvent to assume a

semi-solid gelatinous form, and thus increased the difficulty

of separating the liquid portion.

Among the other solvents which have received considera¬

tion in this connection, benzin is worthy of mention. The re¬

ports of Maisch, Trimble and Beringer, respectively, (see

part I, pages 923 and 924) indicate that it is a good solvent for

the oleoresinous constituents of capsicum and that the pro¬

duct obtained is equal in quality to that yielded by ether.

Experiments conducted in the laboratory confirm these ob¬

servations. The solvent used in the laboratory, however, was

petroleum ether, boiling temp. 45 to 50° C., as the composition

of ordinary commercial benzin varies to a considerable extent.

4) The Pharmacopoeia of 1860 directed that the extraction

of the drug be carried out in an ordinary glass percolator. As

a considerable amount of solvent was lost under these condi¬

tions, the subsequent editions of the Pharmacopoeia have

specified that a form of percolator adapted to the use of vola¬

tile liquids be employed for this purpose. For a description

of such forms, see Part I, under “Apparatus used.”

5.) Of interest in connection with the preparation of this

oleoresin is the fact that the pharmacopoeial directions con¬

cerning the amount of percolate to be collected have been

changed no less than three times. The first change appeared

in the Pharmacopoeia of 1880, and was apparently instituted

for economic reasons as the amount of percolate directed to

1022 Wisconsin Academy of Sciences, Arts , and Letters.

be collected was reduced from approximately 2 cubic centi¬

meters for each gram of drug used (24 fluid ounces for 12 troy

ounces of drug) to 1.5 cubic centimeters. In the succeeding

edition of the Pharmacopoeia (edition of 1890), the second

change was made, the directions being to continue percolation

until the drug is exhausted. The third change occurs in the

Pharmacopoeia of 1900, which directs that 1.6 cubic centi¬

meters of percolate be collected for each gram of drug taken.

The reason for making the second change does not become

apparent from the information at hand. The third change,

however, appears to have been instituted primarily for the

purpose of reducing the amount of solid fats (mainly pal-

mitin and stearin) extracted in order that the separation of

the liquid portion constituting the oleoresin might be ac¬

complished more easily.

In commenting further upon these changes, it is stated that,

in the preparation of the oleoresin in the laboratory, no

greater difficulty was experienced in the separation of the

liquid portion when the amount of sold fats present was large

than when the quantity present was relatively small. From

this standpoint, therefore, the last change does not appear to

have been warranted. For economic reasons, however, the

change was desirable since at least twice as much ether was

required for the complete exhaustion of the drug as is ordin¬

arily used when proceeding according to the directions given

in the last edition of the Pharmacopoeia.

It is thought that the present pharmacopceial method could

be still further improved through the use of some form of con¬

tinuous extraction apparatus for exhausting the drug. Not

only would this procedure result in the saving of a large

amount of solvent, but the time required to complete the

preparation of the oleoresin would be considerably shortened.

6) The Pharmacopoeia of 1860 directed that only % of the

menstruum contained in the percolate be recovered by distil¬

lation on a water bath. In all of the subsequent editions the

directions are to recover the greater part of the solvent, no

specific amount being mentioned. In this connection, it may

be stated that the preparation will not be injured even if all

of the solvent is recovered under the above conditions. In

case this is done, however, it is necessary to use ether in re-

Du Mez — The Galenical Oleoresins.

1023

moving the thick liquid from the flask so that no particular

advantage is gained by such a procedure.

7) In all editions of the Pharmacopoeia in which this prepara¬

tion is official, it is directed that the last traces of solvent be

allowed to evaporate spontaneously at room temperature.

Since the complete removal of the solvent can be accomp¬

lished much more rapidly by heating the ethereal liquid on a

water bath, and without injury to the finished product, it is

thought that such a procedure would be a desirable improve¬

ment over the present pharmacopceial method.

8-9) The liquid portion constituting the oleoresin is directed

to be separated from the solid fats, which precipitate up¬

on the removal of the solvent, by decantation, and straining

through a pledget of cotton. Experience has shown that this

may be accomplished much more rapidly and satisfactorily by

the aid of a force filter. By this procedure a more complete

separation can be effected without washing the residue on the

filter with a portion of the solvent as has been suggested by

some and thus, the necessity of further exposure of the prep¬

aration to the air is done away with.

With further reference to the removal of the solid fats, at¬

tention is called to the fact that the degree to which this is ac¬

complished depends upon the temperature at which the oper¬

ation is carried out. The preparation when made during the

summer may be perfectly homogeneous at the time, but deposit

fat during the winter. In order to secure a more uniform

product, it is therefore, thought that the Pharmacopoeia

should direct that the mixture be chilled to a definite tempera¬

ture previous to the separation of the liquid portion.

10) The oleoresin should be kept in well-stoppered bottles for

the same reasons as are given in the comments on the oleoresin

of aspidium. See page 979.

Yield

The average yield of oleoresin is usually about 15 to 18 per

cent, when ether is the solvent employed in exhausting the

drug. It is about the same when alcohol, acetone, petroleum

ether, carbon disulphide or chloroform are used. In this con¬

nection, attention is called to the fact that the total, amount of

1024 Wisconsin Academy of Sciences , Arts , and Letters.

extract obtained and the oleoresin are not identical, the latter

consisting only of the oily, liquid portion of the former. Thus,

it will be observed, upon examining the tables which follow, that

the total amount of extract obtained with acetone may amount

to 25 per cent, of the drug operated upon, whereas, the yield

of oleoresin is only about 18 per cent. The factor which ap¬

pears to influence the yield to the greatest extent is the tem¬

perature at which the preparation is completed. This is due

to the fact that the oleoresin is saturated with solid fats

(principally palmitin) and, that these will be precipitated to

a greater or lesser degree depending on the temperature at

which the preparation is finally strained. The finished pro¬

duct will, therefore, contain a relatively small amount of these

fats, and the yield will be correspondingly low when made dur¬

ing the cold winter months, whereas, the opposite will be the

case when the oleoresin is prepared in the hot months of sum¬

mer. The following tables show the yield of oleoresin, as re¬

ported in the literature, likewise, that obtained in the labora¬

tory :

Du Mez — The Galenical Oleoresins ,

1025

Table 31. — Yield of oleoresin as reported in the literature.

65— S. A. L.

1026 Wisconsin Academy of Sciences , Arts , and Letters,

Table 31, — Yield of oleoresin as reported in the literature — Continued.

Du Mez — The Galenical Oleoresins.

1027

Chemistry of the Drug and Oleoresin.

Tabulation of Constituents.

The reported analyses1 of the various varieties of red peppers

show the constituents of pharmaceutical interest to be as fol¬

lows: fixed oil, volatile oil, fatty acids, capsaicin, capsicine,

resin, mudilage, starch, coloring matter and inorganic sub¬

stances. Most of these substances have been identified in the

oleoresin prepared by extracting the fruits with ether. They

Occurrence and Description of Individual Constituents.

Fatty Oil. Work on the oil of capsicum has practically been

limited to that obtained from the variety official in most of the

continental pharmacopoeias, namely: Capsicum annum L. The

properties of the oil of Capsicum fastigiatum Bl. as observed by

Goetz appears to indicate that it is very likely identical with

the former.2 The oil as obtained from the seeds of Capsicum

annum Bl.3 is a yellowish brown, mobile liquid, specific gravity

15.5°C 0.91095; iodine value (Huebls) 119.5; saponification

value (Koettsdorffer) 187.2. It is composed of the glyceryl

esters of oleic, palmitic and stearic acids.

The oil of capsicum is located in the seeds and is variously

stated to comprise from 204 to 24.065 per cent, of these organs

in Capsicum annum. The yield as computed by Goetz for the

entire fruit of Capsicum fastigiatum is 8.4 per cent.. The yield

in the case of Capsicum fructescens does not appear to have been

determined.

1 Taylor, Am. Journ. Fharm. (1857), 29, p. 803; Buchheim, Vierteljahrschr.

f. prakt. Pharm. (1872), 4, p. 507; Proc. A. Ph. A. (1873), 22, p. 106;

Strohmer, Chem. Centralb. (1884), 55, p. 557; Pabst, Arch. d. Pharm. (1892),

230, p. 108 ; Tolman and Mitchell, Bull. No. 163, Bur. of Chem., Dep. of Agr.

(1913), p. 9.

2 Goetz obtained 15.7 per cent of a yellowish -brown fixed oil from the

seeds of Capsicum fastigiatum Bl., specific gravity at 25°, 0.919. Goetz, un¬

published results.

3 Buchheim, Z. c. ; Pabst, Z. c.; von Bitto, Landwirt. Versuchs-Stat. (1896),

46, p. 310; Meyer-Essen, Chemiker Ztg. (1903), 27, p. 958.

4 Meyer-Essen, Z. c.

6 von Bitto, Z. c.

1028 Wisconsin Academy of Sciences, Arts, and Letters.

Fatty Acids.6 The free fatty acids present have been iden¬

tified as oleic, palmitic and stearic, palmitic acid predominating

in the fruits of Capsicum annum. The proportions of these

acids as they occur in the fruit of Capsicum fastigiatum or C.

fructescens have apparently not been determined to date.

Volatile Oil. The presence of a volatile oil was first noted in

the fruits of Capsicum annum by Taylor.7 Pabst isolated a

small amount of a volatile liquid having the odor of parsley

from the same. Inasmuch as the oleoresin, when prepared

from Capsicum fructescens has a distinct odor, it is quite prob¬

able that a similar volatile oil is also present in the fruit of

this variety.

Capsaicin 9 Capsaicin is the sharp tasting constituent of the

fruits of the various varieties of red pepper. It crystallizes

from petroleum ether in colorless plates melting at 60.5 °C

(Morbitz), 63 to 63.5°C (Micko), 64.5°C (Nelson).10 The sub¬

stance is stated to be soluble in water (1:30,000), petroleum

ether (1:3,633), ether, alcohol, carbon disulphide and chloro¬

form. According to Morbitz, its composition is represented

by the formula C35H54N304. Micko11 does not agree with the

latter and has proposed the formula ,CH3O.C17H24NO.OH, as

also representing the structure in part.

Capsaicin is stated by Morbitz to be present in the fruit of

Capsicum fastigiatum to the extent of 0.05 to 0.07 per cent.

0 Buchheim, Pabst, von Bitto, l. c.

7 1. c.

9 The term capsicin was first used to designate the sharp tasting principle

principle in red peppers. Bucholz, Taschenb. f. Scheidkuenst. u. Apoth.

(1816), 37, p. 1; Landerer, Vierteljahresschr. f. prakt. Pharm. (1854), 3,

p. 34. The name was also applied to the ethereal extract of capsicum as

marketed by Merck and Co. See note by Buchheim, Vierteljahrschr. f. prakt.

Pharm. (1873), 22, p. 507. Later it was used to indicate a coniine-like

alkaloid isolated from the fruit of Capsicum fastigiatum by Thresh. Pharm.

Journ. (1876), 35, p. 941.

In 1873, Buchheim gave the name Capsicol to a dark red oily liquid (our

present oleoresin) which he considered to be the pungent principle.

Capsaicin is the term which was Introduced by Thresh to denote the sharp

tasting substance isolated by him from the fruits of Capsicum fastigiatum.

Pharm. Journ. (1876), 36, p. 21. It is the name now generally employed to

indicate this substance, although, Morbitz ( l . c.) subsequently proposed the

name Capsicutin.

A more recent investigator, Gabriel de la Puerta, has given the name

“capsic acid” to the irritant principle isolated from pimenta. Ann. de la

Soc. Espanola de fis. y. quim. (1905), No. 23; Am. Drugg. & Pharm. Rec.

(1906), 48, p. 40.

10 Chem. News (1911, 103, p. 111.

11 Chem. Centralbl. (1899), 70, p. 293.

Du Mez — The Galenical Oleoresins.

1029

The amount present in Capsicum fructescens has not been re¬

ported.

Capsicine. According to Felletar12 and Thresh,13 capsicine

is present in the fruits of Capsicum annum and C. fastigiatum.

The latter describes it as an alkaloid possessing an odor simi¬

lar to that of coniine. The hydrochloride is stated to have been

isolated in the crystalline form and to be precipitated from

aqueous solution by the usual alkaloidal reagents. Pabst14

states that the base is not a normal constituent of the fruits

of Capsicum annum, but that it is formed when the latter are

stored or by the action of various reagents.

Resin. Resin is mentioned by several investigators15 as a

constituent of the fruits of the red peppers. Apparently noth¬

ing has been done toward determining its composition or proper¬

ties.

Coloring Matter. The red color of the capsicum fruit as

well as that of the ethereal extract appears to have attracted

the attention of all investigators, although, Pabst, is the only

observer who attempted to identify the substance. He concluded,

from saponification experiments, that it was a cholesterin ester

of a fatty acid.16

Ash. According to von Bitto,17 the ash of capsicum is com¬

posed of the basic elements, K, Na, Mg, Ca, Fe, A1 and Mn

combined with the acid radicles Cl#, Si03", S04", P04"', N03'

and C03".

The ash content of red pepper varies with the variety of the

fruit.18 That of the commercial drug is also influenced by

the presence of sand. The ash of Capsicum fructescens (sand

free) amounts to about 4.90 per cent of the dried fruit.19

12 Vierteljahrschr. f. prakt. Pharm. (1868), 17, p. 360; Buchner’s Repert.

f. d. Pharm. (1828), 27, p. 35; Proc. A. Ph. A., (1871), 19, p. 289.

“Pharm. Journ. (1876), 35, p. 941.

«Z. c.

15 Strohmer, Pabst, Tolman and Mitchell, Z. c.

19 Pabst, Z. c.

17 Landw. Versuchsstat. (1893), 42, p. 369.

18 Tolman and Mitchell give the ash content of sand free Capsicum annum

as 6.69 to 7.54 per cent. Bull. 163, Bur. of Chem., Dept of Agr., Washington,

1913.

19 McKeown gives the ash content of Capsicum fastigiatum as 4.50 to 4.95

per cent. Am. Drugg. (1886), 14, p. 128.

Tolman and Mitchell report the sand free ash content of Capsicum fruc¬

tescens (African) as 4.49 to 5.44 per cent, that of the fruits of the same

variety coming from Japan as 4.60 to 5.35 per cent, Z. c.

1030 Wisconsin Academy of Sciences , Arts, and Letters.

Constituents of Therapeutic Importance

The early investigators assigned the intensely irritating

properties of the oleoresin of capsicum to various substances

supposed to be contained therein. Bracconot1 and Buchheim2

thought it due to the oily constituents, Felletar3 attributed the

action to a liquid organic base, and Pabst4 to a resin intimately

mixed with the red pigment. The irritating principle is now

known to be the crystalline constituent, capsaicin.5 The latter

has not been isolated in sufficient quantities to permit of an

extensive investigation of its physiological . properties. It is,

however, known to act as a rubefacient when applied exter¬

nally, and to be extremely pungent to the taste, its sharpness

being perceptible in aqueous solution, 1 part to 11 million

parts of water.6

Physical Properties

Color: The color of the oleoresin, when the latter is

spread out in a thin layer on a white porcelain surface, is a

characteristic light brownish-red. The descriptions of the

color given in pharmaceutical literature vary to a considerable

extent (light reddish-brown to dark brown) owing very likely to

a difference in the conditions under which the observations were

made.

Odor: The odor of the preparation is rather faint, but char¬

acteristic, resembling that of the red peppers.

Taste: It is extremely pungent and should be tasted with

caution. The taste is usually described as being hot and fiery,-

or burning.

Consistence: The consistence of the oleoresin varies with the

amount of solid fats (palmitin and stearin) present,7 and with

1 Ann. Chim. Phys. (1817), 6. p. 122.

a Vierteljahresschr. f. prakt. Pharm. (1873), 22, p. 507.

3 Ibid. (1868), 17, p. 360.

4 Arch. d. Pharm. (1892), 230, p. 108.

5Micko, Zeitschr. f. Unters. Nahr.-u. Genussm. (1898), 12, p. 215.

6 Morbitz, Pharm. Zeitschr. f. Russland, (1897), p. 372.

7 See under “Methods of preparation".

Du Mez—The Galenical Oleoresins. 1031

the temperature. At ordinary temperatures the degree of

fluidity is usually such that it can be readily poured. It should

be homogeneous and not contain a deposit of fat.

Solubility: The oleoresin, when prepared with ether, is

soluble in acetone, ether, chloroform, carbon tetrachloride, car¬

bon disulphide, petroleum ether, oil of turpentine1 and solu¬

tions of the caustic alkalies. It should not be soluble to any

great extent in 90 per cent, alcohol, solubility therein indicating

that alcohol was the menstruum used in the preparation of the

oleoresin.

Specific gravity: The specific gravity of the oleoresin de¬

termined at 25 °C was found to be 0.925 to 0.932 when ether was

the solvent employed in extracting the drug. When alcohol

or acetone were employed for this purpose, the results were

almost the same, whereas petroleum ether yielded a product

of low specific gravity. The low specific gravity observed in the

one case, where acetone was used in the preparation of the oleo¬

resin, was not due to the nature of the solvent, but to the

more complete removal of the solid fats. The variation in the

amounts of the latter retained in the finished product is thought

to be the chief factor influencing the specific gravity of this

preparation. In the case of the commercial samples, how¬

ever, the presence of unevaporated solvent must also be taken

into consideration as is shown in the tables which follow:

Table 33— Specific gravities of oleoresins prepared in the laboratory.

1 King’s American Dispensatory (1900), p. 1331.

1032 Wisconsin Academy of Sciences , Arts , and Letters.

Table 34 — Specific gravities of commercial oleoresins.

1 o ntained ether

Refractive index: Determinations made in the laboratory

show that the oleoresin should have a refractive index of about

1.47 when observed at 25 °C. A refractive index lower than

this was found to be due to the presence of unevaporated solvent.

The solvent employed in extracting the drug or the variation

in solid fat content appears to have very little influence, if

any, on this constant. The results obtained in the laboratory

in the examination of the oleoresin follow:

Table 35 - Refractive indices of oleoresins prepared in the laboratory.

Table 36. — Refractive indices of commercial oleoresins.

1 Contained ether.

Du Mez — -The Galenical Oleoresins.

r

1033

Chemical Properties.

Loss in weight on heating: Determinations made in the

laboratory show that the oleoresin loses but little in weight on

heating at 110 °C, a loss of but 0.42 to 2.13 per cent, having

been observed for the preparation when free from solvent. The

laboratory preparations as a rule showed a smaller loss than

the commercial samples, which is very likely due to a difference

in the temperature conditions under which the preparations

were made. The results obtained in the determinations made

in the laboratory are given in the following tables :

Table 37 —Laboratory preparation*— loss in weight on heating

1 Contained alcohol.

Table 38. — Commercial oleoresins — loss in weight on heating.

1 Contained ether.

Ash Content: The determinations made in the laboratory

show that the ash content of the oleoresin varies with the solvent

employed in its preparation. When acetone was the solvent

used, the amount of ash obtained did not exceed 0.26 per cent,

whereas, the amount was only 0.09 to 0.12 per cent, when the

oleoresin was prepared with ether. The variable results ob¬

tained in the examination of the commercial samples appear to

1034 Wisconsin Academy of Sciences , Arts , and Letters.

indicate the use of different solvents in their preparation. The

comparatively high value (0.40 per cent.) obtained in one case,

however, may have been due to the copper present. The ash

content of the samples examined in the laboratory is given in

the tables which follow:

Table 39 — Ash contents of oleorsins prepared in the laboratory.

Tabe 40.— Ash contents of commercial oleoresins

1 Contained ether.

Acid number: The acid numbers, when acetone, ether, or

petroleum ether were used in the preparation of the oleoresin,

were found to be 106.6, 103.8 and 105 respectively. When

alcohol was employed for this purpose, the value obtained for

this constant was considerably lower, being 93.5. With respect

to the commercial samples examined, the acid number was in

all cases found to be much lower. This is thought to be due,

in two instances, to a low free acid content (principally pal¬

mitic acid) of the drug from which the oleoresins were pre¬

pared, or to the more complete removal of these acids in the

separation of the deposited material. In the third case, it

was caused, in part, at least, by the presence of unevaporated

solvent. The acid numbers obtained for the preparations ex¬

amined in the laboratory are as ofllows:

Du Mez — The Galenical Oleoresins.

1035

Table 41 - Acid numbers of oleoresins prepared in the laboratory.

Table 42 — Acid numbers of commercial oleoresins.

1 Contained ether.

Saponification value: The saponification values obtained for

the oleoresins prepared in the laboratory were above 200, as a.

rule, regardless of the nature of the solvent used in extracting

the drug. The comparatively slight variations observed were

very likely due to the difference in the degree to which the

solid fats (principally palmitin) had been removed. This also

accounts for the comparatively low values obtained for the

commercial preparations. The exceptionally low value ob¬

tained for the sample from Squibb and Sons is to be attributed

to the presence of unevaporated solvent. The values obtained

for the preparations examined in the laboratory are given in

the tables which follow:

Table 48 — Saponification values of oleoresins prepared in the laboratory.

.cat>3H-oe^ia»tn

1036 Wisconsin Academy of Sciences , Arts , and Letters.

Table 44 — Saponification values of commercial oleoresins.

1 Contained ether.

Iodine value: An iodine value of 122 to 123.9 was obtained

for the oleoresins prepared in the laboratory using ether as the

extracting menstruum. Results very near the same were ob¬

tained when acetone or petroleum ether were the solvents used,

whereas, the preparation when made with alcohol gave a lower

value, 109.3 to 105.7. The principal cause1 for the variation

in this constant (aside from the effect which the quality of the

drug or the solvent may have thereon) as observed in the case

of some of the laboratory preparations, as well as the commercial

samples, is thought to be the difference in the degree to which

the saturated fats (principally palmitin) have been removed.

In the case of one of the commercial samples, however, the

low iodine value is to be attributed to the presence of unevap¬

orated solvent. The results obtained in the determinations

made in the laboratory together with those reported by Kebler

for the total ether extract are given in the tables which follow :

Table 45 _ Iodine values of laboratory preparations.

Sample

No.

2...

3.. .

4.. .

-24

C'.

1. .

9

4...

Date

Observer

1913 Kebler a.

1916 DuMez

Solvent

Ether ,

Alcohol .

Acetone .

Ether . . . . . .

Petrol. Ether

Alcohol . .

Acetone .

Ether .

Benzin .

no

Iodine

value

107.

123.4

125.2

127.3

132.0

137.3

138 0

0to 14-5.7

115.7

125.2

122.0

123.7

109.3

118.0

102.9

116.9

(a) Kebler’s results represent the iodine value of the total ether extract.

1 Lowenstein and Dunn have shown that heating at 110° C. to remove

volatile matter from the total ether extract causes a lowering in the iodine

value due to absorption of oxygen by the unsaturated fats. Journ. Indust,

and Eng. Chem. (1910). 2. p. 48.

Du Mez — The Galenical Oleoresins.

1037

Table 46. — Iodine values of commercial oleoresins.

1 Contained ether.

Special Quantitative Tests.

Physiological Test.

As the active constituent is present in the oleoresin in such

minute quantities that a gravimetric method for its estimation

is not practical at the present time, a physiological method would

appear to be the best means to employ in the standardization

of this preparation. Such a method is reported to be in use

for this purpose by the H. K. Mulford Company. Aside, how¬

ever, from the fact that the test is based on the ability to de¬

tect the pungency of the oleoresin in extremely dilute solutions,

and that the firm takes as its standard a preparation which is

still pungent to the taste in a maximum dilution of 1 to 150,000,

there is no exact information available to show in what man¬

ner the same is actually carried out. It is thought, however,,

that a procedure similar to that developed in this laboratory

some years ago (1910) is made use of. The following is a

description of this method.

Accurately weigh about 1 drop of the oleoresin contained in a small

flask, add 5 cubic centimeters of normal potassium hydroxide solution and

heat on a water bath for a short time to saponify the fats. Transfer

the saponified material to a 100 cubic centimeter flask, using several por¬

tions of water for this purpose, and finally dilute up to the mark with

more water. With the aid of a pipette, measure off 5 cubic centimeters

of this solution and run it into a graduated cylinder (glass stoppered) of

1,000 cubic centimeters capacity. Dilute this with water added in por¬

tions of 100 cubic centimeters, tasting the solution after each addition.

Note the highest dilution in which the pungent taste is still distinctly per¬

ceptible and compare this with the results obtained using a standard

preparation.

As all of the samples prepared in this laboratory were found

to be distinctly pungent to the taste in dilutions of 1 to 250,000,

1038 Wisconsin Academy of Sciences, Arts , and Letters.

it is thought that the standard employed by the H. K. Mulford

Company is rather low. In view of these observations, it would

appear that a standard of 1 in 200,000 would be more desirable.

Adulterations

A trace of copper was found in most of the commercial

samples examined. See under ‘‘Ash content. ’ ’

OLEORESIN OF CUBEB

Synonyms

Aetherisches Cubebenextrakt, Bern. P. 1852.

Aether-szeszes Icubeba Tcivonat, Hung. P. 1888.

Cubeben Extract, Nethl. P. 1902.

Estratto di Cubebe, Swiss P. 1907.

Estratto di Pepe Cubebe, Swiss P. 1865.

Estratto di Pepe Cubebe Etereo, Ital. P. 1902.

Ethereal Extract of Cubeb, Am. Journ. Pharm. (1846), 18, p. 167.

Extract van Staartpeper, Nethl. P. 1871.

Extractu de Cubebe, Bourn. P. 1874.

Extractum Cubebae Fluidum, U. S. P. 1850.

Extractum Cubebarum, Aust. P. 1906.

Extractum Cubebarum aethereum, Swiss P. 1865.

Extractum Cubebarum aether eo-spirituosum, Hung. P. 1888.

Extractum Cubebarum oleoso-resinosum, Strump, Allg. P. 1861.

Extractum Kubebae oleo-resinosum, Pruss. P. 1829.

Extrait de Cubebe, Fr. P. 1884.

Extrait ethere de Cubebe, Bern. P. 1852.

Extrait oleo-sesineux Cubebe, Fr. P. 1884.

Fluid Extract of Cubebs, U. S. P. 1850.

Kubebe Extract, Dan. P. 1869.

KubebenextraPt, G. P. 1872.

KubeberextraTct, Dan. 1893.

Kubeba Kivonat, Hung. P. 1875.

Oelig-Harziges KubebenextraPt, Strump, Allg. P. 1861.

Oleo-Besin of Cubebs, B. P. 1885.

Oleo-Besina Cubebae, B. P. 1885.

Oleoresina Cubebae, U. S. P. 1910.

Oleoresine de Cubebe, U. S. Disp. 1907.

Oleoresinous Extract of Cubeb, Pareira, Mat. Med. 1854.

History

The oleoresin of cubeb, prepared by extracting the drug with

ether and then removing the latter by distillation, was first

Du Mez — The Galenical Oleoresins. 1039

brought to the attention of the European pharmacist by Haus-

mann in 1838. Ten years previous (1828), however, Dublanc

in France and simultaneously Oberdoerffer in Germany had

made known a similar preparation obtained by a rather long

and tedious process involving the distillation of the drug with

steam and subsequent extraction of the marc with alcohol. The

latter became official in the Prussian Pharmacopoeia of 1829

and in the Pharmacopoeia of Schleswig-Holstein in 1846, while

the former first received official recognition in the Baden Phar¬

macopoeia of 1841.

Through the efforts of Procter, a preparation similar to that

made by Hausmann was introduced into the United States

Pharmacopoeia of 1850 under the title Extractum Cubebae

Fluidum . In the edition of 1860, this title was changed to

Oleoresina Cubebae. The preparation official in the United

States at present is the oleoresin obtained by extracting the

cubeb with alcohol, whereas, that which is given recognition

in the late European pharmacopoeias is the product obtained

by exhausting the drug with a mixture of alcohol and ether.

The pharmacopoeias of the countries, states and munieipali-

ities in which this preparation has been officially recognized, to¬

gether with the dates of appearance of the various editions in

which it received such recognition, are enumerated below.

Prussian Pharmacopoeia — 1829, 1833, 1868.

Pharmacopoeia of Baden — 1841.

Pharmacopoeia of Schleswig-Holstein - — 1844.

Pharmacopoeia of Berne — 1852.

Belgian1 Pharmacopoeia — 1854, 1855.

United States Pharmacopoeia — 1850, 1860, 1870, 1880, 1890, 1900, 1910.

Pharmacopoeia of Hannover — 1861.

Pharmacopoeia of Hessen — 1862.

Swiss Pharmacopoeia — 1865, 1872, 1893, 1907.

Austrian Pharmacopoeia— 1869, 1889, 1906.

Danish1 Pharmacopoeia — 1869, 1893.

Hungarian Pharmacopoeia — 1871, 1888, 1909.

Netherlands Pharmacopoeia — 1871, 1902.

German Pharmacopoeia — 1873, 1882, 1890, 1900, 1910.

Roumanian Pharmacopoeia — 1874.

French Pharmacopoeia — 1884, 1908.

British1 Pharmacopoeia — -1885.

Italian Pharmacopoeia — 1902, 1909.

Japanese Pharmacopoeia — 1907.

1 Not official in the recent editions.

1040 Wisconsin Academy of Sciences, Arts, and Letters.

Drug Used, Its Collection, Preservation, Etc.

The drug recognized by the ninth revised edition of the

United States Pharmacopoeia is “the dried, unripe fruits of

Piper Cubeba Linne filius (Fam. Piperaceae), without the pres¬

ence or admixture of more than 5 per cent of stems or other

foreign matter. ” Other botanical synonyms for the same fre¬

quently met with in the literature are : Cubeba Cubeba (Linne

filius) Lyons; and Cubeba officinalis Mique.

The fruit is supposedly gathered when full grown, but before

ripe, and is immediately packed for exportation. That some

of the fruit for sale on the American market is not collected

until after ripening would appear to be the case from the color

of some of the oleoresins prepared by the author, a condition

which has also been noted by the others.1 In addition, it should

also be noted that the so-called false cubebs2 are sometimes sub¬

stituted for the official drug.

As cubeb gradually deteriorates with age,3 and in the

powdered condition becomes rapidly weaker owing to the loss

of volatile oil, it should be stored whole, in closed containers,

and powdered only as it is used.

U. S. P. Text and Comments Thereon.

The oleoresin has been official in the last seven editions of the

Pharmacopoeia, having been recognized for the first time in the

edition of 1850 under the title Extractum Cubebae Fluidum.

1850

Extractum Cubebae Fluidum

Fluid Extract of Cubebs

Take of Cubebs,1 in powder,2 a pound; then distill off, by means of a water-

Ether3 a sufficient quantity. bath, at a gentle heat, a pint and a

Put the Cubebs into a percolator,4 * half of the ether,6 and expose the

and, having packed it carefully, pour residue, in a shallow vessel, until the

Ether gradually upon it until two whole of the ether has evaporated.7

pints of filtered liquor are obtained;6

1 Emanuel (1894) stated that when he reported to the jobber that he had

obtained a brown colored oleoresin from the cubeb purchased, the latter

replied that, while the United States Pharmacopoeia specified the unripe fruit,

this was rarely found on the market.

2 The botanical origin of this fruit is not known. Culbreth, Materia Medica

and Pharmacology (1908), p. 138.

3 The volatile oil, in part, is converted into the so-called cubeb camphor,

especially when stored in a damp place. Schmidt, Ber. d. deutsch chem.

Ges. (1877), 10, p. 188.

Du Mez — The Galenical Oleoresins.

1041

1860

Oleoresina Cubebae

Oleoresin of Cubeb

Extractum Cubebae Fluidum, Pharm ., 1850

Take of Cubeb,1 in fine powder,3 liquid have passed.15 Recover from

twelve troyounces; this, by distillation on a water-bath,

Ether 3 a sufficient quantity. eighteen fluid-ounces of ether,® and

Put the Cubeb into a cylindrical expose the residue, in a capsule, until

percolator,4 press it moderately, and the remaining ether has evaporated.1

gradually pour Ether upon it until Lastly keep the oleoresin in a well-

twenty-four fluid-ounces of filtered stopped bottle.®

1870

Oleoresina Cubebae

Oleoresin of Cubeb

Take of Cubeb,1 in fine powder,2 ed.5 Recover the greater part of the

twelve troy-ounces ; ether by distillation on a water-bath,®

Ether 3 a sufficient quantity. and expose the residue, in a capsule,

Put the Cubeb into a cylindrical until the remaining ether has evapor-

percolator, provided with a stop-cock, ated.7 When, after standing in a close

and arranged with a cover and recep- vessel, the liquid has deposited a waxy

tacle suitable for volatile liquids,4 and crystalline matter, decant the

press it moderately, and gradually oleoresin 8 and keep it in a well-stop-

pour ether upon it, until twenty-four ped bottle.®

fluidounces of liquid have slowly pass-

1880

Oleoresina Cubebae

Oleoresin of Cubeb

Cubeb,1 in No. 60 powder,3 one hun- tillation on a water-bath,® and ex-

dred parts . 100 pose the residue, in a capsule, until

Stronger Ether,3 a sufficient quantity . the remaining ether has evaporated.7

Put the Cubeb into a cylindrical Transfer the remainder to a close ves-

percolator, provided with a cover and sel, and let it stand until it ceases to

receptacle suitable for volatile li- deposit a waxy and crystalline mat-

quids,4 press it firmly, and gradually ter. Lastly, pour off the oleoresin.8

pour stronger ether upon it, until one Keep the oleoresin in a well-stop-

hundred and fifty (150) parts of ped bottle.®

liquid have slowly passed.5 Recover Preparation: Trochisci Cubebae.

the greater part of the ether by dis-

66— S. A. L.

1042 Wisconsin Academy of Sciences , Arts , and Letters.

1890

Oleoresina Cubebae

Oleoresin of Cubeb

Cubeb,1 in No. 30 powder,’ five hun¬

dred grammes . 500 Gm.

Ether,3 a sufficient quantity.

Put the Cubeb into a cylindrical

glass percolator, provided with a

stop -cock, and arranged with a cover

and receptacle suitable for volatile

liquids.4 Press the drug firmly, and

percolate slowly with ether, added in

successive portions, until the drug is

exhausted.5 Recover the greater part

of the ether from the percolate by

distillation on a water-bath,6 and, hav¬

ing transferred the residue to a cap¬

sule, allow the remaining ether to

evaporate spontaneously.7

Keep the product in a well-stop¬

pered bottle.9

NOTE. Oleoresin of Cubeb de¬

posits, after standing for some time,

a waxy and crystalline matter, which

should be rejected, only the liquid

portion being used.8

Preparation: Trochisci Cubebae.

1900

Oleoresina Cubebae

Oleoresin

Cubeb,1 in No. 30 powder,2 five hun¬

dred grammes . 500 Gm.

Alcohol,3 a sufficient quantity.

Introduce the cubeb into a cylindri¬

cal glass percolator,4 pack the powder

firmly, and percolate slowly with al¬

cohol, added in successive portions,

until the cubeb is exhausted.6 Re¬

cover the greater part of the alcohol

from the percolate by distillation on

a water-bath,6 and, having transferred

the residue to a dish, allow the re-

of Cubeb

maining alcohol to evaporate, with

constant stirring, in a warm place.7

Keep the oleoresin in a well-stoppered

bottle.9

NOTE. Oleoresin of cubeb de¬

posits, after standing for some time,

a waxy and crystalline matter, which

should be rejected, the liquid portion

only being used.8

Average dose. — 0.500 Gm. = 500

milligrammes (7% grains.)

/

Du Mez — The Galenical Oleoresins.

1043

1910

Oleoresina Cubebae

Oleoresin of Cubeb

Oleores. Cubeb

Cubeb/ in No. 30 powder/ five hun- alcohol to evaporate, in a warm place,

dred grammes . 500 Gm. stirring frequently.7 Keep the oleo-

Alcohol/ a sufficient quantity. resin in a well stoppered bottle.9

Place the cubeb in a cylindrical NOTE- — Oleoresin of Cubeb, after

glass percolator/ pack the powder standing for some time, deposits a

firmly, and percolate slowly wfith alco- waxy and crystalline precipitate,

hoi, added in successive portions, until which should be rejected, the, liquid,

the drug is exhausted.5 Eecover the portion only being used.8

greater part of the alcohol from the Preparation — Trochisci Cubebae.

percolate by distillation on a water- Average Dose — Metric, 0.5 Gm. —

bath,6 and, having transferred the Apothecaries, 8 grains,

residue to a dish, allow the remaining

1) For a description of the drug, see page 1040 under ‘'Drug

used, its collection, preservation, etc.”

2) The last three editions of the Pharmacopoeia have specified

that the drug used be reduced to a No. 30 powder for perco¬

lation. Previous editions, with the exception of that of 1850,

directed that a fine powder (No. 60) be used for this purpose.

In the Pharmacopoeia of 1850, the degree of fineness was not

specified. The coarser powder corresponds more nearly in its

composition to that of the whole fruit than does the fine pow¬

der, owing to the fact that a relatively large amount of vola¬

tile oil is lost in the preparation of the latter.

3) Previous to the edition of 1900, the Pharmacopoeia speci¬

fied the use of ether for extracting the drug, whereas, the last

two editions have directed that alcohol be employed for this

purpose. The fact, that the latter yields a product differing

but slightly in its physical properties from the oleoresin ob¬

tained with ether, was pointed out by Procter in 1866, and

later confirmed by other investigators. Since the alcoholic

preparation appears to be equally as efficient from a therapeu¬

tic standpoint, as well, the change from ether to alcohol ap¬

pears to be justified. The use of a menstruum consisting of

equal parts of alcohol and ether, as specified in some of the

foreign pharmacopoeias, the Austrian, German and Japanese,

1044 Wisconsin Academy of Sciences, Arts, and Letters.

does not appear to offer any special advantage either from a

pharmaceutic or therapeutic standpoint.

4) In the Pharmacopoeias of 1870, 1880 and 1890, t he drug

was directed to be extracted in a percolator specially adapted

to the use of volatile solvents. See Part I under “Apparatus

used.” With the change in menstruum (ether to alcohol), a

special form of percolator was no longer necessary, and the

Pharmacopoeia now directs that an ordinary cylindrical, glass

percolator be used.

5) In the earlier editions of the Pharmacopoeia (1850 to 1880

inclusive), it was directed that percolation be discontinued short

of the complete exhaustion of the drug, the object evidently

having been to economize in the use of the relatively expen¬

sive solvent, ether. With the reduction in the price of the

latter, however, the economic factor diminished in importance

and as a result the Pharmacopoeia of 1890 directed that perco¬

lation be allowed to proceed until the drug was exhausted.

This is also the procedure given in the more recent editions of

the Pharmacopoeia, in which alcohol has replaced ether as the

extracting menstruum.

In this connection, it is desired to point out that, whereas

percolation, when ether is the menstruum used, should be con¬

tinued to complete exhaustion of the drug in order that the

extraction of the total amount of therapeutically active con¬

stituents may be assured, this procedure does not appear to be

necessary when alcohol is the solvent employed. While this

statement is not in conformity with the present pharma-

copceial directions governing the extraction of the drug and is

not supported by direct experimental evidence, it is thought

to be justified in view of the difference in the solubility of the

therapeutically active resins in the above mentioned men¬

strua. The indifferent resin is but slightly soluble in ether.

It will, therefore, be extracted but slowly by this solvent and

will be present in the percolate even to the last portions. Al¬

cohol, on the other hand, dissolves both, the acid and indiffer¬

ent resins readily. These substances should therefore be con¬

tained in toto in the first portions of the percolate. In this

case, it would therefore hppear that the continuation of the

process of extraction to the complete exhaustion of the drug

Du Mez — The Galenical Oleoresins.

1045

only serves to load the percolate with undesirable extractive

matter such as cubebin.

6-7) The various editions of the Pharmacopoeia, since 1870,

have directed that the greater part of the solvent be removed

from the percolate by distillation on a water bath, and that

the remainder be allowed to evaporate spontaneously.

Experience in the laboratory has shown that it is impos¬

sible to obtain a uniform product, when operating according

to the above directions, unless identical conditions are main¬

tained in each case. This is due to the fact that a compara¬

tively slight variation in the procedure, with respect to the

quantity of the solvent removed by distillation or to the tem¬

perature at which spontaneous evaporation is allowed to pro¬

ceed produces a variation in the volatile oil content of the finished

product, which in turn affects its physical and chemical proper¬

ties. It is thought, therefore, that the amount of solvent to be

removed by distillation, as well as the temperature at which

the last portions are to be removed, should be definitely stated

by the Pharmacopoeia in order that a more uniform product

may be obtained.

8) For a statement concerning the nature of the precipitate

which forms in the oleoresin upon standing, see page 1060 un¬

der “Other properties.”

Since the greater part of the precipitate is composed of ma¬

terial which is of no therapeutic value, it should be removed

before dispensing the preparation as directed by the Pharma¬

copoeia.

9) The oleoresin should be kept in well stoppered bottles ow¬

ing to the fact that it loses volatile oil and undergoes other

changes on exposure to the air. See cubeb camphor, page

1050.

Yield

The amount of oleoresin obtained varies to a considerable

extent, 10 to 30 per cent, having been obtained when alcohol,

acetone or ether were employed as menstrua for the extraction

of the drug. When petroleum ether is the solvent made use of,

the yield is much lower, 4 to 18 per cent, having been reported

in this case. Aside from the effect of the solvent, the principal

1046 Wisconsin Academy of Sciences , Arts , and Letters.

factors influencing the yield appear to be the variation in the

volatile oil content of the drug from which the oleoresin is pre¬

pared and the conditions under which the preparation of the

latter has been accomplished. As the volatile oil content of

the cubeb fruit is stated to vary from 10 to 18 per cent., a var¬

iation of even greater magnitude is to be expected in the amount

of oleoresin obtained. While this (is true when a vacuum pan is

employed in the evaporation of the solvent, the difference is

not so great when the pharmacopceial directions are followed

as the loss in volatile oil in this case is relatively greater when

the fruits contain a large amount of this constituent than when

only a small amount is present. The difference is still further

decreased when the solvent is evaporated on a water bath under

ordinary atmospheric pressures. The following tables show

the yield of oleoresin obtained with the use of various solvents :

Date

1846

1868

1867

1868

1877

1887

1888

1892

1895

1907

1908

1909

1910

1911

Du Mez — The Galenical Oleoresins.

1047

Table 47 — Yield of oleoresin as repwted in the literature.

Observer

Yield of oleoresin to—

Alco¬

hol

Ace¬

tone

Ether

Other

solvents

Remarks

Bell.

Per

cent

Per

cent

Procter .

Pile .

Heydenreich

Griffin .

Kremel

27.00

Per

cent

15.0 to

20.0

21.9

Per cent.

28.75

80.00

Trimble. .

Beringer.

22.00

21.26

Sherrard,

21.75

24.10

25.00

Hyers.

Blome.

14.48

18.48

16.40

18.80

21.06

21.90

23.00

24.70

24.80

22.45

Evans Sons,

Lescher & Webb

Vanderkleed

Southall Bros.

& Barclay....

Vanderkleed

Vanderkleed ..

Southall Bros.

& Barclay ...

Benzin

16.50

Benzin

5.00

Gasolin

16,50

Benzin

16.65

I Petrol.

Ether.

! 13.47

i Solvent(?)

1 18.85 to 26.8

22.08

22.60

21.13

22.80

Solvent(?l

13 69 to 23.60

j Solvent (?)

1 16.49 to 24.34

Petrol

Ether

3.88

4.30

4.45

14.00

16.03

16.54

16.90

18.08

Solvent(?)

18.42 to 24.40

Solvent (?)

22.14

Petrol

Ether

4.66 to 8.78

Yield to benzin, sp. gr.

Baumd.

The cubebs were completely

exhausted.

Reported as yield of oleoresin.

Results obtained in the ex¬

traction of 5 samples of

cubeb.

Reported as yield of oleoresin.

Results obtained in the ex¬

traction of 4 samples of

cubebs.

Reported as yield of oleoresin.

On subsequent ext? action with

alcohol 3.40 to 5.66 per cent,

of extractive matter was ob¬

tained.

Reported as yield of oleoresin.

Results obtained in the ex¬

traction of 6 samples of

cubebs.

Reported as yield of oleoresin .

The average yield of 5 samples

of cubebs is given as 6.95.

1048 Wisconsin Academy of Sciences, Arts, and Letters,

Table 47 — Yield of oleoresin as reported in the literature — Continued.

Table 48 — Yield of oleoresin as obtained in the laboratory .

i

Du Mez—The Galenical Oleoresins.

1049

Chemistry of the Drug and Oleoresin.

Tabulation of Constituents.

We are indebted principally to Bernatzik1 Schmidt2 * and

Schulze5 6 for definite information concerning the constituents

of the cubeb fruit. According to these investigators, the con¬

stituents of importance from a pharmaceutical standpoint are

as follows: volatile oil, fatty oil, fat, cubebin, cubebic acid,

indifferent resin, coloring matter, starch, gum and inorganic

substances. Inasmuch as an attempt to determine the compo¬

sition of the oleoresin does not appear to have been made since

the identification of the above enumerated constitutents, a

definite statement concerning its exact composition can not be

given.4 However, a knowledge of the physical properties of

the constituents of the fruit warrants the statement that the

following are present in the oleoresin when prepared with alco¬

hol or ether:

Volatile oil Cubebin Coloring matter

Fatty oil Cubebic acid (Acid resin) Ash

Fat Resin (Indifferent resin)

Occurrence and Description of Individual Constituents

Volatile Oil.5 The volatile oil of cubeb is a colorless or pale

green, thick fluid possessing a burning, spicy, but not a bitter

taste. Its specific gravity varies (0.915 to 0.937 at 15°C) de¬

pending on the age of the oil after distillation or the length

of time that the fruits have been stored before obtaining the

oil. It is strongly refractive and is laevogyrate,-^39.45° to

1 Buchner’s n. Repert. f. d. Pharm. (1865), 14, p. 97.

3 Arch. d. Pharm. (1870), 191, p. 23.

*Ibid. (1873, 202, p. 388.

The following1 are among the early investigators who have reported analy¬

ses of the fruit: Trommsdorff, Trommsdorff’s n. Journ. der Pharm. (1811),

20, p. 69; Vauquelin, Journ. de Chim. Med. (1820), 21, p. 103; Taschenb. f.

Scheidekuenst. (1822), p. 185; Monheim, Buchner’s Repert. d. Pharm. (1833),

44, p. 199.

4 Vieth in an article on the relation between the chemical composition and

therapeutic activity of various balsams states that Kubebenextrakt consists

of terpenes (25 per cent.) resin acids (10 per cent.) and resins (25 per

cent.) Verh. d. Ges. deutsch. Naturf. u. Aerzte (1905), 2, p. 364.

6 The above description is for the volatile oil obtained from the fruits by

steam distillation and corresponds to the properties as observed by Schmidt,

Arch. d. Pharm. (1870), 191, p. 18.

1050 Wisconsin Academy of Sciences , Arts , and Letters.

— 40.16°. Alcohol, ether, carbon disulphide, petroleum ether,

chloroform and fatty oils dissolve it readily.

The investigation of the composition of this oil has been

undertaken by a number of workers.6 Oglialoro7 noted the

presence of a small amount of a 1-terpene (pinene or camphene).

Wallach8 isolated dipentene and cadinene. The presence of the

latter has been confirmed by others.9 Cubeb camphor10 has also

been obtained from certain samples of the oil. It is a sesqui¬

terpene hydrate (C15H24H20) which forms when the fruits are

stored in a damp place or when the oil is exposed to a moist

atmosphere. It separates out in the form of rhombic octahe¬

drons when the oil is cooled at a low temperature ( - 12 to

-14° C) for some time.

The yield of the oil is stated by Schimmel & Co.11 to be from

10 to 18 per cent. A yield as low as 0.4 per cent, has been re¬

ported.12 Schmidt obtained 14.215 per cent, from fresh cubebs

and 13.041 per cent, from stored cubebs.13

Fatty Oil. Schmidt14 describes the fatty oil as a thick, dark

green liquid congealing at 0°C. It is stated to be slowly but

completely soluble in cold alcohol, more soluble in hot alcohol,

readily soluble in ether, chloroform, carbon disulphide and fatty

oils.

The yield as reported by the above investigator is 1.175 per

cent, for fresh cubebs and 1.096 per cent, for fruits which have

been stored for some time.

“The earliest work on the constituents of the oil is that of Soubeiran and

Capitaine, Ann. d. Chem. (1840), 34, p. 31.

TGaz. Chim. Ital. (1875), 5, p. 497.

“Ann. d. Chem. (1887), 238, p. 78.

0 Schaer and Wyss, Arch. d. Pharm. (1875), 206, p. 216; Umney, Pharm.

Journ. (1895), 25, p. 951.

10Blanchet and Sell, Ann. d. Chem. (1833), 6, p. 294; Winckler, Buchner’s

Repert. f. d. Pharm. (1833), 45, p. 397; Bernatzik, Buchner’s n. Repert. f.

d. Pharm. (1865), 14, p. 97; Schmidt, Ber. d. deutsch. chem. Ges. (1877),

10, p. 188.

11 Schimmel & Co., Ber. (1897), p. 14.

Du Mez — The Galenical Oleoresins.

1051

Fat. Schmidt15 obtained 0.511 per cent, of a semi-solid fat

from fresh cubebs, 0.408 per cent, from old cubebs. It is stated

to be of ointment-like consistence, melting at 30 to 32 °C. Hot

alcohol, ether, carbon disulphide, chloroform, benzene and

petroleum ether dissolve it readily. It is reported to be insoluble

in cold alcohol.

Cubebin.16 Cubebin crystallizes from alcohol in white, odor¬

less needles melting at 125 to 126°C (Schmidt),17 132°C

(Mameli).18 The alcoholic solution has a bitter taste. It is

only slightly soluble in cold alcohol, quite soluble in hot alcohol,

readily soluble in ether, chloroform, carbon disulphide, glacial

acetic acid, fatty and volatile oils. The chloroformic solution

is laevogyrate. Concentrated sulphuric acid dissolves it with a

purple violet color, a reaction which is used as test for the

identity of the cubeb fruit and the oleoresin prepared therefrom.

Cubebin was thought by Heldt19 to be an oxidation product

of the sesquiterpene constituent of the volatile oil, 2 C15H24 -f- 18

O = C30HS0O9 + 9 H20. Later work on the determination of

its structure, however, has shown this theory to be untenable.

The following structural formulas have been brought forward to

represent its composition.

HC

CCH=CH CH.OH

/\,

CH

C

cv«.

Jr

Formula of Pomeranz

(20)

19 Ibid.

18 Monheim, Buchner’s Repert. f, d. Pharm. (1833), 44, p. 199; Cassola,

Journ. d. Chim. Med. (1834), 10, p. 685; Soubeiran and Capitaine, Journ.

de Pharm. et de Chim. (1839), 25, p. 355; Ann. d. Chem. (1840), 34, p. 323;

Steer, Buchner’s Repert. f. d. Pharm. (1838), 11, p. 88; Ibid. (1840), 20, p.

119; Schuck, Buchner’s n. Repert. f. d. Pharm. (1852), 1, p. 213; Engel-

hardt, Ibid. (1854), 3, p. 1; Bernatzik, Ibid. (1865), 14, p. 97; Schmidt,

Arch. d. Pharm. (1870), 191, p. 1; Weidel, Wien. Akad. Ber. (1878), 74,

p. 377.

1T l. c.

18 Chem. Ztg. (1908), 32, p. 46.

19 Arch, der Pharm. (1870), 191, p. 23.

20 Monatsch. f. Chem. (1888), 9, p. 323.

1052 Wisconsin Academy of Sciences , Arts, and Letters .

CH

C-fC«H,(OH)2]-C

HC

0

'c— u

CH

(21)

Formula ef Mamdi

Cubebin occurs in the fruit to the extent of about 2.5 per

cent.22

Cubebic Acid. (Acid Resin) Cubebic acid, C13H14071

(Schmidt),23 C28H30O7H2O (Schulze),24 was first described by

Bernatzik. It is a white, resinous mass melting at 56 °C

(Schmidt), 45 °C (Schulze) and becoming brown on exposure

to the air. It shows only a weak acid reaction. Alcohol, ether,

ammonia and the caustic alkalies dissolve it readily.

There is a considerable variation in the cubebic acid content

of the fruit as reported in the literature. Schmidt25 obtained

0.96 per cent, from fresh cubebs and 1.16 per cent, from the

fruit which had been stored. Bernatzik reports the presence

of 3.458 per cent.26

Resin. The so-called indifferent resin, C13H1405 (Schmidt)27

is a yellowish-brown, pulverulent mass readily soluble in alcohol

and the caustic alkalies, but only slightly soluble in ether, chloro¬

form and carbon disulphide.

The indifferent resin occurs in the fruit to the extent of about

3 per cent, on the average.28

Coloring Matter. Schmidt29 isolated a brown amorphous sub¬

stance to which he attributes the brown color. This substance

is stated to be soluble in dilute alcohol and solutions of the alka-

» z. c.

23 Monheim obtained 4.5 per cent, of a resin resembling piperine which he

designated cubebin. Buchner’s Repert. f. d. Pharm. (1833), 44. p. 199,

Schmidt reports the presence of 2.484 per cent, in fresh cubebs and 2.576

per cent, in cubebs kept in storage for some time. 1. c.

28 Z. c.

24 Arch. d. Pharm. (1873), 202. p. 388.

25 Z. c.

26 Buchner’s n. Repert. f. d. Pharm. (1865), 14, p. 97.

27 Z. .c

28 Schmidt observed the presence of 2.258 per cent .of indifferent resin in

the fresh fruits, 2.968 per cent, in stored fruits, Z. c.

Bernatzik obtained 3.515 per cent, of this resin, Z. c.

» 7. c.

Du Mez — The Galenical Oleoresins.

1053

lies. The green color of the fatty oil as observed by the same

investigator is stated to be due to chlorophyll.

Ash. According to E. Schmidt,30 the ash of the cubeb fruit is

composed of the basic elements, K, Ca, Mg, and Fe in combina¬

tion with the acid radicles Cl', S04", PO/", C03" and Si03",

also free Si02.

Cubeb fruits yield about 5.5 to 6.0 per cent, of ash.31

Constituents of Therapeutic Importance.

The value of the oleoresin of cubeb as a therapeutic agent is

very probably due to its resin content. In addition to its

diuretic action, the acid resin is said to render the urine feebly

antiseptic and to act as an astringent.* 1 Cubebin has been shown

to be physiologically inactive passing through the intestines

unabsorbed.2 The volatile oil is stated to act merely as a car¬

minative3 and its presence is even considered by some to be un¬

desirable4 owing to its irritating action.

Physical Properties

Ash. According to E. Schmidt,30 the ash of the cubeb fruit is

directed by the United States Pharmacopoeia has a grass- green

color when spread out in a thin layer on a white porcelain sur¬

face. The commercial product, however, is often brownish-green

or brown in color due to the use of the ripe fruit5 in its manu¬

facture. In such cases, the desired green color is sometimes im¬

parted to the preparation by the addition of copper salts.6

Odor : The oleoresin has a strong aromatic odor like that of

the crushed cubeb fruit. In fact, the odor is so strongly aro¬

matic that unevaporated solvent (alcohol), even when present

in considerable amounts, cannot be detected by the sense of

smell.

30 Arch. d. Pharm. (1870). 191, p. 11.

31 Schmidt obtained only 3.36 per cent of ash, l. c.

Warnecke reports the yield of ash as 5.45 per cent. Pharm. Ztg. (1886),

31, p. 536.

La Wall and Bradshaw give the ash content of two samples of cubeb as

5.70 and 6.10 per cent., respectively. Proc. A. Ph. A. (1910), 58, p. 751.

1 Vieth, Med. Klin. (1905), p. 1276.

2 Heffter, Arch. f. Exp. Path. u. Pharm. (1895), 35, p. 371.

3 Heydenreich, Am. Journ. Pharm. (1868), 40, p. 42.

4 Bernatzik, Buchner’s neues Repert. (1865), 14, p. 97.

“ See under “Drug used, its collection, preservation, etc.”

* Bedall (1894).

1054 Wisconsin Academy of Sciences, Arts, and Letters.

Taste: The taste is bitter and somewhat spicy, like that of

cnbeb, only more pronounced.

Consistence: The oleoresin is, as a rule, a rather thin liquid

when compared with the other members of this class of prepara¬

tions. Its consistence, however, varies to a considerable extent

owing to a difference in the volatile oil content.1 Some of the

preparations examined in the laboratory were so thick that they

could only be poured with difficulty.

Solubility: The official preparation forms clear or slightly

cloudy solutions with alcohol, acetone, ether, chloroform, carbon

disulphide, and glacial acetic acid. It is almost completely

soluble in petroleum ether. The solubility of the European

product, which is usually prepared with a mixture consisting

of equal parts of alcohol and ether, is about the same.

Specific gravity: The oleoresins prepared in the laboratory

in 1916 showed a specific gravity of 0.99 + at 25° C regardless of

whether the solvent employed in extracting the drug was alcohol,

acetone or ether. The uniformity is attributed to the fact that

particular pains were taken to evaporate the solvent under the

same conditions in each case, thereby insuring approximately

the same volatile oil content for each of the finished prep¬

arations. The variation in specific gravity due to a difference

in volatile oil content is shown in the data given for the first

four of the laboratory preparations. The commercial samples

examined also show a variation due to this influence, except, in

the case of the low specific gravity observed by Procter, which

was stated to be due to the presence of unevaporated solvent

(ether). Tables illustrating these points follow:

Table 49 — Specific gravities of laboratory preparations.

1 A thick preparation containing only 4.71 per cent, of volatile matter.

1 See under “Chemistry of the drug and the oleoresin”.

Du Mez — The Galenical Oleoresins.

1055

Table 50 — Specific gravities of commercial oleoresins.

1 Contained ether.

Refractive index: The results obtained in the laboratory in¬

dicate that the refractive index of the oleoresin should be about

1.499 when determined at 25° C. The solvent employed in ex¬

tracting the drug appears to have little influence on this con¬

stant, except in case petroleum ether is used, when it is slightly

lower. The effect due to variation in volatile oil content is but

slight as is shown in the tables which follow:

Table 51. — Refractive indices of oleoresins prepared in the laboratory.

O) Low in volatile oil content.

Table 52 — Refractive indices of commercial oleoresins.

1056 Wisconsin Academy of Sciences , Arts s and Letters .

. ■ ; ; ■ ' gff|

Chemical Properties.

Loss in weight on heating: An examination of the tables

which follow shows that the oleoresin usually loses between

20 and 40 per cent, on heating at 100 to 110°C, the variation

being due to the difference in the volatile oil content. The

relatively small loss in weight observed in the case of four of

the laboratory preparations is to be attributed to the removal

of a part, or the whole, of the more volatile constituents of the

essential oil in the process of evaporating the solvent. The com¬

paratively great loss noted for two of the commercial samples is

thought to have been due to the presence of unevaporated

solvent. The results obtained in the determinations made in

the laboratory as well as those reported in the literature are

given in the tables which follow :

Table 53. — Laboratory preparations — loss in weight on heating.

Table 54 — Commercial oleoresins—loss in weight on heating .

‘Probably contained unevaporated solvent (alcohol).

UlitkMNM!

Du Mez — The Galenical Oleoresins.

1057

Ash content: The ash content of the oleoresin varies with

the solvent employed in its preparation as is shown in the first

of the tables which follow. The highest values were obtained

for the official product, in the preparation of which alcohol

was the solvent used. The camparatively low ash content ob¬

tained for the commercial samples examined, while suggesting

the use of some other solvent in the manufacture of these

preparations, is thought to have been due to the greater amount

of volatile matter (essential oil) present. Although copper

was detected in the ash of all of the commercial products, the

quantities present were too small to effect the value of this

constant to any considerable extent. The following tables

give the ash content of the oleoresin as reported in the litera¬

ture and as determined in the laboratory:

Table 55. — Ash contents of oleoresins prepared in the laboratory.

Table 56 — Ash contents of commercial oleoresins.

Sample

No.

1

Foreign con¬

stituents

Copper

1 Unevaporated solvent (alcohol) probably present.

Acid number: The acid numbers of the oleoresins prepared

in the laboratory varied from 21.8 to 26.7, depending on the

nature of the solvent employed in their preparation. The num-

67— S. A. L.

1058 Wisconsin Academy of Sciences , Arts, and Letters.

her, 26.7, obtained in the ease of the preparation made with

alcohol agrees very well with that (26.2) obtained by Kremel

for the oleoresin when prepared in a like manner. The low acid

numbers obtained for the commercial samples are explained

by the presence of relatively large amounts of volatile matter

(generally essential oil, but unevaporated solvent in two cases)

in these preparations, which has the effect of reducing the con¬

centration of the free acids. The values obtained for this

constant follow:

Table 57.— Acid numbers of laboratory preparations .

Table 58 . . — Acid numbers of commercial oleorcsins.

0) Probably contained unevaporated solvent (alcohol).

Saponification value; The saponification values obtained for

the oleoresins prepared in the laboratory showed a slight

variation due to the nature of the solvent used in extracting

the drug as is shown in the first of the tables which follow. As

a rule, however, the difference in the volatile oil content of the

oleoresin, due to a variation in the conditions under which it

has been prepared, is thought to be the principal factor in¬

fluencing the value of this constant, as is also brought out in the

first table. In the examination of commercial samples, the

presence of unevaporated solvent must be taken into considera-

Du Mez — TJie Galenical Oleoresins.

1059

tion in this connection. The results obtained in the determina¬

tion of this constant in the laboratory follow:

Table 59 — Saponification values of oleoresins prepared in the laboratory.

1 This preparation contained a relatively small amount of volatile matter (principally

essential oil). See page 1056 under “Loss in Weight on Drying”.

Table 60 _ Saponification values of commercial oleoresins.

0) Unevaporated solvent (alcohol) probably present.

Iodine value: Further observations are necessary before a

definite statement can be made as to what the iodine value of

this preparation should be. Determinations made in the labora¬

tory appear to indicate that it is influenced largely by the

volatile oil content as those preparations which lost the greatest

amount on drying usually gave the highest values for this con¬

stant. Apparent exceptions to this rule are to be found in

the samples obtained from Lilly & Company and Squibb &

Sons, respectively. In these cases, unevaporated solvent

(alcohol) is thought to have been present, although, it could

not be detected by the odor. The following tables show the

values obtained for the preparations examined in the laboratory.

1060 Wisconsin Academy of Sciences , Arts , and Letters.

Table 61 — Iodine values of oleoresins prepared in the laboratory.

Table 62 — Iodine values of commercial oleoresins.

1 Unevaporated solvent probably present.

Other Properties.

The oleoresin, upon long standing, forms a white deposit

consisting of cubebin, indifferent resin, cubebic acid and thick¬

ened oil. As the greater part (80 per cent. ) 1 of this precipitated

material consists of the therapeutically inert cubebin,2 the

United States Pharmacopoeia- directs that it be removed before

dispensing the preparation.

Special Qualitative Tests.

The methods which have been devised for the indentification

of this oleoresin or as a test for its quality are based on the

fact that characteristic color changes are produced when it is

acted upon by certain acids. Sulphuric, sulphomolybdic3 and

1 Schmidt (1870).

3 See under "Constituents of therapeutic importance".

* Dieterich, in 1897, pointed out that sulphomolybdic acid might be used

in place of sulphuric acid. The resulting color, however, was stated to be

a cherry-red instead of a blood-red.

Du Mez—The Galenical Oleoresins.

1061

hydrochloric1 acids have been made use of in this connection,

the first mentioned being the reagent most generally employed.

Attention was first called to the value of sulphuric acid in

the identification of this preparation by Kremel in 1887. He,

however, reported nothing definite, merely stating that a car¬

mine-red color was produced when the “strong” acid and

oleoresin were mixed. It was not until ten years later ( 1897 ) ,

when the firm of Dieterich in Helfenberg published their method

of procedure, that this test assumed a definite form. The test

as carried out by this firm is typical of those in use at the

present time and is as follows:

Upon mixing 0.01 gram of the oleoresin with 3 to 5 drops of concen¬

trated sulphuric acid, the mixture should assume an intense blood-red color.2

The fact that certain constituents of the cubeb fruit, namely,

cubebin, the acid resin (cubebic acid) and the indifferent resin,

formed red colored mixtures with sulphuric acid was noted by

Schmidt in 1870. These observations have been confirmed in

this laboratory in so far as they pertain to the production of a

red color. It was further noted, however, that the shade of

red varies with the particular constituent under consideration,

the cubebin giving rise to a mixture which is brownish-red in

color, whereas, the color is bright red (carmine-red) in the case

of the acid or indifferent resin. As all of the above mentioned

constituents are normally present in the oleoresin, the particular

shade of red (blood-red) obtained in this test must be due to

the blending of the colors produced by the action of the acid

on the several constituents, and cannot be caused by the action

of the acid on the cubebin, alone, as is usually reported in the

literature.

As the shade of red obtained will naturally vary with the

relative quantities of the several constituents present, this test

not only serves as a means of identification, but is also of value

in determining roughly the quality of the preparation as well.3

Thus, a bright red color obtained by the action of the acid may

1 Test of Gluecksmann. See the following pages.

2 The so-called false cubebs give a dirty brown color when triturated with

concentrated sulphuric acid, hence, we may expect the oleoresin prepared

therefrom to form a mixture of a similar color. See Pharm Ztg. (1912),

84, p. 845.

3 Bedall (1894) observed that the oleoresins possessing a green color gave

a more intense red -with sulphuric acid that those which were brown in color.

1062 Wisconsin Academy of Sciences , Arts , and Letters.

be taken as an indication of the presence of relatively large

amounts of the therapeutically active resins, while a dark shade

of red implies that the cubebin content is exceptionally large

or that the resins are present in comparatively small amounts.

The test of Gluecksmann (1912) in which hydrochloric acid

is the reagent made use of, appears to be based on the presence

of cubebin,1 It is carried out as follows:

Dissolve a small quantity (a trace) of the oleoresin in concentrated

acetic acid and dilute with the latter until the solution shows scarcely any

color. Heat to boiling and add 5 drops of a 35 per cent, solution of

hydrochloric acid to a 5 cubic centimeter portion. A faint yellowish-brown

color should appear immediately. Upon standing quietly, the color should

change in 2 to 4 hours to a brownish-violet, and then to a violet blue,

after which it should gradually disappear.

While the foregoing may prove to be a test of considerable

worth in the identification of the oleoresin, the length of time

required for its completion would appear to be a drawback to

its general application.

The tests of this nature prescribed by the various phar¬

macopoeias all involve the use of sulphuric acid. As will be¬

come apparent in the following description of these methods,

the color specified differs to a considerable extent. This may

be due, as already pointed out, to a variation in the relative

quantities of the reacting constituents, or, as has been further

observed in the laboratory, to the strength of the acid employed.

A very slight dilution with water will cause the color to change

from red to purple. The following are the tests prescribed

by the different pharmacopoeias:

Austrian Pharmacopoeia (1906): The oleoresin should give a red color

on being triturated with concentrated sulphuric acid.

French Pharmacopoeia (1908): The oleoresin should give a purple-red

color with concentrated sulphuric acid.

Swiss Pharmacopoeia (1907): If 0.01 to 0.02 grams of the oleoresin

are mixed with a few drops of concentrated sulphuric acid, an intense

brownish -red color should be produced. Upon diluting with a little water,

the color should change to a rose and upon further dilution, it should

disappear.

Hungarian Pharmacopoeia (1909): A drop of concentrated sulphuric

1 This assumption is made in view of the fact that the closely related

compounds, coniferyl alcohol and syringenin, give similar color reactions

with hydrochloric acid. See Euler, Die Ppmzenehemie (1908), Vol. I, p. 87.

Du Mez — The Galenical Oleoresins.

1063

acid added to a drop of the oleoresin spread out in a thin layer on a white

porcelain surface should produce a blood-red mixture.

German Pharmacopoeia (1910): If 1 cubic centimeter of & mixture of

4 parts of concentrated sulphuric acid and 1 part of water is poured over

1 drop of the oleoresin, a red color should be produced. Upon diluting

the mixture with water the color should disappear.

Special Quantitative Tests.

Apparently but one attempt has been made to develope a

method for the quantitative determination of the constituents

of therapeutic importance in this preparation, the same having

been made by Kremel in 1887. As no work of this nature was

done on the oleoresin in the laboratory, and, as there is no

further information on this subject in the literature, a state¬

ment cannot be made as to the value of this method. However,

as a suggestion of what might be accomplished in this direction,

a description of the method is included here. It is as follows :

KremeVs Method for the Estimation of Cubebic Acid (1887): Dissolve

3 to 5 grams of the oleoresin in 4 times the quantity of alcohol (90 per

cent.), filter the solution and add alternately to the filtrate an alcoholic

solution of calcium chloride and ammonia water until a distinct cloudi¬

ness appears. Set the liquid aside for a day or two to allow the cal¬

cium salt of cubebic acid to crystallize. Then, collect the precipitate

on a filter, wash successively with alcohol (90 per cent.) and ether, dry

at 100°C and weigh. Compute the weight of the cubebic acid using the

formula, C H O Ca, for the calcium salt.

7 13 12 7 1

According to the results obtained by Kremel, the oleoresin

prepared with ether shsowed a cubebic acid content of 2.35 per

cent., while the same when prepared with alcohol gave 5.75 per

cent, of cubebic acid.

Adulterations.

Willful adulteration of this preparation does not appear to

be practiced very extensively, although, the occassional use of

fixed oils1 or salts of copper2 3 for this purpose has been reported

1 Schneider and Suess, Handkommentar zum Arzneibuch fuer das deutsche

Reich (1902), p. 376.

3 B6dall (1894).

A trace of copper is usually present in the commercial preparations as a

result of the use of copper utensils in their manufacture. (See under

“Ash”.)

1064 Wisconsin Academy of Sciences , Arts , and Letters.

in the literature. On the other hand, accidental adulteration

effected through the use of ripe instead of unripe fruits in the

preparation of the oleoresin is thought to be quite general.

(See under “Drug used, its collection, preservation, etc.”)

OLEORESIN OF GINGER

Synonyms

Aetherisches Ingwerextrakt, Nat. Stand. Disp. 1884.

Ethereal Extract of Ginger, King’s Am. Disp., (1900), p. 1336.

Extraction Zingiberis aethereum, Hirsh, Univ. P. 1902, No. 1320.

Extractum Zingiberis aethereum, King’s Am. Disp. (1900), P. 1336.

Gingerin, Chem. and Drugg. (1913), 82, p. 470.

Gingerine, Am. Journ. Pharm. (1898), 70 p. 466.

Oleoresma Zingiberis, U. S. P. 1910.

Oleoresine de Gingembre, U. S. Disp. 1907.

Piperoide du Gingembre, Beral, 1834.

Piperoid of Ginger, U. S. Disp. 1865.

Zingiberin, II. S. Disp. 1907.

History

The oleoresin of ginger was prepared in 1834 by Beral, a

Frenchman, but was apparently first brought to the notice of

American pharmacists by Proctor in 1849. It was intro¬

duced into the United States Pharmacopoeia in 1860 and is still

official at the present time. While the oleoresin has never

been officially recognized abroad, a similar preparation is said

to be used extensively in England under the name of gingerin.1

Drug Used , Its Collection , Preservation , Etc.

For this drug, the present pharmaeopceial definition is as

follows: “The dried rhizomes of Zingiber officinale Roscoe

(Fam. Zingiberaceae,) the outer cortical layers of which are

often either partially or completely removed. Preserve it in

tightly-closed containers, adding a few drops of chloroform or

carbon tetrachloride, from time to time, to prevent attacks by

insects.” The official drug has also been described in the

literature under the following botanical synonyms: Amomum

Zingiber Linne, and Zingiber Zingiber (Linne) Rusby.

1 Gingerin is stated to be the extract obtained upon evaporating off the

alcohol from the tincture of ginger. Chem. & Drugg. (1913), 82, p. 470.

Du Mez — The Galenical Oleoresins.

1065

The rhizomes as they are found on the market occur in a

variety of forms characteristic of the source from which they

are obtained. In view of this fact, the Pharmacopoeia recog¬

nizes six different commercial varieties, namely : J amaica ginger,

African ginger, Calcutta ginger, Calicut ginger, Cochin

ginger and Japanese ginger. These commercial forms differ

to a considerable extent, not only through natural causes, but

also through a difference in the conditions under which they are

harvested and prepared for the market.

As a rule the rhizomes are dug after the stems have withered,

January or February, when one or more years old. Experience

has shown the oleoresin content to be the greatest at this period

of the year.1 They are then washed in boiling water to pre¬

vent germination, dried rapidly in the sun, and as such con¬

stitute, what is known as black, coated, or unscraped ginger.

In other cases, after treatment with boiling water, a part or

the whole of the epidermis is removed, the rhizomes dried, and

bleached with sulphur fumes, chlorinated lime, milk of lime or

gypsum. This constitutes the so-called, white, uncoated,

scraped, race or hard ginger.2

In commenting on the relative values of these various forms

of ginger in the preparation of the oleoresin, it should be stated,

first of all, that the yield of oleoresin is influenced to the largest

extent by habitat, African ginger giving the maximum yield.3

Secondly, the extent to which the rhizomes have been decorticated

is an important factor, as the outer corky layer contains none

of the oleoresinous material. These factors will be more fully

discussed under yield. To what degree, if at all, the process

of so-called bleaching effects the yield or quality of oleoresin

does not become apparent from the literature. It is thought,

however, that a heavy coating of gypsum, for instance, would

tend to considerably reduce the percentage of oleoresin ob¬

tainable.

1 Hooper, Fharm. Journ. (1912), 89, p. 391.

2 Culbreth, Mat. Med. and Pharmacol. (1917), p. 130.

3 See reference under “Yield of oleoresin”.

1066 Wisconsin Academy of Sciences , Arts , and Letters .

TJ. S. P. Text and Comments Thereon.

The oleoresin of ginger first became official in the Pharmaco¬

poeia of 1860. It has remained official throughout all of the

subsequent editions.

1860

Oleoresina Zingiberis

Oleoresin of Ginger

Take of ginger,1 in fine powder,2 alcohol until twelve fluidounces7 of

twelve troyounees; filtered liquid have passed. Eecover

Stronger Ether 3 twelve fluidounces ; from this, by distillation on a water-

Alcohol 4 a sufficient quantity. bath, nine fluidounces of ether,8 and

Put the ginger into a cylindrical expose the residue, in a capsule, until

percolator,6 press it firmly, and pour the volatile part has evaporated.®

upon it the stronger ether.* When this Lastly keep the oleoresin in a well-

has been absorbed by the powder, add stopped bottle.10

1870

Oleoresina Zingiberis

Oleoresin

Take of ginger,1 in fine powder,2

twelve troyounees;

Stronger Ether3 twelve fluidounces;

Alcohol * a sufficient quantity.

Put the ginger into a cylindrical

per6olator, provided with a stop-cock,

and arranged with a cover and recep¬

tacle suitable for volatile liquids,6 press

it firmly, and pour upon it the

of Ginger

stronger ether.* When this has been

absorbed by the powder, add alcohol

until twelve fluidounces of liquid have

slowly passed.7 Eecover from this the

greater part of the ether by distilla¬

tion on a water-bath,8 and expose the

residue, in a capsule, until the volatile

part has evaporated.® Lastly, keep

the oleoresin in a well-stopped bottle.1*

1880

Oleoresina Zingiberis

Oleoresin

Ginger,1 in No. 60 powder,2 one hun¬

dred (100) parts . ...100

Stronger Ether,3 a sufficient quantity „

Put the ginger into a cylindrical

percolator, provided with a cover and

receptacle suitable for volatile liquids,6

press it firmly, and gradually pour

stronger ether upon it, until one hun¬

dred and fifty (150) parts of the

of Ginger

liquid have slowly passed, or until the

Ginger is exhausted.7 Eecover the

greater part of the ether by distilla¬

tion on a water-bath,8 and expose the

residue, in a capsule, until the remain¬

ing ether has evaporated.®

Keep the oleoresin in a well-stopped

bottle.10

Du Mez — The Galenical Oleoresins.

1067

1890

Oleoresina

Oleoresin

Ginger,1 in No. 60 powder,2 five hun¬

dred grammes . 500 6m.

Ether,3 a sufficient quantity.

Put the ginger into a cylindrical

glass percolator, provided with a stop¬

cock, and arranged with cover and

receptacle suitable for volatile liquids.3

Press the drug firmly, and percolate

slowly with ether, added in successive

Zingiberis

of Ginger

portions, until the drug is exhausted.1

Eecover the greater part of the ether

from the percolate by distillation on

a water-bath,8 and, having transferred

the residue to a capsule, allow the re¬

maining ether to evaporate spontan¬

eously.®

Keep the oleoresin in a well-stop¬

pered bottle.10

1900

Oleoresina

Oleoresin

Ginger,1 in No. 60 powder,2 five hun¬

dred grammes . 500 Gm.

Acetone,2 a sufficient quantity.

Introduce the ginger into a cylindri¬

cal glass percolator, provided with a

stop-cock, and arranged with a cover

and a receptacle suitable for volatile

liquids.5 Pack the powder firmly, and

percolate slowly with acetone, added

in successive portions, until the ginger

Zingiberis

of Ginger

is exhausted.7 Recover the greater

part of the acetone from the percolate

by distillation on a water-bath,8 and,

having transferred the residue to a

dish, allow the remaining acetone to

evaporate spontaneously in a warm

place.® Keep the oleoresin in a well-

stoppered bottle.10

Average dose.— -0.030 Gm. = 30

milligrammes (% grain.)

1910

Oleoresina

Oleoresin

Oleores.

Ginger,1 in No. 60 powder,2 five hun¬

dred grammes . 500 Gm.

Ether,3 a sufficient quantity.

Place the ginger in a cylindrical

glass percolator, provided with a stop¬

cock and arranged with cover and a

receptacle suitable for volatile liquids.6

Pack the powder firmly, and perco¬

late slowly with ether, added in suc¬

cessive portions, until the drug is ex-

Zingiberis

of Ginger

Zingib.

hausted.7 Recover the greater part

of the ether from the percolate by

distillation, on a water-bath,8 and,

having transferred the residue to a

dish, allow the remaining ether to

evaporate spontaneously in a warm

place.® Keep the oleoresin in a well-

stopped bottle.10

Average dose. — Metric, 0.03 Gm. — ■

Apothecaries, % grain.

1068 Wisconsin Academy of Sciences, Arts, and Letters.

1) For a description of the different commercial varieties of

the official drug, see page 1065 under “Drug used, its collection,

preservation, etc.”

2) As starch, in the shape of fine granules, constitutes about

20 per cent, of the ginger rhizome, the latter can only be ob¬

tained in the form of a uniformly fine powder by reducing

the other tissues to a corresponding degree of fineness. It is for

this reason and for' the purpose of insuring the complete

breaking up of all of the small resin cells that the Pharma¬

copoeia directs that the drug be reduced to a No. 60 powder.

3-4) Ether is the solvent which appears to be best adapted to

the preparation of this oleoresin in that it completely extracts

the pungent principles from the drug and yields a product

containing a minimum amount of undesirable extractive mat¬

ter. According to Garnett and Grier (1909) acetone, which

was directed to be used by the Pharmacopoeia of 1900, does

not completely exhaust ginger, even when a Soxlet’s appara¬

tus is used. It is, therefore, fortunate that the present Phar¬

macopoeia again specifies that ether be used for this purpose.

In the earlier editions of the Pharmacopoeia (editions of

1860 and 1870), alcohol was directed to be used as a “follow

up” solvent to replace the ether with which percolation was

begun. This procedure was abandoned in 1880 for reasons

which will be discussed later.

5) Since 1870, the Pharmacopoeia has directed that percola¬

tion be carried out in a special form of percolater adapted to

the use of volatile liquids. For a description of such forms,

see Part I under “Apparatus used.”

6-7) The method of extracting the drug as outlined in the

earlier editions of the Pharmacopoeia, the editions of 1860 and

1870, was essentially the same as suggested by Beral in 1834.

See Part I, page 929. From a practical standpoint, this method

possessed distinct advantages, especially at the time when it

was adopted, in that a considerable saving in the cost of the

preparation of the oleoresin was effected through the use of

alcohol as a “follow up” solvent for replacing the relatively

expensive ether. The method, however, was not entirely sat¬

isfactory as the finished product contained a considerable

amount of undesirable extractive matter owing to the greater

solvent properties of the alcohol. Another disadvantage lay

Du Mez — The Galenical Oleoresins.

1069

in the fact that a relatively large amount of volatile oil was

lost in the removal of the solvent.

The present edition of the Pharmacopoeia directs that the

drug be completely exhausted by simple percolation with

ether. Here, as in the case of the oleoresin of capsicum, the

extraction of the drug with the aid of some form of continu¬

ous extraction apparatus would effect a considerable saving

in solvent and without injury to the finished product.

8-9) With respect to the removal of the solvent from the per¬

colate, the present edition of the Pharmacopoeia directs that

this be accomplished in greater part by distillation on a water

bath and that the remainder be allowed to evaporate spon¬

taneously in a warm place, a procedure similar to that de¬

scribed in the earlier editions. For reasons, identical with

those given in the comments on the oleoresin of cubeb (see

page 1045), it is thought that the pharmacopoeial directions

should include specific statements with reference to the

amount of solvent to be recovered by distillation and the tem¬

perature at which the remainder is to be removed in order to

insure greater uniformity in the product obtained.

10) Upon exposure to the air, a portion of the volatile oil con¬

tained in the oleoresin is altered (resinified) or lost through

evaporation. The preparation should, therefore, be kept in

well-stoppered bottles.

Yield

With respect to the solvents, alcohol (95 per cent.), acetone

and ether, the yield of oleoresin, in the case of ginger, varies in

magnitude in the order in which the solvents are mentioned.

For these menstrua, a minimum yield of 2.57 per cent has been

reported while the maximum yield has been stated to be as high

as 11.1 per cent. When petroleum ether is the solvent used,

the yield is much lower, being only about one-half that obtained

in the preceding eases. In this connection, the source of the

rhizomes is a factor of first importance. Thus, it has been

found that Jamaica ginger usually gives the smallest yield and

African ginger the highest, while Cochin ginger occupies an

intermediate position in this respect. These facts will be

brought out more clearly in the tables which follow.

1070 Wisconsin Academy of Sciences, Arts , and Letters.

The yield of oleoresin is further influenced by the degree to

which the rhizomes have been deprived of the outer corky layer,

and, in the case of bleaching, to the manner in which the latter

was accomplished. With respect to this statement, the yield,

in the case of the unbleached ginger, will be the greatest when

decortication is complete. When the rhizomes have been

bleached, in addition to being partially or wholly decorticated,

the influence of the latter, may be diminished, in part at least,

by the process employed in accomplishing the former. Thus, if

gypsum or lime have been used for this purpose, the weight of

the insoluble material in the rhizomes will be considerably in¬

creased, which will have the effect of reducing the percentage

yield of oleoresin. These points are also brought out in the

tables which follow.

Du Mez — The Galenical Oleoresins,

1071

Date

1S34

1879

1886

1888

1891

1892

1893

1895

1896

1197

1901

1903

Table 63. — Yield of oleoresin as reported in the literature.

Observer

B6ral...

Thresh .

Jones .

Siggnis.

Trimble.

Riegel. . .

Sherrard ,

Beringer .

Dyer and Gilbard

Davis.

Lirerseege .

Glass and Thresh

Rennet.

Ballard

Southall Bros.

& Barclay..

Yield of oleoresin to—

Alco¬

hol

Per ct.

Alco¬

hol

( sp

gr

0.82)

5.00

4.80

6.65

6 57

6.17

l 7.00

5.00

8.00

Alco

hoi

(90

per

cent.)

3.94to

5.61

3. 41 to

5.67

4. 91 to

6.74

5.41to

6.51

5.14to

6.61

5.14to

16.47

Alco¬

hol

(90

per

cent)

4.35

4.57

l 9.93

Ace¬

tone

Per ct

5.57

Ether

Per ct.

5.20

3.29

4.96

8.06

3.58

3.97

8.00

3.85

4.72

5.20

5.40

3.00 to

5.20

4.80 to

4.84

5.75 to

6.27

5.50

5.00

4.33

6.33

2.57 to

6.41

2.97 to

4.60

3.75

6.33

Eth’r

( Sp.

g r.

0.717)

4.76

6.04

111.09

Other

solvents

Per cent.

Benzin

2.48

Benzin

2.50

Methyl

alcohol

6.50

Remarks

Jamaica ginger.

Cochin

African

Jamaica ginger, unbleached.

“ , bleached

(limed)

East Indian ginger.

African ginger.

Jamaica ginger, unbleached.

East Indian ginger, epidermis

removed.

Upon subsequent extraction

with alcohol 0.80 to 1.50 per

cent, of material was ob¬

tained.

Jamaica ginger.

African

Jamaica ginger.

Cochin

African

Jamaica ginger, whole.

Jamaica ginger, ground.

Cochin ginger, whole.

Cochin ginger, ground.

African ginger, whole.

African ginger, ground.

Tahiti ginger.

Ivory Coast ginger.

Jamaica ginger.

Cochin

African “

Date

1908

1909

1910

1911

1912

1913

1914

1915

1072 Wisconsin Academy of Sciences, Arts , and Letters .

Table 63. — Yield of oleoresin as reported in the literature — Continued.

Yield of oleoresin to—

Remarks

Reported as yield of oleoresin .

Represents the yield from 16

samples of Jamaica ginger.

Reported as oleoresin.

African ginger.

j Jamaica ginger. Reported as

I yield of oleoresin.

African ginger. Reported as

yield of oleoresin.

Jamaica ginger. Reported as

yield of oleoresin.

African ginger, Reported as

yield of oleoresin.

Jamaica ginger. Reported as

yield of oleoresin.

African ginger. Reported as

yield of oleoresin.

Jamaica ginger.

Young rhizomes harvested in

December.

Rhizomes harvested in Feb¬

ruary.

Average yield of 9 samples of

ginger.

Reported as yield of oleoresin .

Results obtained in extract¬

ing 37 samples of Jamaica

ginger.

Results obtained in extracting

17 samples of African ginger.

Results obtained in extracting

8 samples of Jamaica ginger.

Jamaica ginger.

African ginger.

Average yield of 3 samples of

Jamaica ginger.

Average yield of 3 samples of

African ginger.

Yield of Jamaica ginger.

“ “ African ginger.

Du Mez — The Galenical Oleoresins.

1073

Table 64. — Yield of oleoresin as obtained in the laboratory.

1 Jamaica ginger was the variety of the drug used in all cases. When

alcohol was the solvent employed, the process of extraction was that of

simple percolation.

Chemistry of the Drug and Oleoresin.

Tabulation of Constituents.

The chemistry of the constituents of ginger is still incomplete

in many details, although, it has been the subject of a number of

investigations.1 In the light of our present knowledge, the fol¬

lowing may be said to comprise the constituents of importance

to the pharmacist: volatile oil, gingerol, resins, fat, wax, gum,

sugar, starch and inorganic matter. Thresh2 has identified the

following in the oleoresin prepared by extracting the rhizomes

with ether:

Volatile Oil Eesin Wax

Gingerol Fat Ash

Occurrence and Description of Individual Constituents.

Volatile Oil.3 The volatile oil or so-called essence of ginger

is described by Thresh4 as being a pale straw colored liippid

1 Morin, Journ. de Pharm. et de Chim. (1823), 9, p. 256; Thresh, Fharm.

Journ. (1879), 39, p. 171; Jones, Chem. & Drugg. (1886), 28, p. 413; Gane,

Pharm. Journ. (1892), 51, p. 802; Balland. Journ. Pharm. Chim. (1903), 18,

p. 248 ; Reich, Zeitschr. Unters. Nahr. u. Genussm. (1907). 14, p. 549.

»l. c.

3 The description of the volatile oil as given above is for the product ob¬

tained from the rhizomes by steam distillation. The oil as it exists in the

oleoresin prepared from the rhizomes by extraction with a solvent will un¬

doubtedly differ somewhat.

4 Pharm. Journ. (1881), 41, p. 198; Year-Book of Fharm. (1881), 18, p. 393.

1074 Wisconsin Academy of Sciences, Arts, and Letters.

fluid with a somewhat camphoraceous odor and an aromatic, but

not a pungent taste. It is laevogyrate (-25 to 50°) and has a

specific gravity of 0.875 to 0.886. It is soluble in strong alcohol,

petroleum ether, carbon disulphide, benzene, turpentine and

glacial acetic acid. The principal constituent of the oil, a

sesquiterpene, gingerene or zingiberene, (C15H24) was first

definitely described by von Soden and Rojahn5 in 1900. Accord¬

ing to Semmler and Becker,6 it is a monocyclic butadiene having

the following structure :

The former investigators also identified d-camphene and phellan-

drene7 in the lower boiling fractions. In addition to these hy¬

drocarbons, Schimmel & Company8 have reported the presence

of citral, cineol, borneol and probably geraniol, and Dodge9 the

presence of an aldehyde of the probable formula, n-C9H19CHO.

The volatile oil has been found to be present in the rhizomes

in varying quantities depending on their age before harvesting,

the methods of curing and their geographical source.10 Ac-

5 Pharm. Ztg. (1900), 45, p. 414.

6 Ber. d. deutsch. chem. Gesell. (1913), 46, p. 1814.

7 Schimmel & Co. Semi-Ann. Rep. (1905), II, p. 38.

8 Fhellandrene and d-camphene were identified in the oil by Bertram and

Walbaum in 1894. Journ. f. prakt. Chem. (1894), 49, p. 18.

9 Chem. Abs. (1912), 6, 3, p. 2976; Orig. Com. 8th Intern. Congr. Appl.

Chem. 6 p. 77.

10 Gane reports the presence of volatile oil in ginger as follows : Jamaica

0.64 per cent., Cochin 1.35 per cent., African 1.615 per cent., Fijian 1.45 per

cent. Fharm. Journ. (1892), 51, p. 802.

Thresh obtained 0.75 per cent, of oil from Jamaica ginger, 1.35 per cent,

from Cochin and 1.61 per cent, from African. Pharm. Journ. (1879), 39,

p.l. 191.

Haensel states that he obtained only 1.072 per cent, of volatile oil from

Jamaica ginger, whereas other sorts yielded from 2 to 3 per cent. Pharm.

Ztg. (1903), 48, p. 58.

Bennet found 0.20 to 0.90 per cent, of oil in Jamaica ginger, Pharm. Journ.

(1901), 66, p. 522.

Reich gives the following as the volatile oil content of various sorts of

Du Mez — The Galenical Oleoresins.

1075

cording to Cripps and Brown a “good ginger” will yield from

2.24 to 3.48 per cent.* 11

Gingerol. Gingerol or zingiberol12 is the constituent or mix¬

ture of constituents to which ginger is said to owe its pungency.

It is a colorless, odorless, viscid fluid possessing an extreme

pungency. Its exact composition has not been determined, the

most recent investigations indicating that it is a mixture of

phenols.13 It is readily soluble in strong alcohol, carbon disul¬

phide, benzol and oil of turpentine, but only slightly soluble in

petroleum ether.

Gingerol is present in the rhizomes in amounts varying from

0.6 to 1.82 per cent.14

Resins. The resins of ginger have been isolated and described

by Thresh.15 This investigator recognizes four individuals with

respect to their physical properties and their behavior toward

acids and alkalies, viz : a neutral resin, an a-resin, a /?-resin and

a y-resin.

The neutral resin is stated to be a black, pitch-like substance

soluble in ether, alcohol, benzene and oil of turpentine, but in¬

soluble in petroleum ether and carbon disulphide.

The a-resin is a soft, but brittle substance soluble in ether

and alcohol, but insoluble in the remainder of the above men¬

tioned solvents.

The /?-resin is also soft and brittle, but is soluble in all of the

above solvents.

The y-resin is firmer in consistence and is soluble in ether,

alcohol and petroleum ether.

The total resin content of the rhizomes varies to a considerable

ginger: Cochin 1.38 per cent., Japan 1.38 per cent., Bengal 1.6 per cent.,

African 2.54 per cent. Zeitschr. Unters. Nahr. u. Genussm. (1907), 14,

p. 549.

11 Analyst (1909), 34, p. 519.

12 The term gingerol was first used by Thresh in 1884 to designate the

pungent principle of ginger. Year-Book of Pharm. (1884), 21, p. 516.

Zingiberol is evidently a modification of the above, the idea being to bring

the nomenclature in closer conformity with the name of the botanical source—

Zingiberis officinale Roscoe.

13 Garnet and Grier, Year-Book of Pharm. (1907), 44, p. 441.

14 Thresh obtained gingerol in the following quantities : Jamaica ginger

0.66 per cent., Cochin 0.60 per cent., African 1.45 per cent. Pharm. Journ.

(1879), 39, p. 193.

Gane reports the presence of the following percentages: Jamaica 0.84 per

cent., Cochin 0.60 per cent., African 1.45 per cent., Fijian 1.82 per cent.

Pharm. Journ. (1892). 51, p. 802.

15 Pharm. Journ. (1879), 39, p. 193.

1076 Wisconsin Academy of Sciences, Arts, and Letters.

extent and appears to depend principally on their geographical

source. The minimum yield (1.18 per cent.) has been obtained

from Jamaica ginger, the maximum yield (4.47 per cent.) from

the Fijian rhizome.16

Fat and Wax. Little or no work has been done toward de¬

termining the composition of the fat or wax in ginger. The

two substances, combined, are stated to constitute 0.70 to 1.225

per cent, of the rhizome.17.

Ash. The qualitative examination of the ash of ginger has

been undertaken by Thresh,18 who reports the presence of the

basic elements : K, Ca, Mg, Mn,19 and Fe combined with H2C03

and H3P04. The ash of African ginger is stated to contain the

largest amount of manganese.

The ash content20 of the whole rhizome appears to be in¬

fluenced but little by the locality from which obtained, 3.0 to5.5

per cent, being conservative limits for the usual commercial var¬

ieties. Peeling21 appears to decrease the amount of ash while

bleaching22 (liming) increases it.

Constituents of Therapeutic Importance.

The physiological action of the oleoresin of ginger was at one

time thought to be due to the resin content, but the work of

Thresh1 has shown the pungency to be the property of the

phenolic constituents known collectively as gingered. The car-

18 Thresh reports the total resin content of ginger as follows : Jamaica 1.18

per cent, Cochin 1.815 per cent., African 3.775 per cent., Fharm. Journ.

(1879), 39, p. 173.

Gane noted the presence of the following percentages: Jamaica ginger 1.76

per cent., Cochin 1.815 per cent, African 3.775 per cent., Fijian 4.475 per

cent. Pharm. Journ. (1892), 51, p. 802.

17 The combined fat and wax present in ginger is stated by Thresh to be

as follows: Jamaica 0.70 per cent., Cochin 1.205 per cent, African 1.225 per

cent. 1. c.

Gane found the following amounts: Jamaica ginger 0.92 per cent., Cochin

1.20 per cent., African 1.225 per cent., Bengal 0.86 per cent, L. C.

18 Pharm. Journ. (1879). 29 pp. 174 and 193.

19 See also Flueckiger, Ibid. (1872), 32, p. 208.

20 C. Richardson. Bull. 13, Dept Agr. Washington, 1887; Gane, Pharm.

Journ. (1892), 51, p. 802; Diverseege, Vierteljahresschr. Nahrungs-u. Genussm.

(1896), 11, p. 353; Glass, Pharm. Journ. (1897), 58, p. 245; Bennet, Ibid.

(1901, 66, p. 522.

21 Winton, Ogden and Mitchell obtained 3.66 to 4.06 per cent, of ash for un¬

peeled and unbleached Cochin ginger, 3.36 per cent, for the same when peeled

and bleached. Rep. Conn. Agr. Exp. Sta. (1898), p. 202; (1899), p. 102.

22 Davis reports 5.20 per cent, of ash for unbleached Jamaica ginger. 6. 55

per cent, for the bleached. Pharm. Journ. (1895), 54, p. 472.

1 Year-Book of Pharm. (1884), 21, p. 516.

Du Mez — The Galenical Oleoresins.

1077

minative action of the preparation must also be attributed in

part to the volatile oil contained therein.

Physical Properties.

Color: The oleoresins examined in the laboratory were ob¬

served to be rather dark brown in color when spread out in thin

layers on a white porcelain surface. This property, however,

is reported to vary somewhat with the variety and condition of

the ginger used in making the preparation. When African

ginger is employed, the oleoresin is stated to be dark brown in

color, whereas, uncoated Jamaica ginger is said to yield a

preparation comparatively light in color.1

Odor : The oleoresin, when prepared according to the official

process, has the full aroma of ginger, the quality of which is

stated to be influenced largely by the variety of ginger used.2

Taste: The preparation has the sharp pungency and flavor

of ginger. This property, like the odor, is stated to vary with

the variety of ginger used, Jamaica ginger yielding the product

with the best flavor.3

Consistence: The oleoresin is a thick liquid, being of about

the consistence of molasses, as a rule, but varying somewhat

with the variety of the ginger used in its preparation. The

fluidity is said to be the greatest when prepared from Jamaica

ginger and the least when made from the African variety.4

Solubility: The oleoresin is soluble in absolute alcohol, ace¬

tone, ether, chloroform, and glacial acetic acid. It is partially

soluble in petroleum ether, the extent of its solubility depend¬

ing on the solvent used in its preparation as is shown in the fol¬

lowing table:

Table 65 — Solubility of the oleoresin in petroleum ether.

1 Parrish. Treatise on Pharmacy, (1867), p. 233.

2 Idris (1898).

3 Idris (1898).

4 Idris (1898).

1078 Wisconsin Academy of Sciences, Arts , and Letters.

As will be noticed this difference in solubility is quite pro¬

nounced and it should, therefore, serve as a ready means of

identifying the solvent used in the manufacture of the prepara¬

tion.

Specific gravity: At 25 °C a specific gravity of 1.020 to 1.086

was found for this oleoresin when acetone or ether were em¬

ployed in its preparation. This constant was observed to be

slightly higher when alcohol was used as a menstruum and con¬

siderably lower (less than 1.000) when petroleum ether was em¬

ployed. In the case of the commercial samples examined, a low

specific gravity is to be attributed to the presence of unevapor¬

ated solvent in one instance, and in the other, it is thought to be

due to an abnormally large volatile oil content. The data ob¬

tained in the examination of laboratory and commercial samples

are given in the tables which follow.

Table 66 — Specific gravities of oleoresins prepared in the laboratory,

Table 67 — Specific gravities of commercial oleoresins.

1 Contained ether.

Refractive index: A refractive index of about 1.517 at 25 °C

was observed for the preparations made in the laboratory with

acetone or ether. When alcohol was employed in extracting the

drug, the resulting product was found to have a slightly higher

refractive index, while petroleum ether yielded an oleoresin in

Du Mez — The Galenical Oleoresins.

1079

which this constant was observed to be considerably lower. The

low refractive index found for two of the commercial samples

was very likely due to the fact that they contained twice as

much volatile matter (principally essential oil) as the laboratory

preparations. The effect of this influence, together with that

produced by the presence of unevaporated solvent, is brought

out in the following tables :

Table 68. — Refractive indices of the oleoresins prepared in laboratory.

Table 69. — Refractive indices of commercial oleoresins.

1 Contained ether.

Chemical Properties.

Loss in weight on heating: The oleoresins prepared in the

laboratory lost, as a rule, between 11 and 13 per cent, of their

weight on heating at 110° C, whereas the loss in the case of the

commercial samples was about twice as great. While this dif¬

ference may have been due to the employment of different

methods in the making of these preparations (a vacuum pan

having probably been used in the removal of the solvent in the

case of the commercial products), it is more likely the re¬

sult of the presence of a greater amount of volatile oil in the

drugs from which the latter were prepared. The loss in weight

1080 Wisconsin Academy of Sciences, Arts , and Letters .

as found for the preparations examined in the laboratory is given

in the tables which follow.

Table 70 —Laboratory preparations — loss in weight on heating .

Table 80. — Commercial samples — loss in weight on heating.

1 The presence of ether could he detected by the odor.

Ash content: The ash content of the oleoresin prepared with

acetone was found to be 0.28 per cent., whereas, that of the

preparation made with ether was only 0.14 per cent. The values

obtained for the commercial samples examined also showed this

variation due to the nature of the solvent. Copper, although

detected in two of these preparations (commercial oleoresins),

was present in such small quantities that the results were not

affected materially thereby. The following tables show the

results obtained in the ash determinations made in the laboratory.

Table 81. — Ash contents of oleoresins prepared in the laboratory.

Du Mez — The Galenical Oleoresins.

1081

Table 82. — Ash contents of commercial oleoresins.

1 Contained ether.

Acid number: The acid numbers obtained for the oleo¬

resins prepared in the laboratory were found to be fairly

uniform regardless of the solvent employed in extracting the

drug, except in the case of petroleum ether, when the value

found was low, namely, 11.2. The values obtained for the com¬

mercial samples examined were almost identical with those ob¬

tained for the laboratory preparations, even though the former

in all cases contained about twice as much volatile matter (gen¬

erally essential oil, in one case, unevaporated solvent in addi¬

tion) as the latter. The values obtained for this constant in the

laboratory are given in the tables which follow.

Table 83 — Acid numbers of oleoresins prepared in the laboratory.

Table 84 — Acid numbers of commercial oleoresins.

Contained ether.

Saponification value: Saponification values of 103.4 to

110.4 were obtained for the oleoresin when prepared with

1082 Wisconsin Academy of Sciences , Arts , and Letters .

acetone. For the preparation in which ether was employed as

a menstruum in extracting the drug, a saponification value of

102.9 was obtained. The comparatively low values obtained for

the commercial samples examined are to be accounted for by

the fact that in all cases, they contained nearly twice as much

volatile matter (presumably essential oil) as the laboratory

preparations. The values found for this constant are given in

the tables which follow.

Table 85— Saponification values of oleoresins prepared in the laboratory.

Table 86— Saponification values of commercial oleoresins.

1 Contained a trace of ether.

Iodine value : Iodine values of 122.4 to 124.1 were ob¬

tained for the oleoresin when prepared with acetone. The

preparations made with alcohol or ether gave values very

near the same, whereas, the value of this constant was some¬

what higher (126.9) when petroleum ether was the solvent em¬

ployed. With respect to the commercial samples, the values

found were lower in all cases. In one instance, this was due

to the presence of unevaporated solvent, while, in the other cases

it is to be attributed to the relatively large amount of volatile

matter (essential oil) present. The iodine values found for the

preparations examined in the laboratory follow.

Du Mez — The Galenical Oleoresins. 1083

Table 87.-— Iodine values of oleoresins prepared in the laboratory.

1 The drug- in this instance was extracted by simple percolation.

Table 88.— -Iodine values of commercial oleoresins.

1 Contained ether.

Special Qualitative Tests.

Most of the qualitative methods which have been mentioned in

connection with the standardization of this preparation are of

the nature of tests for the detection of adulterations. The oleo-

resin of capsicum1 is the adulterant which appears to have re¬

ceived special attention, several methods for detecting its pres¬

ence having been reported.

Tests for the Presence of the Oleoresin of Capsicum

La Wall, in 1910, pointed out the necessity of a test for the

presence of the oleoresin of capsicum as he had observed that

many of the commercial samples of the oleoresin of ginger used

in the preparation of ginger ale extracts were adulterated with

this substance. At the same time, he also described a method

whereby this form of adulteration might be detected. His

method is almost identical with that of Garnett and Grier pub¬

lished in 1907, both being based on the destruction of the

1 While the oleoresin of capsicum per se may occassionally be added to the

finished product, it is thought that the adulteration is usually accomplished

hy mixing capsicum with the ginger previous to the extraction of the oleoresin.

1084 Wisconsin Academy of Sciences , Arts , and Letters.

pungent principles ( ginger ol) of the oleoresin of ginger with

alkalies, whereby the pungent principle (capsicin) of the oleo¬

resin of capsicum remains unaltered. As it was subsequently

found that the pungent principles of the former were not com¬

pletely destroyed by this treatment, Nelson proposed a modi¬

fication of the above methods, in which he makes use of

manganese dioxide for completing the disintegration of these

constituents. Full descriptions of these methods follow :

Method of Garnett .and Grier (1907): Digest 1 gram of the oleoresin

for 15 minutes on a water bath with a small quantity of caustic alkali

dissolved in alcohol. Evaporate the solution to remove the alcohol and

make the residue faintly acid with hydrochloric acid. Transfer the liquid

to a test tube and shake it with 5 cubic centimeters of ether which have

previously been used to rinse the dish. Allow the mixture to stand quietly

and then taste the separated ethereal layer. If sharply pungent, adultera¬

tion with capsicum is indicated.

Method of La Wall (1910): Add 10 cubic centimeters of half -normal

alcoholic potassium hydroxide solution to 1 gram of the oleoresin contained

in a shallow porcelain dish and evaporate to dryness on a water bath. Dis¬

solve the residue in 50 cubic centimeters of water and transfer the solution

to a separatory funnel. Add 20 cubic centimeters of ether and shake vigor¬

ously. After allowing the mixture to stand until the ether has separated,

run the latter off on a watch glass and expose it until the solvent has all

evaporated. The residue should have a warm camphoraceous taste. A

sharp pungent taste indicates adulteration with capsicum.

Method of Nelson (1902) :2 Add 10 cubic centimeters of double-normal

alcoholic potassium hydroxide solution to one gram of the oleoresin contained

in a porcelain dish and evaporate on a steam bath. Add about 0.1 gram

of powrdered manganese dioxide and 5 to 10 cubic centimeters of water,

and continue heating for about 20 minutes, or until all of the volatile oil

has been expelled. Cool, acidify with dilute sulphuric acid and extract

at once with petroleum ether. Evaporate the petroleum ether solution in a

small crucible, keeping the residue within as small an area as possible. When

all of the solvent has evaporated, apply the tongue to the residue, being

careful to keep the material on the tip. If capsicum is present, the char¬

acteristic burning sensation will soon be felt.

The latter is the method which was employed in making the

test in the laboratory. In no ease, however, was capsicum de¬

tected in the samples examined.

2 Journ. Indust, and Eng-. Chem. (1910), 2, p. 419.

Du Mez — The Galenical Oleoresins.

1085

Special Quantitative Tests.

While the matter of determining the quality of the unadulter¬

ated product has apparently received but little attention, two

distinct methods have, nevertheless, been made use of in its

evaluation. They are the methods of Garnett and Grier for the

determination of the gingerol content, and the physiological test

employed by the H. K. Mulford Company.

Methods for the Estimation of the Gingerol Content.

The only method of an analytical nature which has been sug¬

gested for the quantitative evaluation of this oleoresin is based

on the fact that the pungent principles, gingerol, are more

readily soluble in 60 per cent alcohol, than in petroleum ether.

A description of the manner in which this assay is carried out

follows.

Method of Garnett and Grier (1909): Dissolve the gingerol by boiling

about 1 gram of the oleoresin with several portions of petroleum ether,

filter the solutions thus obtained and remove the solvent bj evaporation

on a water bath. Dissolve the residue in alcohol (60 per cent.) added in

three separate portions, shake the united alcoholic solutions with a small

amount of petroleum ether to remove traces of fat and remove the alcohol

from the hydro-alcoholic portion by evaporation. Shake the residual liquid

with 3 portions of ether added successively, filter the combined shakings

into a tared flask, remove the ether by evaporation on a water bath, dry

at 100 °C and weigh. In the final shaking out, carbon disulphide or chloro¬

form may be used in place of the ether.

The use of this method in the laboratory has shown that it

gives fairly constant results, and, as it is easily carried out, it

should prove to be of practical value. The results obtained in

the examination of oleoresins prepared in the laboratory and

those obtained from commercial sources are given in the fol¬

lowing tables :

Table 89 — Gingerol content of oleoresins prepared in the laboratory.

1086 Wisconsin Academy of Sciences, Arts , and Letters.

Table 90 — Ginger ol content of commercial oleoresins.

The first of the preceding tables shows that the gingerol con¬

tent varies with the solvent employed in the preparation of the

oleoresin. Further, that this variation is not in inverse ratio

to the yield of oleoresin obtained as might be expected, but is

exceptionally low in the case of acetone due to the fact that it is

a difficult matter to completely exhaust the drug when the lat¬

ter is the solvent used.

The low gingerol content of two of the commercial samples as

shown in the second table, points to the use of acetone in their

preparation. A similar effect might, however, be produced when

ether or alcohol are employed if the ginger used is of poor

quality (low in gingerol content,) or if percolation is termin¬

ated before complete exhaustion of the drug has taken place.

The oleoresin obtained from Squibb and Sons is stated to have

been prepared with ether, which statement is confirmed by the

result obtained in the determination of the gingerol content as

is also shown in the second table.

Physiological Tests.

The H. K. Mulford Company reports the use of a physiologi¬

cal test for determining the quality of this oleoresin. As an

arbitrary standard, the firm has taken a preparation which is

pungent to the taste in a maximum dilution of 1 to 20,000.

While there is no information, at hand to indicate what solvent

was employed as the diluent, experience in the laboratory has

shown that dilute alcohol (50 per cent.) may be used for this

purpose. After vigorously shaking the oleoresin with alco¬

hol, the resulting solution should preferably be filtered before

applying to the tongue. Although no extensive series of ex¬

periments were made with this test in the laboratory, the results

obtained would appear to indicate that the above standard is

rather low as the pungency in the preparations examined was

Du Mez — The Galenical Oleoresins.

1087

easily perceptible in dilutions of 1 to 30,000. In view of the

fact that personal idiosyncrasy must be a factor in applying this

test, the use of the previously described method for the estima¬

tion of the gingerol content is thought to be more preferable for

use in this connection.

Adulterations

There is no evidence to show that the oleoresin as prepared

for pharmaceutical use is adulterated. La Wall,1 however, states

that the commercial article used in the manufacture of

ginger ale frequently contains oleoresin of capsicum.

A trace of copper was found in most of the commercial

samples examined. See under “Ash content. ’ ’

OLEORESIN OF LUPULIN

Synonyms

Aetlnerisches Lupulinextrdkt, Nat. Disp. 1879.

Extractum Lupulini, Hirsh, Univ. P. 1902, No. 1222.

Extractum Lupulini aethereum, Nat. Disp. 1879.

Oleoresina Lupulinae , U. S. P. 1860.

Oleoresina Lupulini, U. S. P. 1880.

Oleortisine de Lupuline, U. S. Disp. 3 907.

Ethereal Extract of Lupulin, King’s Am. Disp. (1900), p. 1333.

History

The first mention of the oleoresin of lupulin which could be

found in pharmaceutical literature appeared in Procter’s article,

“Formulae for fluid extracts in reference to their more general

adoption in the next Pharmacopoeia, ’ 9 published in 1859.

Procter’s oleoresin was in reality an ethereal extract, ether hav¬

ing been the menstruum employed in exhausting the drug. In

this connection, it is interesting to note that the extract prepared

with the use of alcohol had previously been brought to the

notice of the American pharmacist by Livermore in 1853, while

the attention of the European pharmacist had been directed to

the same by Planche as early as 1823. The oleoresin was first

admitted to the United States Pharmacopoeia in 1860, in which

it remained official for more than half a century, having been

1 La Wall (1910).

1088 Wisconsin Academy of Sciences, Arts , and Letters.

omitted from the present revised edition. It has never re¬

ceived recognition by any of the foreign pharmacopoeias.

Drug Used, Its Collection, Preservation, Etc.

Lupulin has not been included in the late edition of the United

States Pharmacopoeia. In the preceding edition, it was defined

as “the glandular trichomes separated from the fruit of Humw-

lus Lupulus Linne (Fam. Moraceae).”

The drug, as it occurs on the market, is of varying degrees of

purity due, principally, to the method of obtaining it While

some of it is probably obtained by picking the scales from

the fruits and then shaking or rubbing the glands through a

fine sieve, the bulk of the. commercial article consists of the

sweepings gathered up from the floors of the hop bins.1 Such

being the case, it is only natural to expect contamination with

sand and other earthy materials. The impurities, in part, are

usually removed by washing with water when the sand settles

to the bottom and the lupulin is skimmed off and dried.

The glands, on storing, especially if exposed to the air,

undergo a change, becoming dark brown in color and developing

a rancid odor. Rabak2 and Russell,3 respectively, have shown

one of the changes to be a conversion of the so-called soft resin

into the hard. The development of the disagreeable odor has

been attributed to the formation of valeric acid4 resulting from

the oxidation of one or more of the constituents. In view of the

foregoing, the British Pharmacopoeia directs that the drug be

renewed annually and rejected as soon as it becomes dark in

color or developes a cheesy odor.

In this connection, it should also be stated that hops are often

sulphured previous to storing. To what extent, if any, this

treatment affects the quality of the lupulin obtained therefrom

and later the oleoresin, does not appear to have been determined.

1 Flueckiger, Pharmakognoise des Pflcmzenreichs (1891), p. 255.

2 Bull. No. 271, U. S. Dept, of Agric. (1913), p. 13.

3 Bull. No. 282, U. S. Dept of Agric. (1915), p. 9.

4 Bungener, Pharm. Journ. (1884), 43, p. 1008.

Du Mez — The Galenical Oleoresins .

1089

U, S. P. Text and Comments Thereon.

The oleoresin, which was official in the United States Phar¬

macopoeia from I860 to 1900, has been omitted from the last

edition (edition of 1910).

1864

Oleoresina Lupulinae

Oleoresin of Lupulin

Take of Lupulin 1 twelve troyounces ; distillation on a water-bath, eighteen

Ether2 a sufficient quantity. fluidounees of ether,5 and expose the

Put the lupulin into a narrow cylin- residue, in a capsule, until the remain-

drical percolator, press it firmly, and ing ether has evaporated.6 Lastly,

gradually pour ether upon it until keep the oleoresin in a wide-mouthed

thirty fluidounees of filtered liquid bottle, well stopped.7

have passed.4 Recover from this, by

1870

Oleoresina Lupulinae

Oleoresin of Lapulin

Take of Lupulin 1 twelve troyounces ; ounces of liquid have slowly passed.4

Ether 2 a sufficient quantity. Recover the greater part of the ether

Put the lupulin into a narrow cylin- by distillation on a water-bath,5 and

drical percolator, provided with a expose the residue in a capsule, until

stop-cock, and arranged with cover the remaining ether has evaporated.6

and receptacle suitable for volatile Lastly, keep the oleoresin in a wide-

liquids,3 press it firmly, and gradually mouthed bottle, well stopped.7

pour ether upon it, until twenty fluid-

1880

Oleoresina Lupulini

Oleoresin of Lupulin

[Oleoresina Lupulinae, Pharm., 1870]

Lupulin,1 one hundred parts .... 100. parts of liquid have slowly passed.4

Stronger Ether2, a sufficient quantity,. Recover the greater part of the ether

Put the lupulin into a narrow cylin- by distillation on a water-bath,6 and

drical percolator, provided with a expose the residue, in a capsule, until

cover and receptacle suitable for the remaining ether has evaporated.®

volatile liquids,3 press it firmly, and Keep the oleoresin in a well-stop-

gradually pour stronger ether upon ped, wide-mouthed bottle.7

it, until one hundred and fifty (150)

69—- S. A. L.

1090 Wisconsin Academy of Sciences, Arts, and Letters.

1890

Oleoresina Lupulini

Oleoresin of Lupulin

Lupulin/ one hundred grammes . the drug is exhausted.* Recover the

. . . . 100 Gm. greater part of the ether from the

Ether/ a sufficient quantity. percolate by distillation on a water -

Put the lupulin into a cylindrical bath/ and, having transferred the

glass percolator, provided with a residue to a capsule, allow the re¬

stop-cock, and arranged with a cover maining ether to evaporate spontan-

and receptacle suitable for volatile eously.®

liquids.3 Press the drug very lightly, Keep the product in a well-stop -

and percolate slowly with ether, pered bottle/

added in successive portions, until

1900

Oleoresina Lupulini

Oleoresin of Lupulin

Lupulin/ five hundred grammes...... Recover the greater part of the ace-

. . . . 500 Gm. tone from the percolate by distilla-

Aeetone/ a sufficient quantity. tion on a water-bath/ and, having

Introduce the lupulin into a cylin- transferred the residue to a dish, al-

drical glass percolator, provided with low the remaining acetone to evap-

a stop-cock, and arranged with a orate spontaneously in a warm place.®

cover and a receptacle suitable for Keep the oleoresin in a well-stoppered

volatile liquids.3 Press the powder bottle.7

very lightly, and percolate slowly Average dose. — 0.200 = Gm. 200

with acetone, added in successive por- milligrammes (3 grains),

tions, until the lupulin is exhausted.4

1) For description of the drug, see page 1088 under “Drug

used, its collection, preservation, etc.”

2) The solvents which have been used for the purpose of ex¬

tracting lupulin are ether, acetone and alcohol. Of these, the

first two have been recognized at different times by the

Pharmacopoeia, acetone being the solvent which was directed

to be used by the edition of 1900, whereas ether was specified

in previous editions.

With respect to the relative values of the above, from a

therapeutical standpoint, a statement cannot be made owing

to the lack of specific information on the subject. From a

pharmaceutical standpoint, however, ether and acetone, re-

Dii Mez — The Galenical Oleoresins.

1091

spectively possess an advantage over alcohol in that they ex¬

tract less inert material and yield products which are softer

in consistence and conform more closely in their general

properties to the other members of this clbss of preparations.

The products obtained, even when using acetone or ether, are,

however, more of the nature of an extract than an oleoresin.

A better solvent for use in this connection would appear to

be petroleum ether. While, it has apparently never received

consideration for this purpose, it appears to be particularly

well adapted to the same in that it completely extracts the

valuable constituents of the drug (see soft resins, page 1095)

with but little of the inert material and yields a product of

such consistence that it can be poured.

3) For a description of the various forms of percolation con¬

forming to the pharmacopoeial specifications for use in this

connection, see Part I under “Apparatus used.”

4) The various editions of the Pharmacopoeia in which this

preparation has been official have directed that the material

composing the oleoresin be extracted from the drug by simple

percolation. In the earlier editions, percolation was directed

to be continued until a certain definite amount of percolate

was obtained, whereas, the pharmacopoeias of 1890 and 1900

required that the operation be continued until the drug was

exhausted. In either case, the quantity of solvent required is

considerably greater than that which is necessary to com¬

pletely exhaust the drug when some form of continuous ex¬

tractor is used. Since the quality of the finished product is

the same in both cases, it is thought that the later method of

extraction is to be preferred.

5-6) Owing to the fact that certain constituents of the oleo¬

resin are prone to undergo changes when the latter is exposed

to the air (see page 1088 under “Drug used, its collection, pres¬

ervation, etc.”), the pharmacopoeial directions, that the last

portions be allowed to evaporate spontaneously, are unfortu¬

nate. It is thought that a better procedure would be to evap¬

orate the solvent completely at the temperature of the water

bath, thereby considerably shortening the time of exposure.

8) For the reasons just mentioned, the finished product

should be kept in well-stoppered bottles.

1092 Wisconsin Academy of Sciences, Arts, and Letters ,

Yield

The yield of oleoresin to ether is usually given in the text¬

books and treatises on pharmacy as 50 to 60 per cent., while a

yield of 32.49 to 70.8 per cent, has been reported in the journals.

The irregularity in the quality of the lupulin as ordinarily found

on the market very likely accounts for this variation. The

drug, when of good quality should give a yield of at least 60

per cent. The following tables show the variation in the yield

as reported in the literature, also, the results obtained in the

laboratory.

Table 91 — Yield of oleoresin as reported in the literature.

Date

1853

1888

189:'

1892

1907

1903

1909

1911

1913

1914

1915

Remarks

Results obtained In the ex¬

traction of 10 samples of lu¬

pulin.

Seven of 8 samples yielded

more than 60 per cent, of ex¬

tractive to ether.

Results obtained in the ex¬

traction of 4 samples of lu¬

pulin.

Results obtained in the ex¬

traction of 53 samples of lu¬

pulin.

Eight of 12 samples of lupulin

extracted gave below 60 per

cent, of ether soluble matter.

Du Mez — The Galenical Oleoresins.

1093

Table 92 — Yield of oleoresin as obtained in the laboratory.

Chemistry of the Drug and Oleoresin

Tabulation of Constituents

The chemistry of lupulin* 1 per se has received comparatively

little attention, although, -a very considerable knowledge con¬

cerning its constituents has been gained through the work of

the brewing chemists and others2 3 4 5 6 7 8 on hops. The isolation of the

1 The following have reported more or less complete analyses of lupulin :

Ives, Silliman’s Am. Journ. of Science (1820), 2, p. 303 ; Payen, Pelletan and

Chevalier, Journ. de Pharm. et de Chim. (1822), 8, p. 209; Personne, Ibid.

(1854), 59, p. 329; Chapman, The Hop and its Constituents. The Brew¬

ing Review, London, (1905).

2 Power, Tutin and Rogerson, who have completed one of the most recent

as well as extensive pieces of work on the constituents of the hop, have

isolated the following substances:

I Volatile oil

II Alcoholic Extract soluble in water :

1. Choline (CrHl502N.)

2. 1-Asparagine (C4H8OsN2.)

3. Potassium nitrate

4. Tannin

5. Sugar forming a d-phenylhydrazone, m. p. 208.

6. Amorphous bitter material.

7. Volatile base having a coniine-like odor.

Ill Alcoholic extract insoluble in water:

1. Hentriacontane (C31H64.)

2. Ceryl alcohol (C27H560.)

3. Phytosterol (C27H4eO.)

4. A phytosterolin, phytosterol glucoside (C^H^Og.)

5. Volatile fatty acids: formic, acetic, butyric, valeric, jg-isopro-

pylacrylic (CeH10O2), and nonoic.

6. Saturated and unsaturated non-volatile acids: palmitic, ste¬

aric, cerotic, an isomeride of arachidic (C^H^Oj), cluytinic

and linolic.

7. A new bitter crystalline phenolic substance, humulol

(C]7H1803.)

8. A new tasteless crystalline phenolic substance, xanthohumol

(c13h34o3.)

Journ. Chem. Soc. (1913), 103, p. 1267.

1094 Wisconsin Academy of Sciences, Arts, and Letters.

following constituents of pharmaceutical interests has been re¬

ported: Volatile oil, resin, wax, alkaloids and inorganic sub¬

stances. Chapman3 gives the composition of the ethereal ex¬

tract as follows:

a-resin . . 18.06 per cent.

i8-resin . 67.74 “ “

Wax . 0.28 11 “

Other constituents (fat, oil, 7-resin, etc.) . 13.64 “ “

Ash . 0.27 “ “

Occurrence and Description of Individual Constituents.

Volatile Oil .4 The volatile oil obtained by distillation with

steam is a pale vellow, or colorless, mobile liquid possessing a

fragrant and characteristic odor, and a slightly burning taste.

It is almost insoluble in water, to which, however, it imparts its

odor, and only slightly soluble in dilute alcohol. It is soluble

in ether, petroleum ether, chloroform and the other volatile oil

solvents. The specific gravity at 20 °C is 0.8357 to 0.8776, and

the specific rotatory power, [a]D20, is 0.20 to 0.58.5

According to Chapman,6 the oil is composed of the terpene,

myrcene, (C10H16), 40 to 50 per cent; inactive linalool, a fraction

of 1 per cent; linalyl isononoate, a fraction of 1 per cent; the

sesquiterpene, humulene7 (C15H24), about 40 per cent; and

probably some ether of geraniol with a small amount of a diter-

pene. Rabak,8 who has more recently completed an investiga¬

tion of the constituents of the oil, states that, in addition to

myrcene and humulene, the oil contains the heptoic, octoic and

nonoic acid esters of myrcenol with traces of free fatty acids and

probably some free alcohols.

As much as 2 per cent of volatile oil has been obtained from

lupulin by steam distillation.9

Resin. The chemical constitution of the so-called “hop

resins” is still an unsolved problem, the literature being replete

3 Ibid, p. 81. The hop and its constituents. The Brewing Review, Lon¬

don (1905).

4 The following references are to the earlier literature on the volatile oil :

Payen, Felletan and Chevalier and Personne, 1. c. ; Wagner, Journ. f. prakt.

Chem. (1853), 58, p. 351; Ossipon, Ibid. (1886), 142, p. 238.

5 Chapman, l. c.

6 Ibid.

7 E. Deussen, who has determined the constitution of humulene, finds it to

be 1-caryophyllene. Journ. f. prakt. Chem. (1911), 83, p. 483.

8 Journ. Agric. Research (1914), 2, p. 115.

9 Payen, Pelletan and Chevalier, l. c. See also Semmler, l. c.

Du Mez — The Galenical Oleoresins.

1095

with vague and contradictory statements.10 Foi practical pur¬

poses, the classification of Hayduck* 11 appears to be the most

useful. This investigator distinguishes three resins, which he

designates a, (3 and y, according to their solubility in petroleum

ether and their behavior toward a solution of lead acetate. The

a - and j8- resins are soluble in petroleum ether, and are further

known as the “soft resins, ” being of a soft consistence at the

ordinary temperature. The y-resin is insoluble in petroleum

ether, but soluble in ether or alcohol. It is also known as the

“hard resin. ”

The soft resins are supposed to contain the valuable bitter

substances present in hops. From these resins, Lintner and

Schnell12 isolated two crystalline bitter substances of an acid

nature. One of these, C15H2404, they proposed naming

“ humulon ; ”13 the other, they have designated “lupulic acid.”14

According to Chapman, the total resins constitute more than

55 per cent, of the lupulin.15

Wax. According to Lermer16 the wax is insoluble in 90 per

cent alcohol and can be obtained by treating the ethereal extract

with this solvent. He identified it as myricyl palmitate. As

Power, Tutin and Rogerson17 report the presence of ceryl alco¬

hol and cerotic acid in hops, it is quite probable that ceryl

cerotate is also a constituent of the wax.

Alkaloids. Choline18 (C5H1502N) is the only base occurring

in lupulin, the identity of which has been established. There

is, however, considerable evidence of the presence of a volatile

10 The theory advanced by Seyffert (Zeitschr. ges. Brauw. (1896), 19, p. 1

namely, that the hop resins are mixtures of substances in a progressive state

of change is probably correct. Confirmation of this' theory is to be found

in the work of Russell who states that a portion of the “soft resin’” is con¬

verted into the “hard resin” upon keeping the hops in storage. U. S. Dept.

Agric., Bull. No. 282 (1915), p. 9.

11 Wochenschr. f. Brau. (1887), 4, p. 397; Ibid. (1888), 5, p. 937.

^Zeitschr. ges. Brauw. (1904), 27, p. 666.

13 “Humulon” is very likely identical with the “hop-bitter acid” of H. Bun-

gener, (Bull. Soc. Chim. (18SS6), 45, p. 487), and the “a-lupulic acid” of

Barth. Zeitschr. ges. Brauw. (1900), 23, pp. 509, 537, 554, 572 and 594.

14 “Lupulic acid” corresponds to the “j8-lupulic acid” of Barth, l. c.

15 1. c.

61 Dingier’ s Folytech. Journ. (1863), 169, p. 54.

17 l. c.

18 Griess and Harrow have shown that hops contain not over 0.02 per cent,

of choline. Ber. der deutsch. chem. Ges. (1885). 18, p. 717.

1096 Wisconsin Academy of Sciences, Arts, and Letters.

alkaloid possessing a coniine-like odor. Griessmayer,10 who

first noted its presence, gave it the name ‘ ‘ lupuline. ’ ’

In 1885, Williamson20 reported the isolation of a crystalline

alkaloid from wild American hops. He gave it the name

“hopeine,” and assigned to it the formula, C18H20NO4. H20.

Ladenburg,21 who examined a sample of the material thought

it to be a mixture of morphine and a more soluble base.22 As

further work23 along this line has failed to confirm the findings

of Williamson, the presence of a crystalline alkaloid must be

considered doubtful.

Ash. Analyses of the ash of lupulin have apparently not

been reported to date. However, Wehmer* 1 states that Ca, Cl

and Si02 are present in the ash from all parts of the hop plant,

and, as Na, Mg, Fe, Al, and H3P04 were identified in the ash

of the oleoresins examined in the laboratory, it is quite probable

that the constituents of lupulin ash are identical with those

present in the ash of hops.2

There is a great variation in the quantity of ash obtained

from commercial samples of lupulin owing to contamination

with sand and other earthy matter. Barth3 gives the yield of

ash as 9.5 to 24.4 per cent, while Flueckiger4 states that a good

sample of lupulin should give about 7.0 per cent. Accord¬

ing to Keller,5 lupulin, washed free from all earthy matter,

yielded only 2.37 per cent, of ash.

Constituents of Therapeutic Importance.

There appears to be considerable doubt at the present time

as to the value of the oleoresin of lupulin as a therapeutic

agent. The presence of the soluble bitter principles is said to

10 Dingler’s Polytech. Journ. (1874), 212, p. 67. See also Power, Tutin and

Rogerson, l. c.

30 Pharm. Ztg. (1885), 30 p. 620.

21 Ber. der deutsch. Chem. Ges. (1886), 19, p. 783.

22 Williamson, in a second publication, agrees with the findings of Laden-

burg and assigns the name hopeine to the more soluble base. Chem. Zeit.

(1886), 10, p. 491.

23 Greshoff could not obtain a crystalline alkaloid from lupulin. Dingler’s

Polytech. Journ. (1887), 266, p. 316.

1 Wehmer, Die Pflanzenstoffe. Jena (1911), p. 160.

3 Richardson, in an examination of hop ash, identified the elements, Na, K,

Ca, Mg. Al and Fe, and the acids, H3PG4, H2CG3 and H2SiOa. Wochenschr.

Brau. (1898), 15, p. 160.

3Zeitschr. ges. Brauw. (1900), 23, p. 509.

4 Flueckiger, Pharmakopnosie des Pflanzenreiches. Berlin (1891), p. 257.

6 Pharm. Ztg. (1889), 34, p. 533.

Du Mez — The Galenical Oleoresins.

1097

impart to it the properties of a simple bitter.1 The somewhat

general belief that the oleoresin is a mild sedative does not ap¬

pear to be well founded and is probably based on the doubtful

report that hops contain an alkaloid (hopeine) resembling

morphine in physiological action.2

Physical Properties

Color: When spread out in a thin layer on a white porce¬

lain surface, the color of the oleoresin was observed to be a

dark brown resembling very much that of the oleoresin of gin¬

ger.

Odor: The preparation when made with acetone or ether

has the peculiar odor of lupulin. The odor of the commercial

product, however, is often quite different. In some cases it is

disagreeable and resembles valeric acid,3 while in other cases

it is pleasant and suggests the presence of the ethyl esters of

the lower fatty acids.4

Taste : The taste is bitter and somewhat aromatic resembling

that of lupulin.

Consistence: The oleoresin, when prepared according to the

directions of the United States Pharmacopoeia of 1900 is of the

consistence of a very soft extract. On standing in partially

filled containers, it becomes firmer as a result of the conversion

of a part of the soft resin into hard resin.

Solubility: The official preparation is freely soluble in alco¬

hol (95 per cent.), acetone, ether, chloroform and glacial acetic

acid. It is partially soluble in petroleum ether, the extent of

its solubility depending on the age of the oleoresin (if stored

in partially filled containers) or on the age of the drug from

which the latter is prepared.5 6 It is also slightly soluble in

hot water to which it imparts a bitter taste.

1 Potter, Mat. Med., Pharm. & Therap. (1903), p. 339.

aPharm. Ztg. (1885), 30, p. 620.

8 This is due to the use of old deteriorated drug in the preparation of the

oleoresin or to the storing of the latter under improper conditions. See under

“Drug used, its collection, preparation, etc.”

4 The agreeable fruity odor sometimes noticed is thought to be due to the

presence of ethyl esters of the lower fatty acids formed as a result of the

extraction of old deterioratd drug with alcohol.

6 On aging under ordinary conditions, the soft resin present in the drug or

oleoresin is converted, in part, into hard resin. As only the former is soluble

in petroleum ether, old oleoresins, or those prepared from old drug, are

usually less soluble in this solvent than the preparations freshly made from

unaltered drug. See under “Drug used, its collection, preservation, etc.”

1098 Wisconsin Academy of Sciences, Arts, and Letters.

Specific gravity: The oleoresin has the highest specific

gravity of any of the preparations of this class, specific grav¬

ities of 1.065 and 1.067 having been observed for the same when

made with ether and acetone, respectively. Alcohol yields a pro¬

duct of somewhat greater density, whereas the use of petroleum

ether gives an oleoresin of low specific gravity. The important

factors influencing the specific gravity of this oleoresin, aside

from the effect produced by the use of different solvents in its

preparation, are thought to be the condition of the drug1 when

extracted and the presence of unevaporated solvent in the

finished product. The results obtained in the examination of

laboratory and commercial samples are given in the following

tables.

Table 93 — Specific gravities of oleoresins prepared in the laboratory.

1 The preparation had a slight odor of ether.

Refractive index: The refractive index of the oleoresin, when

prepared with acetone, was found to be 1.516 at 25 °C, which

agrees fairly well with that obtained for the sample from Sharp

and Dohme. The low refractive index observed for the sample

from Lilly and Co. is thought to be due to the presence of un-

1 See under the caption “Chemistry of the drug and oleoresin”.

Du Mez — The Galenical Oleoresins. 1099

evaporated solvent (probably alcohol). The results obtained

in the determinations made in the laboratory are given in the

tables which follow:

Table 95 — Refractive index of the oleoresin prepared in the

laboratory.

Table 96 — Refractive indices of commercial oleoresins.

Chemical Properties.

Loss in weight on heating: A loss in weight of 9.59 to 15.63

per cent, was observed for the laboratory preparations when

heated at 110° C. Except in the case of the oleoresin which

contained unevaporated solvent (alcohol), the loss did not ex¬

ceed 10.32 per cent. Results of a similar magnitude were ob¬

tained for the commercial samples examined as is shown in the

tables which follow.

Table 97 — Laboratory preparations — loss in weight on heating.

1 Contained unevaporated solvent.

1100 Wisconsin Academy of Sciences , Arts , and Letters.

Table 98 — Commercial oleoresins — loss in weight on heating.

1 Contained ether.

2 Probably contained unevaporated solvent (alcohol).

Ash content: The ash contents, in the case of the oleoresins

prepared in the laboratory, were found to be 0.93, 1.46 and 1.82,

depending on whether ether, acetone or alcohol was employed

in their preparation. A somewhat similar variation in the

amount of ash obtained for the commercial samples examined

is, therefore, taken to be an indication of the indiscriminate use

of the above mentioned solvents in their manufacture, instead

of acetone as was directed to be employed by the 1900 edition

of the United States Pharmacopoeia. The slightly higher values

obtained for the commercial samples may have been due to the

copper, which was found to be present in considerable amounts.

The results obtained in the ash determinations made in the lab¬

oratory follow:

Table 99 — Ash contents of oleoresins prepared in the laboratory.

Table 100 — Ash contents of commercial oleoresins.

1 Contained ether.

2 Probably contained unevaporated solvent (alcohol).

Du Mez — The Galenical Oleoresins.

1101

Acid number: The acid numbers given in the first of the

tables which follow are those obtained for preparations which

had stood in the laboratory for six years previous to being

examined. As the acidity of the oleoresin very likely in¬

creases on ageing, when kept under ordinary conditions, due to

the oxidation of some of its constituents, it is thought that a

somewhat lower value is to be expected for this constant in the

case of the freshly made preparation. The relatively low

value found for the oleoresin prepared with alcohol was due to

the presence of unevaporated solvent, which not only acts as a

diluent, but also combines to some extent with the acids present

forming esters, the latter imparting a fruity odor to the

preparation. Viewed in the light of the foregoing statements,

the acid numbers obtained for the commercial samples indicate

that two of them were very probably old preparations and that

the third (the sample obtained from Lilly & Co.) contained

unevaporated solvent (alcohol). The results obtained in the

determination of this constant in the laboratory follow.

Table 101 — Acid numbers of oleoresins prepared in the laboratory.

1 Contained unevaporated solvent.

Table 102 — Acid numbers of commercial oleoresins.

1 Contained ether.

Saponification value: Saponification values ranging from

223.4 to 239.6 were obtained for the oleoresins prepared in the

laboratory, the variation being due, very likely, to the nature of

the solvent employed in extracting the drug. The values found

1102 Wisconsin Academy of Sciences , Arts, and Letters.

for the commercial preparations were somewhat lower, due, in

two cases, to the presence of unevaporated solvent. In the third

instance, the low saponification value obtained was very probably

due to a difference in the quality of the lupulin from which the

oleoresin was extracted. The results obtained in the examina¬

tion of laboratory and commercial preparations follow.

Table 103 — Saponification values of oleoresins prepared in the

laboratory.

1 Contained ether.

Table 104 — Saponification values of commercial oleoresins.

2 Probably contained unevaporated solvent (alcohol).

2 Contained ether.

Iodine value: The oleoresin, when prepared with acetone,

ether, or benzin, was found to have an iodine value varying

from 94.7 to 96.2. When alcohol was the solvent employed

in its preparation, the value obtained was considerably lower,

namely, 82.05. A comparison of thse values with those found

for the commercial samples indicates that alcohol is sometimes

used in their preparation. The extremely low value obtained

for the oleoresin of Lilly & Co. is to be attributed to the pres¬

ence of unevaporated solvent (alcohol) as well as to the effect

produced by its use as a menstruum. The iodine values ob¬

tained for the preparations examined in the laboratory are

given in the tables which follow.

Du Mez — The Galenical Oleoresins.

1103

Table 105 — Iodine values of oleoresins prepared in the laboratory.

1 Alcohol was present.

Table 106 — Iodine values of commercial oleoresins.

1 Alcohol was probably present.

3 The odor of ether was noticeable.

Adulterations.

Adulteration effected through the use of old deteriorated drug

in the manufacture of this preparation has been noted. See

under “Drug used, its collection, preservation, etc.’ ’

The presence of copper was detected in all of the commercial

samples examined. See under “Ash content.’ ’

OLEORESIN OF PARSLEY FRUIT

Synonyms

Aetherisches PetersilieextraTct. Culbreth, Mat. Med. (1917), p. 428.

Green Apiol,1 Brit. Pharm. Cod. 1907.

Oil of Parsley , Parrish. Treat, on Phar. (1867), p. 757.

Oleoresina Petroselini, U. S. P. 1910.

OlGoresine de Persil, Culbreth, Mat. Med. (1917), p. 428.

Liquid Apiol , Brit. Pharm. Cod. 1907.

1 "Green apiol” is stated to be an alcoholic extract of the parsley fruit;

"yellow apiol,” the product obtained on treating this extract with animal

charcoal, or upon saponifying the same with lead oxide; and "white apiol”

the volatile oil obtained on distilling the extract with steam. Brit, and

Col. Drugg. (1910), 58, p. 235.

The compound, C12H1404, spoken of in chemical literature as apiol is known

commercially as crystalline apiol. Brit. Pharm. Cod. (1907), p. 112.

1104 Wisconsin Academy of Sciences , Arts , and Letters.

History.

The oleoresin of parsley appears to have come into existence

through the attempts which were made to discover a simple

method for the preparation of the so-called “apiol” of Homolle

and Joret,1 which was first brought to the attention of the phar¬

macist in 1855. The first mention of the oleoresin, insofar as

could be determined with the information at hand, is to be

found in Parrish’s Treatise on Pharmacy published in 1867.

Since that time, the preparation, or one of a similar nature, has

been on the market under the name of “ green apiol” or “liquid

apiol,” but was never given official recognition until the ap¬

pearance of the present edition of the United States Phar¬

macopoeia.

Drug Used , Its Collection, Preservation, Etc.

In the present edition of the United States Pharmacopoeia,

parsley fruit is defined as follows: “The dried ripe fruit of

Petroselinum sativum Hoffman (Fam. Umbelliferae), without

the presence or admixture of more than 5 per cent, of foreign

seeds or other matter. Preserve Parsley Fruit carefully in

tightly-closed containers protected from light. ” The plant

from which the fruit is obtained has also been known under the

following botanical synonyms: Carum Petroselinum Benth.

and Hook., and Apium Petroselinum Linne.

Parsley is an annual herb commonly cultivated in the gar¬

dens of Europe and America. The fruit ripens in the fall,

when it is gathered, dried and preserved for domestic use or

shipped to market. The fruit as found in the market shows

no marked difference in appearance regardless of its source.

However, it is known to differ in its chemical composition. Thus,

the fruits grown in Germany contain apiol as the principal

constituent of therapeutic importance, whereas, those grown

in France contain myristicin.2 The volatile oil content also

appears to vary with the source as Flueckiger3 states that the

1 The "apiol” of Homolle and Joret is stated to be the product which re¬

mains unsaponifled when the ether or chloroform soluble portion of the alco¬

holic extract of parsley fruit is heated with litharge. Journ. de Fharm. et

de Chim. (1855), 28, p. 212.

2 See under "Chemistry of parsley fruit”.

3 PharmaJcognosie des Pflanzenreichs (1891), p. 938.

Du Mez — The Galenical Oleoresins.

1105

fruits grown in Norway have an exceptionally strong odor.

Both of the foregoing variations in the composition of the drug

would naturally be imparted in an increased degree to the

oleoresins prepared therefrom. As the chemistry of the

American fruit does not appear to have been studied, its value

in this connection cannot be said to be definitely established.

There is good reason, however, to believe that the oleoresins

made in this country, in part at least, are prepared from home

grown fruits.1

The large amount of fixed and volatile oils present in these

fruits requires that they be preserved in tightly closed con¬

tainers protected from the light.

U. S. P. Text and Comments Thereon.

The oleoresin was given official recognition for the first time

by being admitted to the late edition of the United States Phar¬

macopoeia (edition of 1910).

1910

Oleoresina Petroselini

Oleoresin of Parsley Fruit

Oleores. Petrosel. — Liquid Apioi

Parsley Fruit,1 in No. 60 powder,2 tillation on a water-bath,6 and, hav-

five hundred grammes . . . . 500 Gm. ing transferred the residue to a dish,

Ether,3 a sufficient quantity. remove the remaining ether by spon-

Place the parsley fruit in a cylin- taneous evaporation in a warm place,

drical glass percolator provided with a stirring frequently.7 Allow the oleo-

stop-cock and arranged with a cover resin to stand without agitation for

and a receptacle suitable for volatile four or five days, decant the clear

liquids.4 * Pack the powder firmly, liquid portion from any solid residue,8

and percolate slowly with ether, and preserve it in well-stoppered bot-

added in successive portions until the ties.9

drug is exhausted.6 Recover the Average Dose. — Metric, 0.5 mil —

greater portion of the ether by dis- Apothecaries, 8 minims.

1) For a description of the drug, see page 1104 under “Drug

used, its collection, preservation, etc. ”

2) The Pharmacopoeia directs that the fruit be reduced to a

1 Joseph K. Janks in his book on spices states that} parsley is being grown in this

country. Jos. K. Janks, Spices, New York (1915), p. 69.

Culbreth on page 428 of the 1917 edition of his work on Materia Medica also refers

to the cultivation of parsley in the United States.

70— S. A. L.

1106 Wisconsin Academy of Sciences, Arts , and Letters.

No. 60 power for percolation. Owing to the large fatty oil

content, this degree of fineness is difficult to attain, and, as

experiments conducted in the laboratory indicate that a No.

40 powder is equally satisfactory for this purpose, it appears

that a change to this effect in the pharmacopooeial directions

is desirable.

3) Ether is the solvent directed by the Pharmacopoeia to be

used for the extraction of the substances constituting the oleo-

resin. Observations made in the laboratory indicate that

other solvents may also be employed for this purpose without

in any way detracting from the value of the finished product.

Thus, acetone and petroleum ether were found to yield pro¬

ducts almost identical with that obtained by the use of ether.

The latter is to be preferred to benzin as suggested by Bering-

er (1892) since its composition is more constant. Alcohol

which is used commercially in the preparation of some of the

so-called liquid apiols dissolves a considerable amount of col¬

oring matter and other inert substances and, therefore, yields

a product of inferior quality.

4) For a description of the various forms of percolators which

have been designed to meet the specifications of the Pharma¬

copoeia, see Part I under “Apparatus used”.

5) The pharmaeopoeial directions governing the extraction of

the oleoresinous material are to slowly percolate the drug with

ether, added in successive portions, until complete exhaustion

has been effected. Here again, the use of some form of contin¬

uous extraction apparatus would appear to be an improve¬

ment over the present method.

6-7) For comments on this step in the pharmaeopoeial method

of preparation, see under comments on the oleoresin of cubeb.

8) Upon the complete removal of the solvent from the perco¬

late, the residual oily liquid deposits a small amount of waxy

matter which the Pharmacopoeia directs shall be removed by

decantation. When either is the solvent used in extracting

the drug, this deposit amounts to less than 1 per cent of the

oleoresin, while the percentage is somewhat greater, about 1.5

per cent when acetone is used. The deposit resulting when

benzin was the solvent employed was found by Beringer to be

equal to about 3 per cent.

9) The oleoresin should be kept in well-stoppered bottles as

Du Mez—The Galenical Oleoresins.

1107

it loses volatile oil upon exposure to the air, and as the glycer¬

ides are prone to undergo partial decomposition due to the ac¬

tion of the moisture and oxygen.

Yield.

The information at hand is not sufficient to permit of a state¬

ment being made as to what the average yield of oleoresin

should be in this case. The results obtained in the laboratory

and those reported by Beringer show that it is at least 24 per

cent., when ether or acetone are the solvents employed in ex¬

tracting the drug, whereas those reported by Vanderkleed

would appear to indicate that the yield is much lower. The

available information of this nature is given in the following

tables :

Table 107 — Yield of oleoresin as reported in the literature.

Table 108 — Yield of oleoresin as obtained in the laboratory.

1108 Wisconsin Academy of Sciences, Arts, and Letters.

Chemistry of the Drug and Oleoresin.

Enumeration of Constituents.

The following are the known constituents of parsley fruit which

may be considered of pharmaceutical interest; volatile oil, fatty

oil, apiin, and inorganic substances. While analyses of the

oleoresin have not been reported, the first two named constitu¬

ents of the fruit, together with a small amount of inorganic

matter, very likely represent this preparation when made by

extracting the drug with ether, as apiin is stated to be insoluble

in this solvent.

Occurrence and Description of Individual Constituents.

Volatile Oil.1 The volatile oil of parsley fruit is described as a

colorless or yellowish, thick liquid having a specific gravity of

1.03 to 1.10 at 15° C. The angle of rotation in a 100 milli¬

meter tube is given as -5° to -10°. It is soluble in alcohol, ether,

chloroform and petroleum ether. On cooling or shaking with

water, it precipitates apiol.2

The composition of the oil varies with the locality in which

the fruit is grown. The principal constituent of the oil dis¬

tilled from the fruit grown in Germany is apiol. Myristicin

is present only in very small quantities.3 It is stated that the

apiol content is often so great that the oil is a semi-solid at or¬

dinary temperatures. In the French oil, myristicin predom¬

inates, while apiol, together with allyltetramethoxybenzene, is

present in small amount.4 The constitution of these compounds

is represented by the following formulas:

1 The following list comprises the more important references to the earlier

literature on the volatile oil: Bley, Trommsdorff’s neues Journ. (1827), 14,

p. 134; Bolle, Arch, der Pharm. (1829), 29, p. 168; Blanchet and Sell, Ann.

der Chem. (1833), 6, p. 301; Loewig and Weidmann, Ibid. (1839), 32, p.

283; von Gerichten, Ber. der. deutsch. chem. Ges. (1876), 9, pp. 258 and

1477.

2 Schimmel & Co., Ber. (1906), p. 95.

3 Thoms, Ber. der deutsch. chem. Ges. (1903), 36, p. 3451; Ibid (1908),

41, p. 2753; Chevalier, Bull. sci. pharmacologique (1910), 17, p. 128; Chem.

Abs. (1911), 5, p. 1490.

4 Ibid. Also, Bignami and Testoni, Gaz. Chim. ital. (1900), 30, p. 240.

Du Mez — The Galenical Oleoresins.

1109

C.CHj.CH :CH2

C.CHj.CH :CHj

(6)

Myristicin

HC

H,COC

C.CH,.CH : CHa

COCH,

III

Nsi

t-allyl.- 2. 3. 4,5.

teiramethoxybenzene

(7)

Apiol is a crystalline solid possessing in a strong degree the

odor of parsley. Its melting point is 30 °C and the boiling

point 294° C.8 Eykman9 gives the specific gravity at 14° C as

1.176, and the refractive index [n]D as 1.538. It is soluble in

alcohol, ether, chloroform and oils. It also dissolves in con¬

centrated sulphuric acid, the solution formed being blood-red

in color.

Myristicin is a liquid possessing but little odor. It does not

solidify even when cooled to a comparatively low temperature.

Semmler10 gives the specific gravity as 1.141 at 25° C. Its

solubility is similar to that of apiol.

In addition to the foregoing, Thoms* 11 reports the presence

of the following in both, the German and French oils : 1-pinene,

phenols and palmitic acid.

Semmler12 reports the volatile oil content of parsley fruil

to be 2 to 6 per cent.

Fatty Oil.13 The fatty oil of parsley fruit is a greenish yellow

mobile liquid. It is soluble in a mixture of alcohol and ether,

in ether, chloroform and carbon disulphide. A sample from

Schimmel & Co., examined by von Gerichten and Koehler,14

5 Eykman, Ber. der. deutsch. chem. Ges. (1890), 23, p. 862; Thoms, Ihid.

1903, 36, p. 174.

6 Thoms. Chem. Zt g. (1903). 27, p. 938.

7 Thoms. Ber. der. deutsch. chem. Ges. (1908), 41, p. 2761.

8 Ciamician and Silber, Ibid. (1888), 21. p. 1632.

»l. c.

10 Semmler, Die aetherische Oele (1907), 4, p. 168.

11 Arbeit en aus d. Pharm. Inst., TJniv. Berlin (1909), 6, p. 190.

12 Semmler. Die aetherische Oele (1907), 4, p. 173.

13 Grimme obtained 16.7 per cent, of a red-brown oil having the following

properties: specific gravity at 15° C, 0.9243; refractive index at 35° C, 1.4778;

saponification value, 176.5; iodine value, 109.6; acid value, 3.4; unsaponifi-

able matter, 2.18 per cent. He was unable to obtain a test for the presence

of phytosterin in the unsaponifiable residue. Pharm, Centralh. (1911), 52,

p. 663.

14 Ber. der. deutsch. chem. Ges. (1909), 42, p. 1638.

1110 Wisconsin Academy of Sciences , Arts, and Letters.

showed the following properties: specific gravity at 15° C, 0.972;

refractive index at 40°C, 1.4624; saponification value, 190.9;

iodine value, 80.07.

The saponifiable portion of the oil was found to be com¬

posed of the glyceryl esters of oleic, palmitic, stearic and

petroselinic acids. The latter is stated to be isomeric with

oleic acid. From the unsap onifiable residue, Matthes and

Heintz15 isolated a hydrocarbon, C20H42, to which they gave the

name petrosilan; also, myricyl alcohol and a mixture giving a

test for phytosterin.

The average fatty oil content of the fruit is probably about

20 per cent.16

Apiin.17 Apiin (C27H32016) is a glucoside. Its melting

point is stated to be 228 °C. On hydrolysis, it yields a sugar

and apigenin (trioxyflavon) C15H10O5. It is soluble in hot

alcohol or water, insoluble in ether, and therefore, it is not

likely to be present in the oleoresin.

Ash. Avaliable information concerning the constituents of

the ash of parsley fruit is limited to the anaylsis of Rump,18

who reports the presence of the basic elements, K, Ca, Mg and

Fe in combination with the acids, HC1, H2S04, H3P04, H2C03

and H2Si03, also, some free Si02.

The ash content19 of parsley fruit is about 6.50 to 7.00 per

cent. Commercial samples sometimes show a higher percentage

of ash due to contamination with foreign matter.20

Constituents of Therapeutic Importance.

The oleoresin of parsley fruit is said to be used chiefly as an

emmenagogue. Such being the case, its therapeutical value

is undoubtedly due to the volatile oil which it contains as both

apiol1 and myristicin,2 constituents of the essential oil, have

15Ber. der. pharm. Ges. (1909), 19, p. 325.

18 Rump, obtained 22 per cent, of fatty oil. Buchner’s Repert. f. d. Pharm.

(1836), 6, p. 6. Grimme gives the yield as 16.7 per cent. 1. c.

17 von Gerichten, Ber. der deutsch. chem. Ges. (1876), 9, p. 1121.

18 Buchner’s Repert. f. d. Pharm. (1836), 56, p. 26.

19 Rump gives the ash content as 6.5 per cent. Ibid. Warnecke reports

the percentage of ash as 7.04. Pharm. Ztg. (1886), 31, p. 536.

20 La Wall and Bradshaw report two commercial samples of parsley fruit

yielding 6.61 and 9.10 per cent, of ash, respectively. Proc. A. Ph. A. (1910),

58, p. 752.

1 Heffter, Arch. f. exp. Path. u. Pharmak. (1895), 35, p. 365. Chevalier

Bull. Sci. pharmacologique, 17, pp. 128-131.

2 Juerss, Schimmel & Co., Ber. (1904), p. 159.

Du Mez- — The Galenical Oleoresins.

1111

been shown to be severe intestinal irritants. The activity of

the volatile oil may be further accounted for by the presence

of terpenes as these compounds are also known to be irritants.3

Physical Properties

Color: When spread out in a thin layer on a while porcelain

surface, the oleoresin was observed to be greenish-yellow in

color. The so-called fluid apiols of commerce, preparations

made with alcohol, are of a comparatively deep green color.

Odor: The oleoresin has the agreeable aromatic odor of

parsley.

Taste: The taste is spicy like that of the drug from which

it is prepared.

Consistence: The oleoresin is a rather thin liquid, being of

about the consistence of olive oil.

Solubility: The official preparation is soluble in acetone,

ether, chloroform, carbon disulphide and petroleum ether. It

is almost insoluble in alcohol or water.

Specific gravity: The specific gravities of the oleoresins pre¬

pared in the laboratory were found to be 0.937 and 0.940 at 25 °C.

In the making of these preparations ether and acetone, respec¬

tively, were employed as menstrua for extracting the drug. The

specific gravity of the only commercial sample, conforming in its

general properties to the official product, was observed to be

about the same, i. e. 0.943. In the case of the other commercial

products, the greater density is thought to be due to the use of

alcohol in their preparation.1 The results for the determina¬

tions made in the laboratory follow.

Table 109 — Specific gravities of oleoresins prepared in the laboratory.

3Kehrer, Arch. f. Gyn. (1910), 90, p. 169.

1 This statement is also based on the dark green color of the preparations

and the fact that alcohol is the solvent mentiond in the literature in con¬

nection with the preparation of the so-called fluid apiols. See under "His¬

tory” of the oleoresin.

1112 Wisconsin Academy of Sciences , Arts, and Letters .

Table 110 — Specific gravities of commercial oleoresins.

1 Apiol, fluid, — Squibb.

2 Apiol, fluid, green, — Merck.

Refractive index: Observations made in the laboratory in¬

dicate that the oleoresin should have a refractive index of

about 1.477 at 25°C, when ether or acetone are employed in the

extraction of the drug. A result almost identical with the

preceding was obtained for the only commercial sample ex¬

amined. The refractive indices observed in the case of the

so-called liquid apiols were somewhat higher, due very likely

to the use of alcohol in their preparation. The data given in

the following tables illustrate these points.

Table 111 — Refractive indices of oleoresins prepared in the laboratory.

Table 112 — Refractive indices of commercial oleoresins.

1 Apiol, Fluid — Squibb.

2 Apiol, Fluid, Green, — Merck.

Du Mez — The Galenical Oleoresins.

1113

Chemical Properties .

Loss in weight on heating: The oleoresins prepared in the

laboratory, using ether and acetone as menstrua for exhausting

the drug, lost 7.87 and 7.92 per cent, of their weight, respec¬

tively, on heating at 110° C. In the case of the only com¬

mercial sample examined, the loss was about one-half as

great due very likely to a smaller amount of volatile matter

(essential oil) being contained in the drug from which the lat¬

ter was prepared. The results obtained are given in the

tables which, follow.

Table 113 — Laboratory preparations — loss in weight on heating.

Table 114 — Commercial oleoresins — loss in weight on heating.

Ash content: The results obtained in the determination of

the ash content of the oleoresins examined in the laboratory are

given in the tables which follow. Aside from the fact that the

amount of ash obtained varied with the solvent used in the

making of the preparations, the only items of importance

brought out by these results are that ether was evidently em¬

ployed in the manufacture of the commercial product and that

the latter contained copper.

Table 115 — Ash contents of oleoresins prepared in the laboratory.

1114 Wisconsin Academy of Sciences, Arts, and Letters.

Table 116 — Ash contents of commercial oleoresins .

Acid number: The acid numbers obtained for the oleoresins

prepared with acetone and ether were found to be 9.3 and 9.2,

respectively, indicating that the difference in the nature of the

two solvents has but little influence on the value of this con¬

stant. The high value found for the sample obtained from

Sharp & Dohme is thought to be due to the hydrolysis of some

of the glycerides, and, therefore, to indicate an old preparation,

or one that has been prepared from old deteriorated drug. The

acid numbers obtained for the oleoresins examined, also those

found for the so-called liquid apiols, are given in the tables

which follow.

Table 117 — Acid numbers of oleoresins prepared in the laboratory.

Table 118 — Acid numbers of commercial preparations.

1 Apiol, Fluid, Green.

Saponification value: The saponification values of the oleo¬

resins prepared in the laboratory, using ether and acetone as

menstrua for extracting the drug, were found to be 158.5 and

165.6, respectively. The high value (181.6) obtained for Sharp

Du Mez — The Galenical Oleoresins.

1115

& Dohme’s preparation is thought to be due to the presence of a

relatively large amount of the glyceride of petroselinie acid,

which is stated by von Gerichten to have a saponification value

of 191.2. See under “'Chemistry of the drug and oleoresin. ”

Tables showing the saponification values of the preparations

examined in the laboratory follow. For comparison with the

foregoing data, the values obtained for the so-called liquid

apiols have also been included in these tables.

Table 119 — Saponification values of oleoresins prepared in the

laboratory.

Table 120 — Saponification values of commercial preparations.

1 Apiol, Fluid, Green, — Merck.

2 Apiol, Fluid,— Squibb.

Iodine value: The iodine values as found for the oleoresins

prepared in the laboratory are given in the first of the tables

which follow. It will be observed that there is a considerable

difference in these values due to the nature of the solvent em¬

ployed in extracting the drug. The low iodine value observed

for the preparation made by Sharp & Dohme is to be attributed

to the partial oxidation of the unsaturated glycerides. For

comparison, the iodine values of two samples of so-called

“liquid apiols” ( preparations made with alcohol) have been

included in the tables which follow.

1116 Wisconsin Academy of Sciences , Arts , and Letters.

Table 121 — Iodine values of oleoresins prepared in the laboratory.

Table 122 — Iodine values of commercial preparations.

1 Labeled “Apiol-Fluid.”

2 Labeled Apiol, Fluid, Green.

Adulterations.

A trace of copper was found to be present in the commercial

samples examined. See under “Ash content.”

OLEORESIN OF PEPPER

Synonyms

Aetherisches Pfefferextrakt , Nat. Disp. 1884.

Ethereal Extract of Black Pepper, King’s Am. Disp. 1900.

Extractum Piperis, Hirsh, Univ. P. 1902, No. 1244.

Extractum Piperis Fluidum, U. S. P. 1850.

Fluid Extract of Black Pepper, U. S. P. 1850.

Oil of Black Pepper, King’s Am. Disp. 1900.

Oleoresina Piperis, U. S. P. 1900.

OlCoresine de Poivre voir, U. S. Disp. 1907.

History.

The oleoresin of pepper appears to have been first obtained

as a by-product1 in the preparation of piperine. Thus, Dr.

Meli in France as early as 1825, reported having obtained the

so-called “oil of black pepper” as a residue on separating the

piperine from the alcoholic extract of the drug. The first

notice of its use as a therapeutic agent apparently came from

1Jourdan, Univ. P. (1832), p. 346

Du Mez — The Galenical Oleoresins.

1117

America as Carpenter, in 1829, in an article on Peruvian bark,

refers to its use by Dr. Chapman of Philadelphia in connec¬

tion with the administration of quinine. The oleoresin prepared

with ether became official in the United States Pharmacopoeia

in 1850 under the title Extractum Piperis Fluidum. In the

1860 edition, the name was changed to Oleoresina Piperis, under

which title, it is still official at the present time. Neither this

preparation nor one of a similar nature has ever been given of¬

ficial recognition abroad.

Drug Used, Its Collection, Preservation , Etc.

According to the present edition of the United States Phar¬

macopoeia, the drug recognized is “the dried, unripe fruit of

Piper nigrum Linne (Fam. Piperaceae), without the presence

or admixture of more than two per cent of stems or other for¬

eign matter. ’ ’ It has also occassionally been referred to under

the botanical synonyms, Piper trioicum Roxb.

As becomes apparent from the foregoing, only the unripe

fruits should be used. As the fruit reaches maturity, the

chlorophyll content diminishes and it becomes less pungent.1

A variation in the chlorophyll would naturally effect the prop¬

erties of the oleoresin prepared therefrom, while a difference

in piperine content would have no significance in this connec¬

tion as only a small portion of the total piperine (to which pep¬

per owes its pungency)2 remains in solution in the oleoresin,

the greater part being precipitated upon the ermoval of the sol¬

vent.

Pepper, as it occurs on the market, consists of a number of

commercial varieties, viz: Malabar, Cochin, Penang, Singapore,

Siam and others.3 The quality of these varieties is ordinarily

governed by weight, the Malabar being the heaviest. The

Penang, however, is stated to be the most pungent. The man¬

ner in which either of these qualities effect the oleoresin does

not appear to have been determined. While the Pharmacopoeia

makes no provisions for the preservation of this drug, its volatile

oil content necessitates the use of closed containers.

1 Flueckiger, Pharmakognosie des Pflanzenreiches (1891), p. 913.

2Kayser, Chem. Centralb. (1888), 59, p. 261.

3 Jos. K. Janks, Sluices, New York, (1915), p. 10.

1118 Wisconsin Academy of Sciences , Arts , and Letters.

JJ. S. P. Text and Comments Thereon.

The oleoresin of pepper has been official in the United States

Pharmacopoeia since 1850, when it was recognized under the

title of Extractum Piperis Fluidum.

1850

Extractum Piperis Fluidum

Fluid Extract of Black Pepper

Take of Black Pepper,1 in powder,2 heat, apint and a half of ether,® and

a pound; expose the residue in a shallow ves-

Ether,3 a sufficient quantity. sel, until the whole of the ether has

Put the powder into a percolator,4 evaporated,7 and the deposition of

and pour ether gradually upon it until piperin in crystals, has ceased. Lastly,

two pints of filtered liquor are ob- separate the piperin by expression

tained.5 From this distill off, by through a cloth,8 and keep the liquid

means of a water -bath, at a gentle portion.

1860

Oleoresina Piperis

Oleoresin of Black Pepper

Extractum Piperis Fluidum, Pharm., 1850

Take of Black Pepper,1 in fine pow¬

der,2 twelve troy ounces;

Ether,3 a sufficient quantity.

Put the Black Pepper into a cylin¬

drical percolator,4 press it firmly, and

gradually pour ether upon it until

twenty-four fluidounces of filtered

liquid have passed.6 Becover from

this, by distillation on a water-bath,

eighteen fluidounces of ether,® and

expose the residue, in a capsule, until

the remaining ether has evaporated,7

and the deposition of piperin in cry¬

stals has ceased. Lastly, separate

the oleoresin from the piperin by ex¬

pression through a muslin strainer,8

and keep it in a well-stopped bottle.9

Du Mez — The Galenical Oleoresins.

1119

1870

Oleoresina Piperis

Oleoresin of

Take of Black Pepper,1 in fine pow¬

der,2 twelve troy ounces;

Ether,3 a sufficient quantity.

Put the Black Pepper into a cylin¬

drical percolator provided with a

stop-cock, and arranged with cover

and receptacle suitable for volatile

liquids,4 press it firmly, and gradually

pour ether upon it, until twenty fluid

ounces of liquid have slowly passed.0

Black Pepper

Recover the greater part of the ether

by distillation on a water-bath,6 and

expose the residue, in a capsule, until

the remaining ether has evaporated,7

and the deposition of piperin in crys¬

tals has ceased. Lastly, separate the

oleoresin from the piperin by expres¬

sion through a muslin strainer,8 and

keep it in a well-stopped bottle.9

1880

Oleoresina Piperis

Oleoresin of Pepper

Pepper,1 in No. 60 powder,2 one hun¬

dred parts . 100

Stronger Ether,3 a sufficient quantity.

Put the pepper into a cylindrical

percolator, provided with a cover and

receptacle suitable for volatile liquids,4

press it firmly, and gradually pour

stronger ether upon it, until one hun¬

dred and fifty (150) parts of liquid

have slowly passed.6 Recover the

greater part of the ether by distilla¬

tion on a water-bath,6 and expose the

residue, in a capsule, until the re¬

maining ether has evaporated,7 and

the deposition of piperine, in crystals,

has ceased. Lastly, separate the

oleoresin from the piperine by ex¬

pression through a muslin strainer.8

Keep the oleoresin in a well-stopped

bottle.9

1890

Oleoresina Piperis

Oleoresin

Pepper,1 in No. 60 powder,2 five hun¬

dred grammes . . 500 Gm.

Ether,3 a sufficient quantity.

Put the pepper into a cylindrical

glass percolator, provided with a stop¬

cock, and arranged with a cover and

receptacle for volatile liquids.4 Press

the drug firmly, and percolate slowly

with ether, added in successive por¬

tions, until the drug is exhausted.5

Recover the greater part of the ether

of Pepper

from the percolate by distillation on a

water-bath,6 and, having transferred

the residue to a capsule, set this aside

until the remaining ether has evapor¬

ated,7 and the deposition of crystals of

piperine has ceased. Lastly, sepa¬

rate the oleoresin from the piperin by

expression through a muslin strainer.8

Keep the oleoresin in a well-stop¬

pered bottle.9

1120 Wisconsin Academy of Sciences , Arts , and Letters.

1900

Oleoresina Piperis

Oleoresin of Pepper

Pepper,1 in No. 40 powder,2 five hun¬

dred grammes . 500. Om.

Acetone,3 a sufficient quantity.

Introduce the pepper into a cylin¬

drical glass percolator, provided with

a stop-cock, and arranged with a cover

and a receptacle for volatile liquids.4

Pack the powder firmly, and percolate

slowly with acetone, added in succes¬

sive portions, until the pepper is ex¬

hausted.5 Recover the greater part

of the acetone from the percolate by

distillation on a water-bath,6 and,

having transferred the residue to a

dish, set this aside in a warm place,

until the remaining acetone has evap¬

orated,7 and the deposition of crystals

of piperin has ceased. Lastly, sepa¬

rate the oleoresin from the piperin by

straining through purified cotton.®

Keep the oleoresin in a well-stoppered

bottle.9

Average dose. — 0.030 Gm. — 30 mil¬

ligrammes (*4 grain).

1910

Oleoresina Piperis

Oleoresin of Pepper

Oleores.

Pepper,1 in No. 40 powder,2 five hun¬

dred grammes . 500. Gm.

Ether,3 a sufficient quantity.

Place the pepper in a cylindrical

glass percolator, provided with a stop¬

cock, and arranged with a cover and

a receptacle for volatile liquids.4

Pack the powder firmly, and perco¬

late slowly with ether, added in suc¬

cessive portions until the drug is ex¬

hausted.6 Recover the greater part of

the ether from the percolate by dis-

Piper.

tillation on a water-bath,6 and, hav¬

ing transferred the residue to a dish,

set this aside in a warm place until

the remaining ether has evaporated,7

and the deposition of piperine has

ceased. Lastly, separate the oleo¬

resin from the piperine by straining

through purified cotton.8 Keep the

oleoresin in a well-stopped bottle.9

Average Dose. — Metric, 0.03 Gm. —

Apothecaries, % grain.

1) For a description of the official drug, see page 1117 under

“Drug used, its collection, preservation, etc.”

2) The last two editions of the Pharmacopoeia have specified

that the drug be in the form of a No. 40 powder for percolation.

Previous editions, with the exception of that of 1850, in which

the degree of fineness was not stated, required that a fine

Du Mez—The Galenical Oleoresins. 1121

powder (No. 60) be used for this purpose. The coarser

powder possesses the advantages of being more readily pro¬

duced and of being better adapted to the rapid exhaustion of

the drug.

3) The solvents which have been experimented with in the

preparation of this oleoresin are alcohol, ether, acetone, ben-

zin and petroleum ether. Of these, ether has proven to be the

most satisfactory and is the solvent specified for this purpose

by the present Pharmacopoeia. Acetone, which was directed

to be used by the Pharmacopoeia of 1900, like alcohol, is un¬

satisfactory as the large amount of extractive matter obtained

interferes with the separation of the piperine. Benzin or pe¬

troleum ether, on the other hand, dissolves piperine but

slightly and, therefore, yield a product low in piperine con¬

tent. See tables on page 1134.

4) For a description of percolators adapted to the use of

volatile liquids, as specified for use in this connection by the

Pharmacopoeia, see Part I under “Apparatus used.”

5) With respect to the manner of exhausting the drug, it is

thought that the process of continuous extraction would be a

distinct improvement over the present pharmacopoeial method.

The reasons for this statement have already been given in

the comments of the preceding oleoresins and need not be re¬

peated here.

6-7) As this oleoresin does not appear to undergo any notice¬

able changes upon exposure to the air, except to lose a small

amount of volatile oil, the conditions under which the solvent

is removed from the percolate are not as important as in the

case of the other oleoresins. The time necessary to complete

the preparation, however, can be considerably shortened if

the operation is completed at the temperature of the water

bath, for which reason, this procedure is thought to be justi¬

fied.

8) The Pharmacopoeia directs that the mixture obtained on

evaporating the solvent from the percolate be allowed to stand

until the deposition of the piperine is complete and that the

latter then be separated from the liquid portion by straining

through purified cotton. The object to be attained in allow¬

ing the piperine to deposit is not understood as it has been

found in actual practice that the liquid portion does not sep-

71— S. A. L.

1122 Wisconsin Academy of Sciences , Arts, and Letters.

arate as a rule, but that the whole sets to form a semi-solid

mass owing to the large amount of piperine present. The

means by which the separation of the piperine was accomp¬

lished in the laboratory appears to be more rational and is as

follows : the mixture was heated on the water bath until the

portion constituting the oleoresin was quite fluid when it was

filtered through cotton with the aid of a suction pump. The

piperine which deposited from the filtered oleoresin on cool¬

ing was finally separated by decantation.

9) As the oleoresin loses volatile oil on exposure to the air,

it should be kept in well-stoppered bottles.

Yield .

The yield of oleoresin to acetone or ether is about 4.5 to 6.5

per cent. With petroleum ether, a yield of 3.2 per cent, was ob¬

tained in the laboratory. Aside from the effect which the solvent

has upon the amount of the oleoresin obtained, the temperature at

which the piperin is separated is a factor to be considered. The

higher the temperature at which this is accomplished, the greater

the amount of piperine remaining in solution and the greater

the yield of finished product, and visa versa.

In the tables which follow, the yield of total extract is fre¬

quently reported as oleoresin. These reports should not be

confused with those pertaining to the official preparation, which

consists of the liquid portion only, the precipitated piperine

and other insoluble material having been removed. Data of

this kind have been included here for the sake of comparison

with results of a like nature obtained in the laboratory and in

order to point out the erroneousness of such reports.

Du Mez—The Galenical Oleoresins,

1123

Table 12.3 — Yield of oleoresin as reported in the literature.

Date

1888

1892

1903

1913

Represents total

yield of extract¬

ive matter.

Yield of oleoresin.

Reported as yield

of oleoresin, (x)

Pepper from the

Indies. Total ex¬

tract.

Pepper from Gua¬

deloupe. Total

extract.

Pepper from the

coast of Dahomey.

Total extract.

Represents total

yield of extract.

Reported as yield

of oleoresin. 0 )

(1) Undoubtedly represents total extract.

Table 124 — Yield of oleoresin as obtained in the laboratory.

1124 Wisconsin Academy of Sciences, Arts, and Letters.

Chemistry of the Drug and Oleoresin.

Tabulation of Constituents.

The chemistry of black pepper has been the subject of a

number of investigations1 conducted during the past century.

As a result of these investigations, the presence of the follow¬

ing substances of pharmaceutical interest has been established:

volatile oil, piperine, resin, starch, coloring matter and inor¬

ganic constituents. In addition to the foregoing, the presence

of fatty oil, piperidine and methyl pyrroline has been reported.

The following are stated by Kayser and others2 3 to be present

in the oleoresin when prepared with ether :

Volatile Oil

Fatty Oil

Piperine

Resin

Coloring Matter

Ash

Occurrence of Description of Individual Constituents.

Volatile Oil:5 According to the report of Schimmel and

Company,4 the volatile oil of pepper is a colorless or yellowish-

green liquid, having a phellandrene-like odor. At 15°C, the

specific gravity is given as 0.88 to 0.905 and the angle of ro¬

tation in a 100 millimeter tube as -5° 2' to -j- 2° 27'. It is

stated to be soluble in 15 parts of alcohol (90 per cent).

Early attempts to determine the composition of the oil were

made by Dumas,5 and Soubeiran and Capitaine.6 In 1887,

Eberhardt7 isolated a 1-terpene which he failed, however, to

1 Among those who have reported more or less complete analyses of pepper

the following may be mentioned: Pelletier, Ann. de Chim. et de Phys. (1821),

16, p. 337; Luca, Tschenb. f. Scheidekiinstl. u. Apoth, (1822), 43, p. 81; H.

Rottger, Arch. f. Hygiene (1886), 4, p. 183; Richardson, U. S. Dept, of

Agric. Bull. No. 13, (1887), p. 206; Johnstone, Chem. News (1888), 58, p.

235; Kayser, Chem. Centralb. (1888), 59, p.261 ; Weigle, Apoth. Ztg. (1893),

8, p. 468; Hebebrand, Zeitschr. Unters. Nahr. u. Genussm. (1896), p. 345 ;

Winton, Ogden and Mitchell, Ann. Rep. Conn. Exp. Sta. (1898), p. 198;

Balland, Journ. de Pharm. et de Chim. (1903). 157, p. 296.

2 Kayser, Weigle, Balland, l. c.

3 The description of the oil as here given is for that obtained from the

fruit by distillation with steam.

1 Schimmel & Co., Semi-Ann. Rep.. Oct. 1893, p. 34.

6 Ann. d. Chem. (1835), 15. p. 159 ; Journ. f. prakt. Chem. (1835), 4, p. 434.

6 Journ. de Pharm. et de Chim, (1840), 26, p. 83\

TArch. der Pharm. (1887), 225, p. 515.

Du Mez — The Galenical Oleoresins.

1125

identify. Schimmel and Company8 have reported the presence

of phellandrene and cadinene.

From 0.70 to 2.2 per cent, of volatile oil has been obtained

from the fruits by steam distillation.9

Piperine.10 Piperine (C17H19N03) was first isolated by

Oersted in 1819.11 It is a weak base crystallizing from alcohol

in colorless, shining, four sided prisms, the melting point of

which is 128 to 129 °C. It is slightly soluble in boiling water,

readily soluble in alcohol, ether, chloroform, benzene and volatile

oils, slightly soluble in petroleum ether. When acted upon by

solutions of the alkalies, it is hydrolyzed breaking down into

piperidine and piperic acid. Its constitution is represented

by the following structural formula:12

The quantity of piperine present in the fruit of black pepper

as obtained on the market varies to a considerable extent. This

variation is very probably due in greater part to natural causes,

such as the age of the fruit before harvesting, climatic condi¬

tions under which grown, et cetera.13. The yield is variously

stated as being from 4.05 to 13.02 per cent.14

8 1. c. .

9 A yield of 0-7 to 1.69 per cert, of volatile oil is reported by C. H. Rich¬

ardson l. c. W. Johnstone obtained 0.98 to 1.87 per cent. Analyst (1889),

14, p. 41. G. Teyxeira and B. Ferrucio give the yield as 1.4 per cent. Bull.

Chim. Fharm. (1900), 38, p. 534; Chem. Centralb. (1900), 71, p. 736. Schim¬

mel & Co. (1. c.) report the yield as 1.3 to 2.2 per cent.

10 Rochleder, Ann. d. Chem. (1845), 54, p. 255; Babo and Keller, Journ. f.

prakt. Chem. (1857), 72, p. 53 ; Rugheimer, Ber. d. deutsch. chem. Ges.

„ (1882), 15, p. 1390.

11 Schweitz. Med. Journ. (1819), 29, p. 80; Buchner, Repert. f. die Pharm.

(1820), 10, p. 127.

12 Ladenburg and Scholtz, Ber. d. deutsch. chem. Ges. (1894), 27, p. 2958.

13 Caseneuve and Caillot report the piperine content to be as follows :

Sumatra. 8.10 per cent; Singapore, 9.15 per cent; Penang, 5.24 per cent. 1. c.

G. Graff gives the following percentages of ether soluble nitrogenous matter

as piperine: Java, 5.85 to 9.5 per cent.; Lampong, 5.13 to 7.09 per cent.;

Penang, 9.12 to 9.42 per cent. ; Saigon, 6.16 per cent. ; Singapore, 11.08 per

cent. Zeitschr. f. offentl. Chem. (1908), 14, p. 425.

14 W. Johnstone obtained 5.21 to 13.03 per cent of piperine from nine

samples of black pepper, l. c.

C. Heisch gives the yield as 4.05 to 9.38 per cent. Analyst (1886), 11.

p. 186.

F. Stevenson reports the presence of 7.14 per cent, or piperine. Ibid. 12,

p. 144.

1126 Wisconsin Academy of Sciences , Arts , and Letters.

Resin . The presence of 1.25 to 2.08 per cent, of resin in

black pepper has been reported.15 Buchheim,16 the only in¬

vestigator who appears to have attempted to isolate the same

in sufficient purity to determine its composition, states that it

is a condensation product of piperidine with an acid, to which

he gives the name Chavicinsaure. He assigns the name Chavicin

to this compound, and describes it as a yellowish-brown mass

soluble in alcohol, ether, petroleum ether and the other com¬

mon solvents.

Coloring Matter. The green coloring matter in pepper is

stated to be chlorophyll.17 The brown coloring matter observed

in the ethereal or alcoholic extracts has not been identified.

Fatty Oil.18 The presence of a fatty oil in black pepper must

be considered doubtful at the present time. Hirsch19 states that

a microscopical examination of the fruit revealed the presence

of a fatty oil in the endosperm. Kayser,20 Weigle,21 and others

mention fatty oil as one of the constituents. None of these

investigators, however, appear to have isolated the oil in a pure

state or to have described it in detail. Ditzler,22 who made this

matter the subject of a special investigation, concluded that

glycerides were absent. Likewise, Gerock23 could obtain no

fat from white pepper.

Piperidine ,24 Piperidine has been named as a constituent of

black pepper by Johnstone,25 who found the average content

of nine samples to be 0.56 per cent. Kayser26 disputes the find¬

ings of Johnstone and states that the base obtained by distilla¬

tion is ammonia.

15 Teyxeira and Ferrucio give the resin content as 1.25 per cent., F.

Stevenson as 1.44 per cent. 1. c.

F. Blyth reports the presence of 1.7 to 2.08 per cent. Foods, Their Com¬

position and Analysis (1903), p. 496.

18 Buchner’s n. Repert. f. Pharm. (1876), 25 p. 335; Pharm. Journ. 1876,

36, p. 315.

17 Arthur Meyer, Das Chlorophyllkorn, Leipzig (1883), p. 2.

18 In the literature on food chemistry, the non-volatile ether extract is

usually spoken of as fat or fatty oil. See WTnton, Ogden and Mitchell, l. c.

19 Flueckiger, Pharmakognosie des Pflanzenreiches (1891), p. 914.

21 l. c.

»Z. c.

23 Arch. d. Pharm. (1886), 224, p. 103.

28 Ibid.

24 As piperidine is one of the products obtained when piperine is hydrolysed,

it is quite probable that it is not a normal constituent of the fruit but is

formed when the powdered material is subjected to distillation.

25 1 c.

29 1 c.

Du Mez ■ — The Galenical Oleoresins.

1127

Piperidine is a colorless limpid liquid having a specific

gravity of 0.8591 at 25 °C, and boiling at 106.3 °C.27 It is

stated to have an odor resembling both, that of ammonia and

pepper. It is a powerful base behaving generally like am¬

monia in its action on the metallic bases. It is soluble in all

proportions in alcohol or water. It has the following struc¬

tural formula.28.

Methyl-Pyrroline. Pictet and Court20 report the occurrence

of 0.01 per cent of methyl-pyrroline in black pepper obtained

from Singapore. The exact constitution has not been deter¬

mined, but the authors are of the opinion that it is a C-methyl

pyrroline represented by one of the following formulas:

Ash. The basic elements, K, Na, Mg, Ca, Fe and Mn, com¬

bined with the acids, HC1, H3P04, H2S04, H2Si03 are the com¬

ponents of the ash of black pepper as determined by Rottger30

and others.31

The average ash content of black pepper is stated by Blyth32

27 Perkin, Chem. Soc. Journ. (1889), 55, p. 699.

25 Hofmann, Ber. der. deutsch. chem. Ges. (1879), 12, p. 985; Koenigs,

Ibid., p. 2341; Ladenburg, Ibid. (1885), 18, pp. 2956 and 3100.

29 Pictet states that he was able to isolate pyrrolidine and N-methyl pyrro¬

line from various leaves by steam distillation after treatment with sodium

carbonate. He is of the opinion that the methyl pyrrolines undergo re¬

arrangement forming pyridine and quinoline rings, thus giving rise to the

more complex alkaloids. Arch. Sci. Phys. Nat. (1905), 19, p. 329; Ber. d-

deutsch. chem. Ges. (1907), 40, p. 3771.

39 Arch. Hyg. (1886), 4, p. 183. „

31 Blyth, Chem. News (1874), 30, p. 170.

32 Ibid.

1128 Wisconsin Academy of Sciences , Arts, and Letters.

to be 4.845 per cent. As high as 8.99 per cent, has been re¬

ported.33.

Constituents of Therapeutic Importance

The oleoresin of pepper is said to be used chiefly in the South,

where it is administered with quinine in the treatment of “in¬

termittent fever.” Its value in this connection is accounted

for by the presence of piperine which has been shown to be an

active antiperiodic.* 1 Piperdine and methyl pyrroline, if pres¬

ent, would impart similar properties,2 while the composition of

the contained volatile oil would indicate a carminative action.

Physical Properties

Color: The color of the oleoresin, when the latter was spread

out in a thin layer on a white porcelain surface, was observed

to be a greenish-brown, closely resembling that of the oleoresin

of cubeb when prepared from the ripe fruits. The so-called oil

of black pepper, sometimes sold as a substitute for the official

oleoresin, is stated to be considerably darker in color due to the

removal of the greater part of the volatile oil.

Odor: The odor, while slight, resembles that of ground

pepper.

Taste: The taste is sharp and spicy, the sharpness becom¬

ing more noticeable after the oleoresin has been retained in the

mouth for a short time.

Consistence: The oleoresin is a thick, sticky liquid which

can only be poured with difficulty. The fluidity is greatly in¬

creased by heating the preparation on a water bath.

Solubility: The oleoresin is completely soluble in alcohol,

ether, acetone, chloroform, carbon disulphide and glacial acetic

acid. It is only partially soluble in petroleum ether and is

insoluble in water.

Specific gravity: The specific gravity of the oleoresin is

fairly constant, only, when similar conditions with respect to

83 Heish reports the ash content of 8 samples of black pepper to be from

4.35 to 8.99 per cent. Analyst (1886), 11, p. 186. Others who have reported

on the ash content of pepper are Bergman, Zeitschr. f. Analyt. Chem. (1882),

21, p. 535, and von Raumer, Zeitschr. angew. Chem. (1893), p. 453.

1Wood, Therapeutics , Principles and Practice , (1908), p. 482.

2 Tunnicliffe and Rosenheim, Centralbl. f. Physiol. (1902), 16, p. 93.

Du Mez—The Galenical Oleoresins.

1129

temperature have been observed during the separation of the

precipitated piperine. A comparatively slight difference in tem¬

perature causes a considerable variation in the amount of the

latter constituent retained in solution, which results in a cor¬

responding variation in the specific gravity of the finished pro¬

duct. This effect is further noticed in connection with the

menstruum employed in extracting the drug, e. g. petroleum

ether which is a poor solvent for piperine yields an oleoresin

relatively low in specific gravity. With respect to the com¬

mercial samples examined, a low specific gravity was, in one in¬

stance, found to be due to the presence of unevaporated solvent.

The tables which follow show the specific gravity of the samples

examined in the laboratory.

Table 125 — Specific gravities of oleoresins prepared in the laboratory .

Table 126 — Specific gravities of commercial oleoresins.

1 The odor of ether was very noticeable.

Refractive index: The refractive index of this preparation

as observed in the laboratory was not constant, varying from

1.521 to 1.696. From an inspection of the first of the tables

which follow, it would appear that this variation was a result

of the influence of the solvent employed in extracting the drug.

While the solvent undoubtedly exerts an influence in this con¬

nection, it does so indirectly, that is, through its effect on the

piperine content.1 The latter, however, is also influenced by

1 See discussions under “Piperine content” and “Yield of oleoresin,” re¬

spectively.

1130 Wisconsin Academy of Sciences, Arts, and Letters.

the temperature at which the preparation is finished— the tem¬

perature at which the liquid oily portion, which constitutes the

official oleoresin, is separated from the deposited material, in¬

cluding the excess of piperine. In the case of commercial

samples, the piperine content and, therefore, the refractive in¬

dex may also be affected by the presence of unevaporated

solvent. The results obtained in the laboratory in the deter¬

mination of this property are given in the tables which follow.

Table 121— Refractive indices of oleoresins prepared in the laboratory.

Table 128 — Refractive indices of commercial oleoresins .

(a) Contained ether.

Chemical Properties .

Loss in weight on heating : A loss in weight varying from

9.49 to 11.52 per cent, was obtained for the laboratory prepara¬

tions, when heated at 110° C, showing that the nature of the

solvent employed in extracting the drug has but little influence

on this property. With respect to the commercial samples ex¬

amined, the loss was much greater, being as high as 32.64 per

cent, in one case. The comparatively great loss in the latter

instance was due to the presence of unevaporated solvent

(ether.) The results obtained in the determination of this

constant in the laboratory follow.

Du Mez — The Galenical Oleoresins.

1131

Table 129 — Laboratory preparations — loss in weight on heating.

Table 130 — Commercial oleoresins — loss in weight on heating.

1 Unevaporated solvent (ether) was present.

Ash content: The ash determinations made on the oleoresins

prepared in the laboratory show that the solvent employed in

their preparation is the chief factor influencing the results ob¬

tained. The official product, in the making of which ether was

the solvent used, yielded 0.11 per cent, of ash, which was about

the percentage yield obtained for one of the commercial samples

examined. The other commercial oleoresin gave 0.29 per cent,

of ash indicating the use of acetone in its preparation. Both

samples contained copper, apparently, however, in quantities

too small to noticeably affect the weight of the ash. The re¬

sults of the determinations made in the laboratory follow:

Table 131 — Ash contents of oleoresins prepared in the laboratory.

1132 Wisconsin Academy of Sciences , Arts , and Letters.

Table 132 — Ash content of commercial oleoresins.

1 Contained ether.

Acid number: The acid number of the oleoresin when pre¬

pared with alcohol, acetone or ether was found to be about 19.

In the case of the two commercial samples examined, however,

the values obtained differed to a considerable extent, being 19.2

in one instance and 27.5 in the other. As the preparation

represented by the first number contained considerable unevap¬

orated solvent, this difference can be accounted for in part. The

high values obtained for the commercial samples are thought to

be due to their relatively low piperine content or to a partial

decomposition of the resin. The values obtained for this con¬

stant in the laboratory follow.

Table 133 — Acid numbers of oleoresins prepared in the laboratory.

Table 134 — Acid numbers of commercial oleoresins.

(a) Contained ether.

Saponification value: As will be observed in an inspection

of the first of the tables which follow, the saponification value

of the oleoresin varies with the solvent employed in its prepara¬

tion. This appears to be due principally to the effect which

the nature of the solvent has upon the pipeline content of the

Du Mez—TJte Galenical Oleoresins . 1133

finished product, e. g. the piperine content of the preparation

made with acetone was found to be 54.36 per cent and the

saponification value 88.6, while the oleoresin when prepared with

petroleum ether, contained only 15.06 per cent, of piperine and

gave a saponification value of 109.5. Other influences, besides

the nature of the solvent, affecting the piperine content may

likewise produce a variation in the saponification value, e. g.

the temperature at which the preparation is made and the

presence of unevaporated solvent in the finished product. The

latter may also have a direct influence. The saponification

values as found for the oleoresins examined in the laboratory

are given in the following tables.

Table 135 — Saponification values of oleoresins prepared in the

laboratory.

Table 136 — Saponification values of commercial oleoresins.

(a) Contained ether.

Iodine value : Iodine values ranging from 88.6 to 95.4 were

obtained for this oleoresin when acetone, alcohol or ether were

the solvents employed in its preparation. This variation is

due to the difference in the piperine content of these oleo¬

resins as a result of operating under different conditions of

temperature when preparing the same, as well as to the nature

of the solvent. Jn addition to these influences, the presence

of unevaporated solvent must also be taken into consideration

in the case of the commercial samples, as is indicated by the

values given in the following tables.

1134 Wisconsin Academy of Sciences, Arts, and Letters.

Table 137 — Iodine values of oleoresins prepared in the laboratory.

(a) Contained ether.

Special Quantitative Tests.

At the present time, there does not appear to be a method in

use for the evaluation of this oleoresin. As its therapeutic

properties are due, in greater part at least, to its pipeline con¬

tent,1 a quantitative method for the estimation of this con¬

stituent appears to offer the best means of determining its

quality.

Method for the Estimation of the Piperine Content.

In the laboratory, the amount of piperine present was com¬

puted from the nitrogen content of the oleoresin, the latter

being determined by the Gunning- Arnold2 method. The re¬

sults obtained are given in the following tables:

Table 139 — Piperine content of oleoresins prepared in the laboratory.

1 See "under “Constituents of therapeutic importance.”

8 Bull. No. 107, Bur. of Chem. (1912), p. 162.

Du Mez — The Galenical Oleoresins.

1135

Table 140 — Piperine content of commercial samples.

The laboratory samples were prepared and tested during

the warm months of summer, which accounts for the high

piperine content. A very considerable amount of the latter

precipitated out during the colder months which followed. It

is, therefore, thought that the results obtained in the case of

the commercial products are the more typical.

Adulterations.

Copper was found to be present in all of the commercial

samples examined. See under “Ash content.”

Bibliography.

Planche 1823

Von den pharmaceutischen Zubereitungen des Lupulins.

Mag. f. Pharm., 1, p. 183. [Trommsdorff’s n. Journ. d.

Pharm., 7, p. 345.]

A method for preparing the alcoholic tincture of lupulin is given. It is

further stated that an extract similar in all respects to the resin said to

have been isolated by Ives results when the alcohol is removed from the

tincture by evaporation.

Geiger, Ph. L. 1824

Versuche liber die chemisehe Zusammensetzung der Wurzel

des maennlichen Farrenkrauts, Polypodium ( Aspidium , Neplt-

r odium) Filix Mas.

Mag. f. Pharm., 7, p. 38.

The article is a review of Morin's analysis of the rhizome of male fern

with a note pointing out that Morin was not the first investigator to make

such an analysis, but that Gebhardt had already published an analysis of

the same in 1821 in an inaugural dissertation delivered at Kiel. Gebhardt

is stated to have used ether for extracting the “oil."

1136 Wisconsin Academy of Sciences , Arts, and Letters.

Morin 1824

Sur la composition chimique de la racine de fougere male,

Polypodium filix mas Linn.

Journ. de Pharm. et de Chim., 10, p. 223. [Mag. f. Pharm.,

7, p. 38.]

In making a chemical examination of the male fern rhizomes, the author

used the method of selective solvents. Upon extracting with ether, as the

first solvent, and subsequently evaporating of the ether, a thick green fatty

oil was obtained. The author considers this fatty substance the active

principle.

Meli 1825

Neue Erfahrungen und Beobachtungen ueber die Art, das

Alkaloid nnd das scharfe Oel des Pfeifers zu gewinnen.

Trommsdorff ’s n. J. d. Pharm., 11, p. 174. [Bull, de seien.

math., phys. et chim., 1825, p. 191.]

It is stated that more than an ounce and a half of piperine and about

four ounces of a sharp tasting oil were obtained from three pounds of

black pepper by extraction with alcohol.

Peschier, Ch. 1825

Oel des maennlichen Farrenkrauts (Aspidium Filix Mas),

ein sehr vorzuegliches und sicheres Mittel gegen den Bandwurm.

Biblioth. univers., Nov. 1825, p. 205. [Mag. f. Pharm., 13,

p. 188.]

The so called oil, Euile de Fougere Mtile, is directed to be prepared by

extracting the powdered male fern rhizomes with ether and subsequently re¬

moving the ether by warming gently.

Buchner, A. 1826

Extractum Filicis maris resinosum.

Repert f. d. Pharm., 23, p. 433.

The preparation of this extract by means of alcohol instead of ether

is recommended. The product thus obtained is spoken of as an Extractum

resinosum. The Euile de Fougere of Peschier is spoken of as the harz-

haltiges Oel. A chemical analysis of the extract is also given.

von Esenbeck, Nees 1826

Farrnkrautwurzelextrakt.

Arch. d. Pharm., 19, p. 153.

The extract is reported to have been prepared by the process of macera¬

tion, ether being the solvent employed. Pour ounces of rhizomes gathered

in August gave 108 grains of extract.

Du Mez — The Galenical Oleoresins.

1137

_ _ 1827

Verhandlungen des pharmaceutischen Vereins in Wuertem-

berg. Repert. f. d. Pharm., 26, p. 441.

Zeller is stated to have prepared the Extractum radicis Filicis marts

resinosum according to the method suggested by Buchner; extraction with

alcohol. The extract obtained in this manner from rhizomes gathered

in September amounted to 30 per cent, of the air dried drug.

Batso, Y. 1827

Dissertatio inangur. chemica de Aspidio filice mare

Quam cons, et anchor, praes et direct, etc., pro summis in scient.

et arte chemica honor, et doct. laurrite cappess. in univers.

vindobon. publ. erudit, disq. submittit Valentinus Batso, N. H.

Debreczino Bibariensis p. 37, 8. Vindobonae, typis Antonii

Pichler. 1826. [Trommsdorff ’s n. Journ. d. Pharm., 14, 2, p.

249.]

In addition to oil, resin and fatty wax, the author finds a free acid and

an alkaloid in the ethereal extract of male fern. He calls the acid Acidum

filiceum and the alkaloid Filicina. He attributes the activity of the extract

to these two substances.

Brandes, R. 1827

Ueber das Extractum oleo-resinosum Filicis.

Arch d. Pharm., 21, p. 253.

The physical properties of the extracts obtained by extracting male

fern rhizome with ether and with Liquor anodynus, respectively, are de¬

scribed.

Buchner, A. 1827

Zur medicinischen und chemischen Geschichte der Filix mas.

Repert. f. d. Pharm., 27, p. 337.

The author speaks of the ethereal extract of male fern as the Extractum

oleoso-resinosum Filicis maris. It is stated to contain a volatile oil, a

green fatty oil, a fatty wax, a brown resin and a volatile acid (probably

acetic acid.)

Van Dyk 1827

Ueber das Oleum Filicis maris.

Arch. d. Pharm., 22, p. 141.

Two ounces of powdered male fern rhizome gave 70 grains of ethereal

extract, while 8 ounces of the rhizome yielded 3 ounces of extractive matter

72 — S. A. L.

1138 Wisconsin Academy of Sciences , Arts, and Letters.

to alcohol. The extract prepared with ether is stated to be dark olive-

green in color and of the consistence of honey, that prepared with alcohol

greenish-brown in color and much thicker.

Geiger, Ph. L. 1827

Analytische Versuche mit der Wurzel des maennlichen

Farrenkrauts und Darstellung des Oels (01. FUicis Maris)

aus derselben.

Mag. f. Pharm., 17, p. 78.

The ethereal extract when prepared from green rhizome, by extraction

with ether in a Realsche Presse is said to be a yellowish -green oily sub¬

stance.

An analysis of this extract showed the presence of 30 per cent, of resin¬

ous material soluble in alcohol, 50 per cent, of a fixed oil and a considerable

amount of volatile substances.

Tilloy 1827

Bereitungsart des Oels des maennlichen Farrenkrauts.

Journ. de Chim. med., 3, p. 154. [Geiger’s Mag. f. Pharm.,

18, p. 157.]

The so-called oil of male fern is directed to be prepared by extracting

the rhizome with alcohol. The alcoholic liquor thus obtained is treated

with lead subacetate, filtered, and the solvent removed by distillation.

The resulting oil is further purified by dissolving in ether and evaporating.

Dublanc, H. 1828

Extrait oleoresineux de Cubebe.

Journ. de Pharm. et de Chim., 14, p. 41.

The author’s method for preparing the oleoresinous extract consists

in distilling off the volatile oil with water, exhausting the dried marc with

alcohol, evaporating off the alcohol, and mixing the residue so obtained

with the volatile oil.

Meylink 1828

Ueber das Extractum oleo resinosum Filicis.

Arch. d. Pharm., 25, p. 243.

Two ounces of the powdered male fern rhizome are reported to have

yielded 58 grains of a dark green, oily extract to ether.

Oberdoerffer 1826

Ueber die Darstellung des Cubeben Extracts.

Arch. d. Apoth. Ver., 24, p. 178.

In the method of preparation, the oil is first obtained by steam distilla¬

tion, the marc remaining in the still, after drying, is then extracted with

Du Mez — The Galenical Oleoresins.

1139

alcohol. The residue remaining after removing the alcohol by evapora¬

tion is mixed with the volatile oil, this mixture constituting the so-called

extract.

Peschier, Ch. 1828

Ueber mehrere schon frueher erschienene Analysen der

Farrenkrautwurzel (Aspidium filix mas L.) und ueber die

Gewinnung seines harzigen Oels.

Trommsdorff ’s n. Journ. d. Pharm., 17, p. 5.

The vermifuge properties of male fern are said to be due to its ol€o-

resine (oelharz) content. This the author prepares by extracting the

drug with ether and subsequently evaporating the solvent, (p. 8.) It is

further stated that this oleosesine remains perfectly homogenous after

months if prepared from freshly gathered rhizomes, but deposits a white

granular substance when old rhizomes are used (p. 9.)

According to the author’s analysis the oleoresine consists of a volatile

aromatic oil, a fatty oil, resin, stearin, green and red coloring materials,

acetic and gallic acids.

Winkler, F. L. 1828

Einige Worte ueber die Bereitung des 01. Filic. Maris.

Geiger’s Mag. f. Pharm., 22, p. 48.

The “oil” extracted with ether is said to be a mixture of oil, resin

and oxidized tannin. Twelve ounces of rhizomes gathered in February

yielded 15 drachms of extract. Two drachms of this extract yielded 43

grains of fatty oil.

Allard 1829

Note sur l’huile de fougere.

Journ. de Pharm. et de Chim., 21, p. 292.

The powdered rhizome of the male fern is directed to be extracted with

alcohol and the alcoholic extract after evaporating off the solvent, washed

with water. The extract is then further purified by solution in ether and

subsequent evaporation.

Carpenter, G. W. 1829

Observations and Experiments on Peruvian Bark.

Silliman’s Am. Journ., 16, p. 28. [Buchner’s Repert f. d.

Pharm., 34, p. 446.]

In the discussion of the therapeutic uses of the various constituents of

Peruvian bark, it is stated that Dr. Chapman of Philadelphia prescribed

piperin and oil of pepper in combination with quinine. The oil of pep¬

per is said to be the more active therapeutically, one drop of oil being

equivalent to three grains of piperin (p. 39.)

1140 Wisconsin Academy of Sciences , Arts , and Letters.

Haendess 1829

Ueber 01. filieis maris.

Arch. d. Pharm., 28, p. 212.

Four ounces of powdered male fern rhizomes gave 170 grains of ethereal

extract. Upon treating this ethereal extract with alcohol, 20 grains were

dissolved leaving a residue of 150 grains. The extract first obtained was

of a brownish color, after treating with alcohol it assumed a beautiful

green color.

Voget 1829

Notiz ueber 01. filieis maris.

Arch. d. Pharm., 30, p. 104.

According to the author’s method of preparing the Oleum filieis maris ,

the powdered male fern rhizome is first extracted with water. After dry¬

ing the drug is then extracted with ether. Twenty-eight grains of a

brownish-green extract were obtained from 9 drachms of the marc.

Schuppmann 1830

Extractum resinosum Seminis Cynae.

Buchner’s Repert. f. d. Pharm., 35, p. 430.

The extract is directed to be prepared by macerating 4 ounces of the

coarsly powdered seed with 16 ounces of ether for 3 or 4 days, decanting

the liquid portion and evaporating to remove the solvent.

Beral 1834

Du principe du gingembre, et formules de plusieurs com¬

poses pharmaceutiques dont il est la base medicamenteuse.

Journ. de Chim. med., Pharm. et Tox., 10, p. 289.

The product obtained by extracting ginger with ether is designated

Piperoide du Gingembre. It is directed to be prepared by extracting in a

percolator 4 ounces of ginger with 6 ounces of ether, the rate of flow being

so regulated that the operation will consume not less than 2 hours. It is

stated that 5 scruples of piperoide were obtained in this manner, and that

6 scruples can be obtained if the residual ether is forced out by subse¬

quent percolation with alcohol (40°). The piperoide is reported to be

soluble in ether, anhydrous alcohol and oils.

- 1838

Extrait Oleo-Resineaux de Cubebe,

Journ. de Chim. med., Pharm. et Tox., 14, p. 366.

It is stated that Hausman prepared the oleoresinous extract of cubebs

by macerating the powdered drug with ether (625 grams of ether to 250

grams of drug), then decanting and evaporating the ethereal solution to

remove the solvent.

Du Mez — The Galenical Oleoresins .

1141

Hornung 1844

Pharmaceutiseh-Chemigehe Mittheilnngen.

Arch. d. Pharm., 89, p. 34.

Three ounces of fresh, powdered rhizomes of male fern, treated with

3 ouncs of ether in a V erdraengungsapparat, are reported to have yielded

2 drachms of extract.

Luck, E. 1845

Ueber einige Bestandtheile der Radicis Filicis.

Ann. d. Chem., 54, p. 119.

Upon standing, the ethereal extract deposits a granular substance which

can be obtained quite pure by pouring off the supernatant oily layer and

washing the deposit rapidly with ether. The washed precipitate, dis¬

solved in ether, crystallizes, upon evaporation, in rhombic leaflets, m. p.

160°C, insoluble in alcohol or water. The crystals were not obtained in a

sufficient degree of purity to determine their chemical constitution.

Procter, Wm., Jr. 1846

On the Ethereal Extract of Cubebs. •

Am. Journ. Pharm., 18, p. 167. [Pharm. Journ., 6, p. 319.]

At Dr. Goddard’s request, Procter prepared a * ‘ true oleoresin” of cubebs

by extracting the drug with ether. This method is regarded by him as a

great improvement over the method of Soubeiran.

Bell 1846

Oleoresinous Extract of Cubebs.

Pharm. Journ., 6, p. 319.

The report includes a reprint of Procter’s paper on the ethereal ex¬

tract of cubebs and remarks by Ure, at whose request the preparation was

made and by whom it is stated to have been used with success. A yield of

15 to 20 per cent, of oleoresin was obtained.

Procter, Wm., Jr. 1849

Remarks on oleoresinous ethereal extracts, their preparation

and the advantages they offer to the medical practitioner.

Am. Journ. Pharm., 21, p. 114.

A method for the preparation of the following ethereal extracts is given:

capsicum, chenopodium, semen contra, ginger, cardamom and pellitory.

(p. 116.) Several forms of apparatus, including a tin percolator, Mohr 7s

apparatus for extracting with ether and Gilbertson’s diplacement appara¬

tus are also described as being useful in this connection.

1142 Wisconsin Academy of Sciences , Arts , and Letters.

Bock, H. 1851

Analyse der Wurzel und des Wedels von Filix mas.

Arch. d. Pharm., 115, p. 257. [Am. Journ. Pharm., 24,

p. 61.]

The powdered rhizomes were extracted with ether, specific gravity 0.720.

By this means, 2000 grains of the powder are reported to have yielded 257.4

grains of an oily extract which was found to be composed of volatile oil,

tannic acid, resin, fatty oil stearin and chlorophyll.

The author recommends preparing the oleoresin from fresh rhizomes as

he states that the greater part of the volatile oil is lost upon drying and

the fatty oil tends to become rancid.

Lucke, E. 1851

Ueber einige Bestandtheile der Wurzel von Aspidium

Filix mas.

Jahrb. f. prakt. Pharm., 22; p. 130. [Arch. d. Pharm., 119,

p. 178; Journ. de Pharm. et de Chim., 54, p. 476.]

A crystalline substance resembling the Filicin obtained by Trommsdorff

eight years previous was isolated from the ethereal extract. The author

calls it Filixsaeure and assigns it the formula C20II15O9 It is further stated

that extracts prepared with ether contain no tannic acid or sugar, but

filix acid, pteritannic acid and fatty oil are present. Upon being saponi¬

fied, the oil yielded Filixolinsaeure (C42H40O4 -fHO) and Filosmylsaeure.

Von der Marck, W. 1852

Ueber Verfaelschung der Radicis Filicis maris.

Arch. d. Pharm., 120, p. 87.

The botanical characteristics of other than the official species are

enumerated and the manner in which they differ from those of male fern

pointed out.

With respect to the male fern rhizomes, the author gives the following

information: rhizomes gathered in September are the most active as they

contain the greatest amount of oil. In the preparation of the extract, only

that portion of the rhizome having borne fronds in the year collected,

should be taken. The following results were obtained using different

parts of the rhizome:

1. ) Extract from portion of rhizome which had borne fronds the

previous year. Yield 7.8% of a brownish -green extract.

2. ) Extract from portion bearing fronds during year collected. Yield

8.2% of a beautiful green extract.

3. ) Extract from portion which will develop fronds the coming year.

Yield, 8.5% of a beautiful green extract.

Du Mez — The Galenical Oleoresins.

1143

Schuck, F. 1852

Ueber Cubebin

Buchner’s n. Repert. f. d. Pharm., 1, p. 213. [Jahresb. d.

Pharm., 12, p. 34.]

Cubebin is stated to be slowly deposited from the ethereal extract of

cubeb upon standing. The extract prepared from 17 ounces of cubeb

gave 15 grains of cubebin.

Bakes, W. C. 1853

Extract of Capsicum.

Am. Journ. Pharm., 25, p. 513.

The extract was prepared at the request of a physician. Dilute alcohol

was employed for exhausting the drug. Eight ounces of Capsicum yielded

two ounces of extract.

It is stated that a simple ointment which acts as a rubiafacient in 20

minutes may be prepared by mixing one drachm of this extract with 1

ounce of simple cerate.

Livermore 1853

Extract of Lupulin.

Am. Journ. Pharm., 25, p. 294.

The extract is directed to be prepared by maceration, using alcohol as

the solvent. Sixty-six per cent, of extractive matter was obtained by this

treatment.

Garot and Schaeuffele 1857

Rapport sur le produit oleo-resineux de cubebe obtenu a

l’aide du sulfure de carbone.

Journ. de Pharm. et de Chim., 65, p. 368.

The article is on the experimental preparation of the oleoresin of cubebs

with carbon disulphide. This solvent is proven to be worthless for this

purpose on account of the large amount necessary for extracting the drug

and on account of the difficulty in removing it by evaporation.

Landerer, X.

Ueber Cubebinum.

Arch. d. Pharm., 139, p. 302.

The so-called cubebin was obtained in the preparation of Extractum

CubelfaruTn oleoso-resinosum, for which a mixture of ether and alcohol was

used. Upon standing in a cool place, needle-like crystals adhering in

groups were noticed. These crystals were soluble in warm alcohol and

gave a carmine red color with sulphuric acid.

1144 Wisconsin Academy of Sciences , Arts , and Letters.

Procter, Wm., Jr. 1859

Formulae for the fluid extracts in reference to their more

general adoption in the next pharmacopoeia.

Proc. A. Ph. A., 8, p. 265. [Am. Journ. Pharm., 31, p. 548.]

It is suggested that the preparations made by extracting drugs with

ether be designated as Oleoresinae in the next pharmacopoeia. Methods for

preparing the following oleoresins are described: “ Oleoresina Cardamoni,

Oleoresina Carophylli, Oleoresina Cubebae, Oleoresina Filicis maris, Oleo¬

resina Lupulinae, Oleoresina Fiperis Nigri, Oleoresina Pyrethri, Oleoresina

Sabinae, Oleoresina xanthoxyli and Oleoresina Zingiberis.’ ’

Girtle 1863

Extractum Cubebarum oleoresinosum.

Pharm. Centralh., 3, p. 608. [Canstatt’s Jahresber., 23, p.

178.]

The preparation is an aqueous -alcoholic-ethereal extract with which the

volatile oil, previously obtained by distillation, has been incorporated. It

is said to represent the therapeutic properties of the entire drug. It is

also stated that this preparation is not identical with the Extr. Cub. oleoso -

resinosum of Landerer (1857.)

Parrish, E. 1864

On Capsicum.

Proc. A. Ph. A., 12, p. 262. [Jahresb. f. Pharm. 1, p. 68.]

In discussing the constituents of capsicum, Parrish refers to the

ethereal extract as the oleoresin.

Bernatzik, W. 1865

Chemische Untersuchung der Cubeben mit besonderer

Beruecksichtigung der Wirkungsweise ihrer wesentlichen

Bestandtheile.

Buchner’s Repert. f. d. Pharm., 14, p. 97. [Arch.

Pharm., 179, p. 123.]

The article is a comprehensive discussion of the constituents of cubebs

and their physiological and therapeutic action.

Based on the results of clinical experiments, it was concluded that the

desired therapeutic principle is the resinous constituent and that the

volatile oil, cubeb camphor and cubebin are practically of no therapeutic

value. A method for preparing the Extractum Cubebarum resinosum, in

which cubebs freed from the volatile oil are extracted with alcohol, is

given (p. 139.)

Du Mez — The Galenical Oleoresins.

1145

Procter, Wm., Jr. 1866

Note on Oleoresina Cubebae.

Am. Jonrn. Pharm., 38, p. 210. [Pharm. Journ., 25, p. 620.]

The author reports the results obtained in the extraction of cubebs with

ether, alcohol and benzine. The yield of oleoresin obtained was as fol¬

lows: ether, 21.9 per cent., alcohol, 27 per cent., benzine, 16.5 per cent,

(p. 212). The use of benzine in the preparation of this oleoresin is

not recommended as it does not extract the eubebin completely.

Rittenhouse, H. N. 1866

On Substitutes for Ether and Alcohol in the Preparation

of the Official Oleoresins.

Proc. A. Ph. A., 14, p. 208. [Am. Journ. Pharm., 38, p. 24.]

The feasibility of displacing the ether remaining in the exhausted drug

with benzine, glycerine or water is discussed. From experiments conducted

along this line, it was concluded that benzine would be the most preferable

for this purpose. A working formula in which benzine is used to this

end is described. Cubebs and ginger were the drugs employed in the

experiments.

Paul, C. 1867

Sur l’extrait oleoresineux de cubebe.

Journ. de Pharm., et de Chim., 84, p. 197.

The extract is directed to be prepared by treating the powdered drug

successively with water, alcohol and ether. The extract so prepared is

said to contain all of the medicinal principles of the original drug.

Pile 1867

On the preparation of Oleoresins with benzine.

Proc. A. Ph. A., 15, p. 94.

One pound of cubebs percolated with 2 pounds of light benzine, specific

gravity 86°, Beaume, is stated to have yielded a trifle over 5 per cent, of

oleoresin of a pale ash color.

It is further stated that neither benzine nor ether completely exhaust

ginger, but that alcohol is a much better solvent for this purpose.

Heydenreich, F. V. 1868

On Cubebin and the Diuretic Principle of Cubebs.

Am. Journ. Pharm., 40, p. 42.

Eighty ounces of cubebs yielded, when extracted with ether, 19 ounces

of oleoresin or nearly 24 per cent.

The results obtained in the administration of cubebin, the volatile oil

and the soft resin are given.

1146 Wisconsin Academy of Sciences, Arts, and Letters.

Rump, C. 1869

Extractum Lupulini aether enm.

Arch. d. Pharm., 189, p. 232. [Jahresb. d. Pharm., 4, p. 39.]

The extract of lupulin is directed to be prepared by macerating the

fresh drug with ether, decanting and evaporating the ethereal solution to

the consistence of a thin syrup.

Squibb, E. 1869

Report of the Committee on the Pharmacopoeia.

Proc. A. Ph. A., 17, p. 298.

The process of repercolation is stated to be well adopted to the prep¬

aration of the oleoresins and that it materially lessens their cost.

Lefort, M. J. 1870

Memoire sur les extraits sulfocarboniques, et sur leur emploi

dans la preparation des hniles medicinales.

Journ. de Pharm., 90, pp. 102-110.

In considering the methods of medicating oils, the author proposes pre¬

paring the extract of the leaves of Coniium maculatum by exhausting the

drug with carbon disulphide and subsequently removing the solvent by

evaporation.

Hager, 1871

Zur Bereitung des Extractum Filicis aethereum.

Pharm. Centralh., 12, p. 457. [Am. Journ. Pharm., 44, p.

104.]

It is stated that, if the rhizomes are dried over burned lime previous

to extraction, and anhydrous ether (Sp. gr. below 0.723) used as the ex¬

tracting solvent, the oleoresin does not deposit on standing but remains

perfectly clear.

Maisch, J. M. 1872

On the use of Petroleum-Benzine in Making Oleoresins.

Am. Journ. Pharm. 44, p. 208. [Pharm. Journ., 31, p! 968;

Proc. A. Ph. A., 21, p. 138; Year-Book of Pharm., 10, p. 328.]

Petroleum benzine, sp. gr. 0.700, is stated to have been used to advantage

in the preparation of the oleoresins of capsicum, cubeb and ginger, but,

the author regards the use of this solvent in the place of ether as inad-

missable until it has been proven that the proximate principles not ex¬

tracted by the benzine are medicinally inert.

Du Mez — The Galenical Oleoresins.

1147

Buchheim 1873

Fructus Capsici.

Vierteljahresschr, f. prakt. Pharm., 22, p. 507.

[Proc. A. Ph. A., 22, p. 106.]

The capsicin sold by the firm of E. Merck is stated to be the ethereal

extract of the capsicum fruit.

Remington, J. P. 1873

On the Use of Petroleum Benzin for Extracting Oleo-

resinous Drugs.

Proc. A. Ph. A, 21, p. 592.

It is stated that benzin does not extract all of the diuretic principles

from buchu and that its use for extracting the oleoresinous drugs is limited

on account of its inflammability and great volatility.

Patterson, J. 1875

Aspidium marginale, Wildenow.

Am. Journ. Pharm., 47, p. 292.

The ethereal extract compared very favorably in appearance, taste and

color with the best German oleoresin of male fern which could be obtained

upon the market. An acid resembling the filicie acid of Luck was isolated

therefrom.

Kruse 1876

Yersuch einer vergleichenden Analyse der in den Monaten

April, Juli und October 1874, in der Umgegend Wolmars gesam-

melten Radicis filics maris.

Arch. d. Pharm., 209, p. 24.

The results obtained in the analyses of rhizomes gathered during the

months of April, July and October are tabulated. The rhizomes gathered

in April and October were found to have a more intensive green color and

stronger odor than those gathered in July. The rhizomes gathered in

April and July yielded a yellow colored extract while those gathered in

October gave a beautiful green colored product.

Griffin, L. F. 1877

Preparations of Cubebs.

Am. Journ. Pharm., 49, p. 552.

The author found that cubebs yielded 16.5 per cent, of oil and resin to

gasoline, while the wax and cubebin were not extracted. He, therefore,

concludes that gasoline is adapted to the making of a good oleoresin of

cubebs.

1148 Wisconsin Academy of Sciences , Arts , and Letters.

Wolff, L. 1877

On the use of Petroleum Benzin in Pharmacy.

Am. Journ. Pharm., 49, p. 1.

It is stated that benzin does not extract any of the pungent resins from

ginger, no cubebic acid from cubebs, no piperin from pepper, and no

santonin or resin from wormseed.

Cressler, C. H. 1878

On Aspidium marginale, Swartz.

Am. Journ. Pharm., 50, p. 290.

The author prepared an oleoresin from what he thought was male fern,

but later proved to be Aspidium marginale. According to his report, it

proved effective in expelling tapeworm.

Rohn, E. 1878

Recovering Ether in the Preparation of the Ethereal

Extracts.

Schweiz. Worchenschr. f. Chem. u. Pharm., — , p. — [Year-

Book Pharm., 16, p. 250.]

The author recommends mixing the exhausted drug with water and

then heating the mixture over a direct flame up to 60° C, when the ether

remaining in the marc distills over. In this manner three kilos of ether

are stated to have been recovered from eight to ten kilos of male fern used

in the preparation of the extract.

Kennedy, 1879

Aspidium marginale.

Am. Journ. Pharm., 51, p. 382.

Favorable results in the expulsion of taenia by the administration of

oleoresin of Aspidium marginale a**e reported.

Thresh 1879

Proximate Analysis of the Rhizome (Dried and Decorti¬

cated) of Zingiber Officinalis and Comparative Examination of

Typical Specimens of Commercial Gingers.

Pharm. Journ., 39, pp. 171 and 191.

The yield of ether extract is given as follows: Jamaica ginger, 3.29 per

sent., Cochin, 4.965 per cent., African, 8.065 per cent. It is further stated

that twice as much ether is required to exhaust the African ginger as it

is necessary in the ease of the other sorts (p. 191.)

Du Mez—TJie Galenical Oleoresins.

1149

Bowman, J. 1881

Aspidium rigidum.

Am. Journ. Pharm., 53, p. 389. [Pharm. Journ. 12, p. 263.]

A crystalline substance thought to be identical with the Filixsaeure of

Luck was obtained from the ethereal extract of Aspidium rigidum.

Seifert, 0. 1881

Einiges ueber Bandwurmkuren.

Wien. Med. Woehenschr., 31, p. 1364. [Centralb. f. klin.

Med. 3, p. 1884.]

The author contends that the extract should be prepared from the

peeled fresh drug gathered in May or October as drying causes the loss of

a greater part of the volatile oil. The ether should not be evaporated

until just before the extract is to be dispensed.

Maiscb, J. M. 1883

Comparison of Galenical Preparations of the United States

and German Pharmacopoeias.

Am. Jonrn. Pharm., 55, p. 398.

In the preparation of oleoresin of cubebs, the German Pharmacopoeia

directs that a mixture of equal parts of ether and alcohol be used as a

menstruum, while the TJ. S. Pharmacopoeia, directs that ether alone be used.

In the preparation of oleoresin of aspidium, the solvents are the same

(ether) but the German Pharmacopoeia directs that the oleoresin be pre¬

pared by maceration instead of percolation as in the TJ. S. Pharmacopoeia.

Kramer 1884

Extractum filicis maris.

Pharm. Centralh., 25, p. 578.

The fresh rhizomes gathered in May or October, are directed to be ex¬

tracted with ether containing a little alcohol. The tincture thus obtained

is to be preserved in a cool place and the oleoresin prepared therefrom

immediately before dispensing.

Berenger-Feraud 1886

Valeur taenifuge de la fougere de Normandy.

Jonrn. de Pharm. et de Chim., 14, p. 321. [Arch. d. Pharm.,

224, p. 134.]

The author states that the rhizomes gathered in Normandy have scarcely

any action while those gathered in the Vosges or Jura mountains are very

active as taeniafuges.

1150 Wisconsin Academy of Sciences , Arts , and Letters.

Jones, E. W. 1886

Amount of Starch in Ginger.

Chem. & Drugg., 28, p. 413. [Arch. d. Pharm., 224, p. 769.]

The yield of ethereal extract is given as 3.58 per cent., of alcoholic extract

as 3.38 per cent.

— - - - - 1887

Extr actum Cubebarum aethereum.

Gehe & Co. Handels -Ber. Sept., 1887, p. 50.

It is stated that, upon long standing, the extract of cubebs deposits a

crystalline substance. The firm, therefore, cannot guarantee that the

extract will remain clear.

Kremel, A. 1887

Notizen zur Pruefung der Arzneimittel.

Pharm. Post, 20, p. 521. [Archiv. d. Pharm., 225, p. 880.]

Methods for the identification and evaluation of the ethereal extract

of cubebs are presented. The chemical constants of both the alcoholic

and ethereal extracts are tabulated (p. 522.) Analytical data on the

alcoholic and ethereal extract of male fern are also given (p. 523.)

Lippincott, C. P. 1887

What Are the uses of Benzine and the Lighter Petroleum

Products in Pharmacy?

Proc. Penn. Pharm. Assoc., 10, p. 156.

The six official oleoresins were prepared using ‘ * benzole ' 1 as the ex¬

hausting menstruum.

Keefer, C. D. 1888

Aspidium marginale, Willdenow.

Am. J ourn. Pharm., 60, p. 230.

The author states that the ethereal extract of the rhizomes of Aspidium

marginale contains 0.61 per cent, of resin, and chlorophyll. Filicic acid

could not be identified.

Siggnis, F. M. 1888

Comparative value of commercial gingers.

Am. J ourn. Pharm., 60, p. 278.

The following percentages of resin were

with alcohol, sp. gr. 0.820.

Jamaica, unbleached . .

Jamaica, bleached . . .

East Indian . .

East Indian .

African . .

African .

obtained on extracting ginger

. 5.0 per cent.

. 4.8 “ “

. . . 6.65 “ “

. 6.57 “ “

. 6.17 “ “

_ _ ... 7.00 “ “

Du Mez — The Galenical Oleoresins.

1151

Trimble, H.

The Comparative Extractive Powers of Ether and Benzin.

Proc. Penn. Pharm. Assoc., 11, p. 60.

The following percentages of oleoresin were obtained on extraction

with ether: aspidium, 6.51 per cent; capsicum, 19.5 per cent; cubebs,

21.26 per cent; lupulin, 60.59 per cent; pepper, 7.89 per cent, and ginger,

3.07 per cent. The same drugs yielded to benzin 5.9, 18.5, 16.65, 7.04, 2.8

and 2.48 per cent., respectively.

Greenwalt, W. G. 1889

Oleoresin of Male Fern.

Am. Jonrn. Pharm., 61, p. 169. [Proc. A. Ph. A., 37, p.

379.]

The sediment deposited by the ethereal oil of male fern was found by

actual test to be as active as the supernatant oil; experiment is thus said

to help out the statement (U. S. P. 1880) that the granular deposit should

be thoroughly mixed with the liquid portion before being used.

Minner, L. A. 1890

Oleum Peponis.

Am. Jour. Pharm., 62, p. 274. [Proc. A. Ph. A., 38, p. 323.]

The pumpkin seeds comminuted with pumice stone are directed to be

extracted with ether. Such a preparation is stated to have proved to be

an effective taenifuge, whereas Oleum Peponis was ineffective.

Dieterich 1891

Extracta.

Helfenberger Ann., 1891, p. 29.

One sample of extract of male fern examined showed a il moisture con¬

tent’ ’ of 2.7 per cent, and gave 0.40 per cent, of ash.

Kuersten, R. 1891

Ueber Rhizoma Pannae, Aspidium athamanticum Kunze.

Arch. d. Pharm., 229, p. 258.

The author found no filix acid in the ethereal extract, but a substance

Pannasaeure having the formula CnH1404. A fatty and volatile oil were

also isolated. The extract was found to be as active as the extract of

male fern in the expulsion of tape worm.

1152 Wisconsin Academy of Sciences, Arts, and Letters.

Poulsson, E. 1891

Ueber den giftigen und bandwurmtreibenden Bestand-

theil des aetherischen Filixextractes.

Arch. f. exper. Path. u. Pharm., 29, p. 1.

Filix acid is stated to occur in two forms, amorphous and crystalline.

The first is reported to be therapeutically active, the latter is not. The

crystalline acid is thought to be an anhydride or lactone of the amorphous

acid. The author gives the name Filicin to the crystalline acid.

Rayman 1891

Wirkung des Extractnm Filicis aetherenm.

Pharm. Post, 24, p. 933.

It is stated that the extract of male fern is not well borne when taken

internally if the ether has not been completely removed.

Reuter, Ludwig 1891

Ueber die Beziehungen des Filixsaeuregehaltes zur Wirk¬

ung des Extractum Filicis aethereum.

Pharm. Ztg., 36, p. 245. [Pharm. Post, 24, p. 511; Am.

Journ. Pharm., 63, p. 288.]

It is stated that, in 14 out of 15 cases, prompt action was obtained using

an extract which showed no deposit of filix acid and which left no residue

of filix acid after treating with petroleum ether. On the other hand

extracts which were rich in a deposit of filix acid also showed prompt action.

Professor Kobert is cited as stating that the Russian extract is about

ten times as active as the German extract and twenty times as active

as the French extract.

Riegel, S. J. 1891

Ginger and its Oleoresin.

Am. Journ. Pharm., 63, p. 531. [Year-Book of Pharm., 29,

p. 168.]

Unbleached Jamaica ginger and East Indian ginger (having epidermis

removed) yielded 5 and 8 per cent., respectively, of oleoresin to alcohol.

The unbleached Jamaica ginger gave 2.5 per cent, of extractive matter

to benzin and the East Indian ginger gave 8 per cent of oleoresin to ether.

All of the foregoing oleoresins were found to be completely soluble in

alcohol and chloroform.

- - 1892

Extractum Alcannae aethereum.

Gehe & Co., Handels-Ber. Apr. 1892, p. 46.

The ether extract of alkanet root is stated to be completely soluble in

oil which is said not to be true of all commercial alkanet extracts.

Du Mez — The Galenical Oleoresins.

1153

Beringer, G. M. 1892

Oleoresins.

Am. Jonrn. Pharm., 64, p. 145. [Proc. A. Ph. A., 40, p.

474; Pharm. Centralh., 33, p. 314; Jahresb. d. Pharm., 27,

p. 589.]

The author presents experimental data to show that acetone might be

used to advantage in the preparation of the official oleoresins. He es¬

pecially recommends the use of this solvent in the preparation of the

oleoresin of ginger. The yield of oleoresin, using acetone as the extract¬

ing solvent for the various drugs, is reported to be as follows: aspidium,

18 per cent; capsicum, 18 per cent. (25 per cent, when the drug was com¬

pletely exhausted); cubebs, 21.75 to 25 per cent; lupulin, 71 per cent;

pepper, 5.93 per cent; ginger, 5.57 per cent; and parsley seed 24 per cent.

Dieterich 1892

Extracta spissa et sicca.

Helfenberger Ann., 1892, p. 44.

Three lots of extract of male fern gave 1.50, 2.10 and 1.50 per cent.,

respectively, of “moisture’7 and showed an ash content of 0.55, 0.55 and

0.55 per cent., respectively.

Kobert 1892

Ueber die wirksamen Bestandtheile im Rhizoma Filicis

maris.

Pharm. Post, 25, p. 1325. [Apoth. -Ztg., 8, p. 77 ; Chem.

Oentralb., 64, p. 269 ; Arch. d. Pharm., 231 ; p. 350, Pharm. Ztg.,

38, p. 64.]

The author states that the volatile oil of male fern is therapeutically

active and that Poulsson’s statement based on the work of Carlbohm,

Liebig and Rulle, that the activity is due to filix acid alone is erroneous.

He cites as an example the activity of Aspidium athamanticum Kunze, which

contains no traces of filix acid but contains the volatile oil.

Sherrad, C. C. 1892

Value of Oleoresinous Drugs.

Chem. and Drugg., 40, p. 523. [Year-Book Pharm., 29, p.

157.]

The yield of oleoresin obtained using ether as a menstrum is reported

to be as follows:

Capsicum, 4 samples, 15.5, 17.4, 18.3 and 18.4 per cent; cubebs, 9 samples,

16.4, 18.8, 21.06, 21.9, 23, 24.7, 24.8, and 24.8 per cent; ginger, 4 samples,

3.85, 4.72, 5.2, and 5.4 per cent; lupulin, 1 sample, 66.5 per cent; crude

whole male fern rhizomes, 2 samples, 9.27 and 9.87 per cent; peeled male

fern rhizomes, 3 samples, 7.1, 7.26 and 8.9 per cent.

73— S. A. L.

1154 Wisconsin Academy of Sciences , Arts , and Letters.

Weppen and Lueders 1892

Ueber Extr actum Filicis.

Apoth. -Ztg., 7, p. 514. [Pharm. Ztg., 38, 922 ; Pharm.

Post, 25, p. 1173.]

It is stated that the extract prepared according to the D. A. Ill should

have a yellowish-green color but not a deep green color. Preparations

having a deep green color probably have chlorophyll or copper salts added

to them. Copper can best be detected by dissolving the ash in hydro¬

chloric acid and making the usual tests for the metal.

Two samples (commercial) of a deep green color were found to contain

0.056 and 0.044 per cent, of copper, respectively.

- 1893

Extractum Filicis aethereum.

Gehe & Co., Handels-Ber., Apr., 1893, p. 43.

The condition of the season in which the rhizomes are harvested is

stated to have a marked effect on the color of the extract. Sometimes

the genuine extract is very dark green in color, especially in dry seasons.

Beckurts and Peters. 1893

Extractum Filicis.

Apoth.-Ztg., 8, p. 549.

Upon examination, two beautiful green samples of the commercial ex¬

tract were found to contain 0.135 and 0.044 per cent, of copper, respectively,

evidently added for the purpose of coloring the product. An extract pre¬

pared by the author was yellowish green in color and contained no copper.

A warning is issued against the use of copper utensils in the preparation

of the extract.

Dieterich 1893

Extracta spissa et sicca.

Helfenberger Ann., 1893, p. 38.

One sample of extract of cubeb showed a “moisture” content of 32.7

per cent, and gave 0.50 per cent of ash (p. 39).

Three samples of extract of male fern contained 1.15, 1.60 and 1.75 per

cent, of “moisture” and gave 0.50, 0.50 and 0.50 per cent, of ash,

respectively (p. 39).

Dyer and Gibbard 1893

Determination between Genuine and Exhausted Ginger.

Analyst, 18, p. 197. [Proc. A. Ph. A., 42, p. 936.]

The ether extract of genuine ginger is stated to be 3.0 to 5.2 per cent.

After exhausting with ether, alcohol was found to yield 0.8 to 1.5 per cent,

additional extractive matter.

Du Mez — The Galenical Oleoresins.

1155

Bedall 1894

Extractum Cubebarum Aethereum.

Pharm. Ztg., 39, p. 49.

The author states that the extracts having a green color give a more

intensive reaction for eubebin than those having a brownish color. This

does not apply when the green color is due to the presence of salts of

copper.

Dieterich 1894

Extracta spissa et sicca.

Helfenberger Ann., 1894, p. 72.

Three samples of extract of male fern were found to contain 3.65, 2.32

and 1.90 per cent., respectively, of 1 * moisture. ” The same samples gave 0.55,

0.42 and 0.50 per c^nt., respectively, of ash.

Emmanuel, L. 1894

Do Drugs Supplied by the Jobber Comply with Pharmaco-

pceial Requisition. If Not, Who is Responsible, The Jobber or

the Retailer?

Am. Journ., Pharm. 56, p. 358.

A sample of powdered cubebs obtained from an Eastern firm yielded 18

per cent, of a brown oleoresin. This was reported to the seller who re¬

plied: “the TJ. S. Pharmacopoeia specifies the unripe fruit, but this is

rarely found in the market, the regular article of commerce being the ripe

fruit which contains less chlorophyll.7’ p. 360.

Hell & Co.

Zur Kritik liber Extract-Vorschriften und ueber fabrik-

maessig dargestellte Extracte.

Pharm. Post, 27, pp. 168-171. [Journ. de Pharm. et de

Chim., 139, p. 493.]

Copper is stated to be a natural constituent of the male fern rhizome.

Duplicate analyses of a sample of the rhizomes carefully powdered in an

iron mortar, and incinerated in a porcelain dish showed 0.0144 and 0.0148

per cent, of copper, respectively. An ethereal extract prepared in the

company’s laboratory showed 0.033 per cent, of the metal and a com¬

mercial sample of the extract gave 1.96 per cent. Likewise, a commer¬

cial sample of extract of eubeb was found to contain 0.40 per cent, of

copper.

1156 Wisconsin Academy of Sciences , Arts, and Letters.

Poulsson, E. 1894

Beitraege zur Toxicologie der Farnkrauter.

Pharm. Post, 27, p. 238.

Two new acid substances C34H38014 and are reported to have

been isolated from the rhizomes of Polystichum spinulosum. They were

found to be toxic.

- 1895

Extractum Orleanae aethereum.

Gehe & Co., Handels-Ber. Apr., 1895, p. 53.

It is stated that good ‘ 1 bixinreiche ’ ’ orlean species are rare. The ex¬

tract is said to be used for coloring 1 1 Genussmitteln. ' 1

- - 1895

Extractum Cubebarum aethereum liquidium.

Gehe & Co., Handels-Ber., Apr., 1895, p. 53.

A note concerning the precipitation of resin.

Bourquelot, Em. 1895

Reactions d’identite de quelquess medicaments galeniques

offieinaux.

Journ. de Pharm. et de Chim., 140, p. 361.

The Extrait de Cubele of the French Codex is semi-liquid, that of the

German and Austrian pharmacopoeias of the consistence of fresh honey.

To identify the oleoresin, a small quantity is placed in a white porcelain

dish and a few drops of concentrated sulphuric acid are added. The gen¬

uine oleoresin gives a purple -red color immediately.

Davis, R. G. 1895

Ginger.

Am. Journ. Pharm. 67, p. 597. [Proe. A. Ph. A., 44, p. 538.]

The yield of oleoresin obtained from ginger by the official process was

found to be as follows:

Jamaica ginger, whole rhizome, bleached, 4.53 to 4.62 per cent; Jamaica

ginger, whole rhizome, unbleached, 2.82 to 4.41 per cent; Jamaica ginger,

powdered unbleached, 4.48 per cent; Races ginger, powered, bleached,

4.09 to 5.40 per cent; Races ginger, whole rhizome, bleached, 4.02 to 5.75

per cent; African ginger, whole rhizome, 5.75 per cent; African ginger,

powdered, 6.27 per cent.

Du Mez — The Galenical Oleoresins.

1157

Dieterich 1895

Extracta spissa et sicca.

Helfenberger Ann., 1895, p. 17.

One sample of extract of cubebs contained 20.90 per cent, of ‘ ‘ mois¬

ture’ f and showed an ash content of 0.47 per cent. (p. 17).

A sample of extract of male fern showed a ‘ 1 moisture ’ 1 content of 1.75

per cent, and gave 0.50 per cent, of ash (p. 18.)

Hyers, P. 1895

Fluid Extract of Cubeb.

Am. Journ. Pharm., 67, p. 519.

The following percentages of oleoresin are reported to have been yielded

by cubebs to different solvents: ether, 22.45 per cent; alcohol, 14.48 per

cent; acetone, 18.48 per cent; petroleum ether, 13.47 per cent.

- 1896

Extractum Filicis Ph. G. III.

Caesar and Loretz, Geschaefts-Ber., Sept. 1896, p. 46.

The firm attributes the uniform activity of their extract of male fern to

the fact that the rhizomes are obtained from the same locality each year,

that they are collected in the autumn and, after carefully garbling, are

immediately made into extract.

Fromme’s method for estimating the filix acid content of the extract is

given.

Alpers, W. C. 1896

Oleoresin Capsicum.

Merck’s Rep. 5, p. 593.

The author states that he obtained a yield of 19 per cent, of oleoresin

after removing the fat by Alteration instead of 5 per cent, as usually given

in the text-books.

Bocchi, I. 1896

Methoden zur Feststellung der Identitaet und der Guete

des aetherischen Filixextraktes.

Boll. Cbim. farm., 1896, p. 449. [Apoth-Ztg., 11, pp. 597

and 837 ; Pharm. Ztg., 41, p. 596.]

Reactions for the identification of filix acid, and a method for the eval¬

uation of the extract of male fern are given.

1158 Wisconsin Academy of Sciences , Arts, and Letters.

Daccomo and Scoccianti 1896

Die Bestimmung des Gehaltes an Filixsaeure im kaeuflichen

Extractum Filieis.

Boll. Chim. farm., 5, p. 129. [Pharm., Ztg., 39, p. 280;

Jahresb. d. Pharm., 31, p. 583; Apoth.-Ztg., 11, p. 174; Proc.

A. Ph. A., 44, p. 433.]

The filix acid content of a number of samples of extract of male fern

(self prepared and commercial) was found to vary from 11.86 to 42.53

per cent., when assayed according to the method devised by the authors.

The average yield of extract obtained is given as 10 per cent.

The quantity and quality of the extract is stated to be influenced by

the locality in which the rhizomes are grown, the moisture content of the

drug when extracted, and the solvent. Ether, specific gravity, 0.720, is

stated to be the most suitable menstruum for this purpose. Ether, specific

gravity, 0.756, yielded 17 per cent, of a brownish colored extract of a

tarry consistence. The presence of alcohol is said to retard the complete

extraction of the filix acid.

Dieterich 1896

Extracta spissa et sicca.

Helfenberger Ann., 1896, p. 33.

One sample of extract of male fern contained 1.62 per cent, of “mois¬

ture” and gave 0.45 per cent, of ash.

Kraft, P. 1896

Ueber die Wertbestimmung von Extractum Filieis und

eine neue Bestimmungsmethode der Filixsaeure.

Schweiz. Wochenschr. f. Chem. u. Pharm., 34, p. 217.

[Zeitschr, d. Allg. Oesterr, Apoth. Ver. 34, p. 798; Zeitschr. f.

Anal. Chem., 39, p/531.]

It is stated that the method of Daccomo and Scoccianti for the evalua¬

tion of the extract of male fern does not give the filix acid content but

the total acid content. Extracts examined by the author’s method gave

from 0.4 to 10.0 per cent, of filix acid.

A new constituent which the author calls Filixwachs was isolated from

the extract.

Liverseege 1896

The Effect of Solvents on the Analytical Character of

Ginger.

Pharm. Joum., 57, p. 112. [Apoth.-Ztg., 11, p. 639.]

The ethereal extract of ginger is stated to amount to 5.5 per cent.

The yield to methyl alcohol is given as 6.5 per cent.

Du Mez — The Galenical Oleoresins.

1159

— _ _ _ _ 1897

Extractum Filicis, Ph. G. III.

Caesar and Loretz, Geschaefts-Ber., Sept. 1897, p. 62.

[Pharm. Centralh., 38, p. 34.]

Investigations carried on by the firm showed that the best time for

harvesting the rhizomes of male fern is from the middle of September

to the end of October. Ehizomes collected in the spring yielded an ex¬

tract low in filix acid content.

The consistence of the abstract is said to be dependent upon variations

in the rhizomes, thus rhizomes rich in wax give an extract which is not

fluid at ordinary temperatures.

Fromme ’s improved method for estimating the filix acid is given.

— - - 1897

Extractum Filicis aethereum, P G.. III.

Gehe & Co., Handels-Ber., Apr. 1897, p. 60.

The results obtained in the assay of male fern extracts by the methods

of Daccomo and Seoccianti, Bocchi, and Fromme are tabulated.

Boehm, R. 1897

Beitraege zur Kenntniss der Filixsaeuregruppe.

Archiv. f. exp. Path. u. Pharm., 38, p. 35.

In addition to the volatile oil, fixed oil and filix acid, Boehm isolated

four acid substances from the extract of male fern, viz*, aspidm (C23H3207),

flavaspidic acid (C23H2808), albaspidin (C22H2807) and aspidinol (C12H1604).

Candussio 1897

Ueber die Bereitung des Extractum Filicis aethereum.

Pharm. Post, 30, p. 7.

The author is impressed with the low cost of the commercial extract of

male fern as compared with the cost when prepared by the apothecary him¬

self. The examination of a number of samples from the best German

houses showed a low filix acid content when estimated according to the

method of Daccomo and Seoccianti. They were all of a beautiful green

color, however.

Dieterich 1897

Extracta spissa et sicca.

Helfenberger Ann., 1897, p. 244. [Apoth.-Ztg., 13, p. 788 ;

Pharm. Centralh., 39, p. 775.]

Two samples of extract of male fern, D. A. Ill, lost 4.5 and 4.72 per

cent., respectively, on drying at 100°C; and gave 0.43 and 0.52 per cent,

of ash, respectively.

Dieterich contends that a standard, which does not take into consideration

1160 Wisconsin Academy of Sciences , Arts , and Letters.

the volatile oil as well as the filix acid, is worthless, as the former is also

active as a taenifuge. Old extracts which are inactive show the normal

amount of filix acid. The diminution in activity is said to be due to the

loss of the volatile oil by resinification and evaporation (p. 248.)

Dieterich 1897

Extractum Filicis aetherum, D. A. III.

Extractum Cub eb arum aethereum.

Erstes Dezennium d. Helfenberger Ann., 1886-1895, p. 322.

Eighteen samples of extract of male fern examined during 10 years

showed a loss upon drying at 100°C of from 0.60 to 9.73 per cent. The

same samples showed an ash content varying from 0.40 to 0.63 per cent.

Four samples of ethereal extract of cubeb showed a loss upon drying

at 100°C of 20.13 to 32.7 per cent., and gave 0.10 to 0.52 per cent, of ash.

Glass and Thresh 1897

Commercial Gingers and Essence of Ginger.

Pharm. Journ., 58, p. 245. [Am. Journ. Pharm., 69, p. 320.]

Jamaica ginger was found to yield 6.0 per cent of extractive matter

to ether; Cochin, 4.33 per cent; African, 6.33 per cent.

Lauren, W. 1897

Extractum Filicis spinulosae.

Finska Laekaresaellsk. Handl., 1897, p. 9. [Pharm. Cen-

tralh., 39, p. 975.]

The ethereal extract prepared from the rhizomes of Aspidmm spinulosum

is stated to be as active a taeniafuge as that prepared from Aspidium filix

mas.

Madsen, H. P. 1897

Meddelelser fra Vesterbro Apotheke Laboratorium.

Arch. f. Pharm. og Chem., 54, p. 269. [Jahresb. d. Pharm.,

32, p. 591; Apoth.-Ztg., 12, p. 461.]

Extracts of male fern from Denmark, Germany, Bohemia, central Rus¬

sia and Livonia were tested quantitatively for filix acid according to

Fromme’s method. Those from Bohemia and central Russia gave from

0.71 to 0.97 per cent, of filix acid; two samples from Germany gave 5.58

and 9.58 per cent., respectively; an extract from Wolmar in Livonia gave

13.07 per cent; the extracts from Denmark, with two exceptions (6.07 and

8.25 per cent.), gave below 2 per cent. (p. 277.)

Du Mez — The Galenical Oleoresins.

1161

- 1898

Extraction Filicis aetherum.

Gehe & Co., Handels-Ber., 1898, p. 68. [Pharm. Centralh.,

39, p. 298.]

In the analyses of 11 extracts obtained during different years, 6 were

found to contain aspidin, 0.2 to 3.0 per cent., but no filix acid; 4 samples

contained filix acid but no aspidin; 1 sample showed a trace of aspidin

and a small quantity of filix acid.

- 1898

Zur Arzneiform und Werthbestimmung des Filixextracts.

Pharm. Centralh., 39, p. 873.

The dilution of the extract of male fern with castor oil to a definite

filix acid content is discussed.

- 1898

Extractum Filicis, Ph. G. III.

Caesar and Loretz, Geschaefts-Ber., Sept. 1898, p. 72.

A continuation of the firm’s investigations concerning the influence of

time of harvesting upon the quality of the male fern rhizomes has shown

that they do not contain the maximum amount of active constituents until

the month of August. They, therefore, conclude that the rhizomes should

only be harvested in the months of August, September and October.

It is further reported that analyses of the extracts recently prepared

show that the present year’s (1898) crop of rhizomes is, on the whole, lower

in crude filicin content than that of the preceding year (1897.)

Beliingrodt, Fr. 1898

Ueber Rhizoma und Extractum Filicis.

Apoth.-Ztg., 13, p. 869.

The crude, and purified filicin content of 8 different extracts of male

fern prepared by the author from rhizomes obtained from different sources

are given. Similar data in the examination of 9 commercial extracts are

also reported.

Dieterieh, K. 1898

Zur Wertbestimmung und Arzneiform des Filixextraktes.

Apoth.-Ztg., 13, p. 788.

The addition of castor oil to the extract of male fern in sufficient quantity

to bring the filix acid content to a definite standard is recommended.

1162 Wisconsin Academy of Sciences , Arts, and Letters .

Duesterbehn, F. 1898

Rhizoma und Extractum Filicis in therapeutisoher, chem-

ischer und toxicologischer Beziehung.

Apoth.-Ztg., 13, pp. 713, 720, 729 and 734.

The article is principally a review of the literature on the extract of

male fern and its constituents.

Lefils 1898

Zur Herstellung von Filixextract.

Pharm. Centralh., 39, p. 901. [Zeitschr. d. oest. Apoth.

Ver., 37, p. 167 ; Pharm. Ztg., 43, p. 939.]

The author advises the mixing of the powdered rhizomes with castor oil

before preparing the extract as he is of the opinion that this procedure

will retard the evaporation of the volatil oil and the precipitation of the

crystalline filix acid.

Idris, T. H. 1898

Notes on Extract of Ginger.

Am. Journ. Pharm., 70, p. 466.

The alcoholic extract of ginger known as gingerine does not contain all

of the aromatic principles of the rhizome, as most of the essential oil is

lost on removing the alcohol upon evaporation. Acetone boiling at 58 °C

was found to be the most suitable solvent for extracting ginger. The

acetone extract is a dark brown substance of treacly consistence, intensely

pungent and at the same time possessing the full aroma of ginger, the

quality of which largely depends on the variety of ginger used.

Miehle, Feodor 1898

Eine empfehlenswerte Form der Verordung von Extractum

Filicis.

Apoth.-Ztg., 13, 777. [Pharm. Centralh., 39, p. 873.]

The author recommends diluting the extract with castor oil in order to

make a standard preparation containing a definite amount of filix acid.

He advises the introduction of such a preparation into the D. A. IV,

under the name Extractum Filicis oleatum .

Plzak, F. 1898

Extractum Filicis.

Pharm. Centralh., 39, p. 687. [Jahresb. d. Pharm., 33,

p. 547.]

The author found 6.48 per cent of filix acid in the extract of male fern

by the Kraft method, 6.0 per cent, by Fromme’s old method and 5.2 per cent,

by Fromme ’s improved method.

Du Mez — The Galenical Oleoresins.

1163

Winton, Ogden and Mitchell 1898

Capsicum.

Rep. of Conn. Agr. Exp. Sta. (1898), p. 200.

The amount of extractive matter obtained with ether from different

samples of red peppers is given as follows: Chilli Colorado, 15.81 per

cent; peppers from Natal, 16.85 per cent; from Nepaul, 21.31 per cent;

and from Zanzibar, 16.19 per cent.

- 1899

Recently Introduced Remedies.

Am. Drugg. & Pharm. Rec., 34, p. 129.

It is stated that the extract of Filix Spinulosa is an ethereal extract of

the rhizome of Aspidium spinulosum and that it has been recommended as

a substitute for the preparation made from Aspidium Filix-mas.

- 1899

Extractum Filicis, Ph. G. III.

Caesar and Loretz, Geschaefts-Ber., Sept. 1899, p. 73.

A table showing the crude filicin and filix acid content of extracts pre¬

pared from 15 of the better samples of male fern rhizomes obtained from

different sources in Germany is given.

Results showing the difference in extractive power of ether, sp. gr. 0.720

and ether, sp. gr. 0.728 are also given.

Hausmann, A. 1899

Ueber Extractum Filicis aethereum.

Arch. d. Pharm., 237, p. 544.

The examination of 21 commercial extracts of male fern obtained from

various sources showed that aspidin was a constituent of 4 of them. As

aspidin is said to be found only in Aspidium spinulosum, the author infers

that the rhizomes of this species have been used to adulterate the official

drug.

A method for the detection of aspidin is given.

- - 1900

Extractum Filicis.

Caesar and Loretz, Geschaefts-Ber., Sept. 1900, p. 77.

A table showing the crude and purified filicin content of 12 samples

of extract of male fern is given

Attention is also called to the greater tendency of the extract, prepared

with ether, specific gravity 0.728, to deposit than that prepared with

ether, specific gravity 0.720. The deposited material is reported to have

been identified by Boehm as filix acid and a wax-like substance.

1164 Wisconsin Academy of Sciences, Arts , and Letters.

- - 1900

Extractum Filicis aethereum.

Gehe & Co., Handels-Ber., Apr. 1900, p. 63.

The constituents of the extracts of Aspidium filix mas , A. filix femina

and A. spinulosum are discussed.

Maish, H. C. C. 1900

Oleoresins. Economical preparation.

P. C. P., Alumni Report, March, 1900, p. 49. [Proc. A. Ph.

A., 48, p. 495.]

Maish advises the use of the Soxhlet extraction apparatus for pre¬

paring the oleoresins on a small scale.

Patch, E^. L. 1900

Answere to queries issued by the Scientific Section of the

American Pharmaceutical Association.

Proc. A. Ph. A., 48, p. 199.

The commercial oleoresins frequently show the presence of acetone, p. 205.

- - 1901

Extractum Filicis.

Caesar and Loretz, Geschaefts-Ber., Sept. 1901, p. 68.

The crude and purified filicin contents of 8 batches of extract of male fern

prepared during the year are presented in tabular form.

Bennet 1901

Report on Commercial Ginger.

Pharm. Journ., 66, p. 522.

The yield of extractive matter obtained on exhausting ginger with ether

and alcohol is given as follows:

Per cent, of ether extract:

Jamaica ginger (whole), 2.57 to 6.41.

il “ (ground), 2.97 to 4.6.

Per cent, of alcoholic extract after ether:

Jamaica ginger (whole), 3.09 to 5.16.

11 li (ground), 3.01 to 4.16.

Per cent, of alcoholic extract.

Jamaica ginger (whole), 3.94 to 5.61.

t

Du Mez — T1 te Galenical Oleoresins.

1165

Dieterich 1901

Extracta spissa et sicca.

Helfenberger Ann., 1901, p. 170.

One sample of extract of male fern, D. A. IV, gave 5.23 per cent, of

“moisture” and 0.32 per cent, of ash (p. 171).

Matzdorff, M. 1901

Wertbestimmung des Rhizoma Filicis.

Apoth.-Ztg., 16, pp. 233, 256 and 273.

The various constituents of the extract of male fern are discussed with

respect to their therapeutic activity. Of these filix acid is thought to

be the most important. Tables showing the crude filicin and filix acid

content of ethereal fluid extracts prepared by ordinary percolation and

by extraction with a Soxhlet’s apparatus are given.

Stoeder 1901

Bestimmnng der Filixsaenre in Extractum Filicis.

Pharm. Ztg., 46, p. 541.

A method very similar in all respects to that of Fromme for the esti¬

mation of the filix acid in the extract of male fern is described.

- - - 1902

Oleoresin of Insect Powder.

Southall Bros. & Barclay, Lab., Rep., 10, p. 20.

This oleoresin is said to be extracted from the powdered drug and is

offered for sale, in the crude form, as an extract, or precipitated, in the

form of a coarse powder.

It is said to be useful as a basis for nursery hair lotions, dusting pow¬

ders and similar articles.

- - 1902

Extractum Filicis.

Caesar and Loretz, Geschaefts-Ber., Sept. 1902, p. 73.

It is stated that the crude filicin contains the amorphous acid recently

shown by Kraft to be the active principle of male fern extract. The

estimation of the crude filicin will, therefore, be continued by the firm.

Buttin, L. 1902

Extract de Fougere male.

Schweiz. Wochenschr. f. Chem. u. Pharm., 40, p. 234.

A short review of the early work on the constituents of the extract of

male fern is given.

The variation in the constituents of the rhizomes due to the locality in

1166 Wisconsin Academy of Sciences , Arts , and Letters.

which they are grown, the time of the year when harvested, storing, etc.,

and the effect of the same upon the activity of the extract is emphasized.

Eight per cent of extract is reported as having been obtained from

rhizomes harvested in the spring.

Kraft, F. 1902

Untersuchung des Extraetum Filicis.

Schweiz. Wochenschr. f. Chem. u. Pharm., 40, p. 322.

[Chem. Centralb., 73, 2, p. 53; Pharm. Ztg., 48, p. 275.]

Two new substances were isolated by the author from the ethereal ex¬

tract of male fern, flavaspidin and an amorphous acid. The amorphous acid is

reported to be the active principle and to be present to the extent of 5 per

cent, in a good extract.

- 1903

Table showing suggested standards, ranges of specific

gravity, etc., for galencial preparations.

Southall Bros., & Barclay, Lab. Rep., 11, p. 23.

The standard range for the specific gravity of Extraetum Filicis liquidum

is given as 1.000 to 1.019 at 15.5 °C p. 24.)

- 1903

Extraetum Filicis.

Caesar and Loretz, Geschaefts-Ber., Sept. 1903, p. 77.

It is reported that extracts prepared from the male fern rhizomes har¬

vested during the previous year, when assayed according to the method of

Kraft, yielded 27.08 to 36.6 per cent, of crude filiein.

- 1903

Ginger.

Southall Bros. & Barclay, Lab. Rep., 11, p. 13.

The following table shows the proportion of oleoresin found in three

varieties of commercial ginger.

Jamaica Cochin African

Per cent. sol. in alcohol (90 per cent.) . 4.35 4.57 9.93

Per cent. sol. in ether, Sp. gr. 0.717 . 4.76 6.04 11.09

- 1903

Capsicum.

Southall Bros. & Barclay, Lab. Rep., 11, p. 13.

A sample of Capsicum minimum yielded ,5.67 per cent, of material soluble

in ether, Sp. gr. 0.717, and a sample of Capsicum annum yielded 15.34

per cent, to the same solvent.

Du Mez — The Galenical Oleoresins .

1167

Ballard 1903

Sur quelques condiments des colonies francaise (Anise

etoile, Cannelle, Cardamome, Curcurma, Gingembre, Girofle.

Journ. de Pharm. et de Chim., 157, pp. 248 and 296.

Ginger from the Ivory Coast is reported to have yielded 6.33 per cent,

of ether extract, that from Tahiti, 3.75 per cent, p. 248.

Black pepper yielded the following percentages of extractive matter

to ether: 10.15, 8.70 and 5.50.

Beythien 1903

Capsicum.

Zeitschr. Unters. Nahr. u Genussm., 5, p. 858. [Pharm.

Ztg., 47, p. 549 ; Proc. A. Ph. A., 51, p. 747.]

The examination of a number of commercial samples of powdered capsi-

sicum showed the following:

Yield of extract to ether (total) . 12.54 to 19.70 per cent.

“ “ “ “ “ (av.) . 14.94 “ “

“ “ “ “ alcohol (total) . 26.55 to 35.71 “ “

“ “ “ “ “ (av.) 28.94 “ “

Dieterich 1903

Extract a spissa et sicca.

Helfenberger Ann., 1903, p. 240.

Three samples of extract of male fern examined showed a “ moisture’ 1

content of from 5.52 to 7.38 per cent., and gave from 0.27 to 0.39 per

cent, of ash (p. 241.)

Penndorff, O. 1903

Untersuchungen ueber die Beschaffenheit kaeuflicher Filix-

Rhizoma und Extrakte.

Apoth.-Ztg., 18, p. 150.

The author states that the rhizomes turn brown on aging due to the

breaking down of the filix-tannic acid into filix-red and sugar.

An examination of 20 samples of commercial rhizomes showed that

12 of them or over 50 per cent, contained rhizomes of Aspidium spinulosum,

1 sample consisted of 90 per cent, of this species.

Twenty samples of commercial extracts were examined with the fol¬

lowing results :

4 samples — Starch present in small quantities.

1 sample — Aspidin present.

20 samples — 6.65 to 18.31 per cent, crude filicin.

20 samples — 1.06 to 7.48 per cent, filix acid.

20 samples — 0.40 to 3.00 per cent, filix acid in solution.

20 samples — 0.40 to 6.05 per cent, filix acid deposited.

7 samples — copper, more or less.

1168 Wisconsin Academy of Sciences, Arts, and Letters.

- 1904

Extractum Filicis.

Caesar and Loretz, Geschaefts-Ber., Sept. 1904, p. 77.

It is stated that for years the firm has placed upon the market under

their name an extract of male fern containing not less than 29 per cent,

of crude filicin.

Dieterich 1904

Ueber Extractum Filicis, D. A. IV.

Helfenberger Ann., 1904, p. 182.

The results obtained in the examination of 3 samples of the extract of

male fern are tabulated. The results include the per cent, of “moisture”

and ash, and the iodine and saponification values.

- - 1905

Extractum Filicis.

Caesar and Loretz, Geschaefts-Ber., Sept. 1905, p. 7.

It is stated that, although the year’s crop of male fern is poor, the firm

guarantees a crude filicin content of 28 per cent, for their extract, (p. 71.)

Fromme’s method for estimating the crude filicin content is given (p. 85.)

- 1905

Ueber die wirksamen Bestandtheile des Farnwurzel-

extrakts. Pharm. Ztg., 50, p. 651.

The work of Boehm, also that of Kraft, is commented on, special ref¬

erence being made to F Umar on isolated from the extract by the latter.

- 1905

The Newer Remedies.

Am. Drugg. & Pharm. Rec., 46, p. 135.

Capsolin which is recommended as a substitute for mustard papers, is

said to consist of a mixture of oleoresin of capsicum, the oils of turpentine,

cajuput and croton, with an ointment base. It is manufactured and

marketed by Parke, Davis & Co., Detroit.

- - 1905

The New U. S. P., Changes in Composition and Strength.

Drug Topics, 20, p. 210. [Am. Journ. Pharm., 78, p. 412.]

The new edition of the TJ. S. P. specifies acetone as the solvent for

making all of the oleoresins with the exception of oleoresin of cubebs, which

Du Mez — The Galenical Oleoresins.

1169

is prepared with alcohol. It is stated that manufacturers have long since

seen the folly of employing an expensive solvent like ether, and the

adoption of acetone for this purpose is a recognition of commercial phar¬

maceutical advances, (p. 214.)

Dieterich 1905

Extracta spissa et sicca.

Helfenberger Ann., 1905, p. 159.

A sample of the ethereal extract of cubeb, D. A. IV, showed a “mois¬

ture” content of 55.91 per cent, and an ash content of 0.87 per cent.

(p. 160.)

A sample of extract of male fern D. A. IV, gave a “moisture” content

of 5.06 per cent., an ash content of 0.46 per cent, and yielded 23.22 per

cent, of crude filicin (p. 161.)

Dieterich 1905

Rhizoma Zingiberis.

Helfenberger Ann., 1905, p. 131.

The following percentages of extract were obtained by exhausting ginger

with different solvents, evaporating the latter and drying the residue at

100°C:

1) One part alcohol, 8 parts water — 7.86 per cent.

2) Sixty-eight per cent, alcohol — 4.88 per cent.

3) Ninety per cent, alcohol — 2.79 per cent.

Dieterich 1905

Rhizoma Filicis.

Helfenberger Ann., 1905, p. 130.

During the year, a number of lots of male fern rhizomes were examined.

The air-dried rhizomes yielded 9.94 to 10.60 per cent, of ethereal extract.

The rhizomes when dried at 100°C yilded as high as 11.20 per cent, to

the same solvent.

Francis, J. M. 1905

The New Pharmacopoeia: A Detailed Commentary on the

Eighth Revision of the U. S. P.

Bull, of Pharm., 19, p. 317. [Am. Journ. Pharm., 78, p. 412.]

Under acetone, it is stated that oleoresins prepared with this solvent will

separate in two layers on standing owing to the fact that this ketone pos¬

sesses in a measure the combined solvent properties of both alcohol and

ether.

74— S. A. L.

1170 Wisconsin Academy of Sciences, Arts, and Letters.

Vanderkleed, C. E. 1905

Report of the Committee on Adulterations.

Proc. Penna. Pharm. Assoc., 28, p. 47.

Eight assays of capsicum gave 9.4 to 23.9 per cent, of oleoresin, the

average being 18.13 per cent. The standard for a good drug is stated

to be 15 per cent.

Vieth, H. 1905

Ueber die Beziehung zwischen chemischer Zusammenset-

zung und medizinischer Wirkung einiger Balsamika.

Verh. d. Ges. deutsch. Naturf. u. Aerzte, 2, p. 364. [Jah-

resber. d. Pharm., 66, p. 13.]

Kubebenextralct is reported to consist of terpenes (65 per cent.), resin

acids (10 per cent.), and resins (25 per cent.)

- 1906

Apiolin

Merck’s Ann. Rep., 20, p. 34.

Apiolin is the raw ethereal oil obtained from the seed of Petroselinum

sativum or from Apiol viride by extraction with a suitable solvent. It is a

yellow fluid, sp. gr. 1.25 to 1.135, boiling at 280 to 300°C.

- - 1906

Extractum Filicis.

Caesar and Loretz, Geschaefts-Ber., Sept. 1906, pp. 82 and

99.

The firm reports that the crude filicin content of the extract obtained

from the current year’s crop of male fern averages 27 per cent. (p. 82).

Fromme’s method for estimating the crude filicin is given (p. 99).

Naylor, A. H. 1906

Progress in pharmacapceias : drugs and their constituents.

Year-Book of Pharm., 43, p. 204.

It is stated that in the present state of our knowledge, neither Daccomo

and Scoccianti ’s, Kraft’s nor Stoeder’s process for the quantitative esti¬

mation of filicic acid is a measure of the anthelmintic value of the ex¬

tract of male fern.

Du Mez — The Galenical Oleoresins.

1171

Roeder, Ph. 1906

Rhizoma Filicis.

Jahresb. d. Pharm., 41, p. 46.

The author states that the rhizomes of Aspidium filix mas should give at

most 3 per cent, of ash and should yield at least 8 per cent, of extractive

matter to ether, allowing the latter to evaporate spontaneously and then

heating for 2 hours at 95 °C, cooling in a desiccator and weighing. Three

samples of rhizomes gave 2.52 to 2.92 per cent, of ash, respectively, and

9.22 to 10.1 per cent, of ether-soluble extract.

Wollen weber, W. 1906

Ueber Filixgerbsaenre.

Arch. d. Pharm., 244, p. 466.

In connection with his work on the tannic acid in the male fern rhizomes,

the author presents the results obtained in extracting the drug in a Soxh-

let’s apparatus with various solvents, ether, benzol, and petroleum ether.

At the end of six hours, extraction was found to be practically complete in

all cases. The yield obtained in each case is given as follows; ether, 10.0

per cent., benzol, 9.06 per cent., petroleum ether, 9.08 per cent.

Extraction with alcohol of varying strength yielded extractive matter

in the following quantities: alcohol (90 per cent.), 20.0 per cent., alcohol

(96 per cent.), 16.6 per cent.

The fixed oil content of the ethereal extract is stated to be 70 to 75

per cent.

- 1907

Cubebs.

Evans Sons Lescher & Webb, Analyt. Notes, 1, p. 21.

The oleoresin extracted by ether from four samples of cubebs amounted

to (1) 22.08, (2) 22.6, (3) 21.13 and (4) 22.8 per cent., respectively.

Blome, W. H. 1907

Cnbeba.

Proe. Mich. Pharm. Assoc., 1907, p. 68. [Bull. Hygienic

Lab., No. 63, p. 225.]

Five samples of cubeb are reported which assayed from 18.85 to 26.88

per cent, of oleoresin.

1172 Wisconsin Academy of Sciences, Arts, and Letters.

Van der Harst, J. C. 1907

Lnpnlin.

Pharm. WeekbL, 44, p. 1506. [Bull. Hygienic Lab., No. 63,

p. 301.]

Two samples of lupulin were found to contain 52 and 65 per cent, of

ether-soluble matter, respectively.

Patch, E. L. 1907

Report of Committee on Drug Market.

Proc. Am. Pharm. Assoc., 55, p. 314.

The samples of capsicum examined yielded from 16.2 to 26.5 per cent,

of alcoholic extract (p. 324.)

Smith, 0. W. 1907

Galenicals of the U. S. P. VIII.

Proc. Mo. Pharm. Assoc., 29, p. 132.

The author is of the opinion that the oleoresin of cubeb might well have

been included in the class made with acetone, as the drug yields but little

on subsequent extraction with alcohol. Alcohol on the other hand is

open to the objection that its boiling point is so high that a considerable

loss of volatile substances from the cubeb occurs when the solvent is

evaporated (p. 134.)

- - 1908

Extractum Filicis.

Caesar and Loretz, Geschaefts-Ber., Sept. 1908, pp. 76

and 99.

It is stated that for years the firm has estimated the crude filicin con¬

tent of the extract of male fern and marketed a standard product contain¬

ing 28 per cent, of this constituent as required by the Swiss Pharmacopoeia,

VI, (p. 76.)

Fromme’s method for estimating the crude filicin is given (p. 99.)

Dohme and Engelhardt 1908

Purity of some official and non-official drugs and chemicals.

Proc. Am. Pharm., Assoc., 56, p. 814.

A sample of lupulin yielding only 56 per cent, of ether-soluble matter is

reported (p. 817.)

Du Mez — The Galenical Oleoresins.

1173

Patch, E. L. 1908

Report of Committee on Drug Market.

Proc. Am. Pharm. Assoc., 56, p. 765.

The different samples of capsicum examined yielded from 15 to 25.2 per

cent, of alcoholic extract (p. 768.)

Spaeth, Eduard 1908

Die chemische und mikroskopische Untersuchung der

Gewiirze und deren Berurteilung.

Pharm. Centralh., 49, p. 581.

The paper discusses the characteristics of several commercial varieties

of ginger and the composition of the drug. The quantity of material

extracted by ether, alcohol, petroleum ether and methyl alcohol is given.

Vanderkleed, C. E. * 1908

Report of Committee on Adulteration.

Proc. Penna. Pharm. Assoc., 31, p. 65.

Three samples of capsicum yielded from 11.59 to 18.35 per cent, of oleo-

resin; four samples of cubebs, 16.39 to 23.6 per cent; two samples of

ginger, 5.58 to 9.55 per cent; three samples of male fern, 6.68 to 17.9 per

cent., average 10.002 per cent. (p. 88.)

- 1909

Pharmacy Committee’s Report.

Chem. & Drugg., 74, p. 288.

The Committee of Reference in Pharmacy asserts that cubebs should

yield not less than 20 per cent, of oleoresin to ether, sp. gr. not over

0.720. (p. 292.)

- 1909

Extractum Filicis.

Caesar and Loretz, Geschaefts-Ber. Sept. 1909, pp. 67 and 84.

A crude filicin content of 28 per cent, is guaranteed by the firm for the

new lot of extract of male fern (p. 67.)

Fromme’s method for the estimation of the crude filicin is given (p. 84.)

- 1909

Apiol.

Evans Sons Lescher & Webb, Analyt. Notes, 4, p. 11.

A sample of apiol of French manufacture examined by the firm is re¬

ported as having been liquid and green in color. It yielded 40 per cent, of

1174 Wisconsin Academy of Sciences , Arts , and Letters.

xcs bulk to steam distillation. It is, therefore, thought that the sample

was prepared by the extraction of parsley fruits with a suitable light

solvent.

Rernegau, L. H. 1909

Report of the Committee on Adulteration.

Proc. Penna. Pharm. Assoc., 32, p. 119.

Ten samples of lupulin examined yielded from 34 to 65.8 per cent, of

ether-soluble matter (p. 125.)

Dohme and Engelhardt 1909

Purity of some official and non-official drugs and chemicals.

Proc. A. Ph. A., Assoc., 57, p. 713.

Three samples of lupulin examined were low in ether-soluble matter

yielding but 47.50, and 43 per cent., respectively (p. 716.)

Dunn, J. A. 1909

Suggested Modifications of U. S. P. and N. F. Formulas.

Proc. A. Ph. A., 57, p. 942.

It is stated that the oleoresin of male fern prepared by the U. S. P.

method, using acetone, contains so much undesirable extractive matter that

it is necessary to purify it by dissolving in ether. It is suggested that it

might be worth while to consider whether the U. S. P. should not go

back to the use of ether (p. 949.)

Parson, W. A. 1909

Report of the Committee on Adulteration.

Proc. Penna. Pharm. Assoc., 32, p. 119.

Three samples of lupulin yielded 66.1 and 54 per cent, of ether-soluble

matter, respectively (p. 125.)

Patch, E. L. 1909

Report of Committee on Drug Market.

Proc. A. Ph. A., 57, p. 721.

The alcoholic extract from specimens of ginger examined varied from

3.7 to 6.2 per cent. (p. 739.)

Du Mez — The Galenical Oleoresins.

1175

Vanderkeed, C. A. 1909

Report of the Committee on Adulteration.

Proc. Penna. Pharm., Assoc., 32, p. 119.

Samples of capsicum, cubebs, ginger, and male fern examined are re¬

ported to have yielded oleoresin as follows: five samples of capsicum, 14.34

to 17.95 per' cent; four samples of cubebs, 16.49 to 24.34 per cent; sixteen

samples of Jamaica ginger, 3.142 to 6.91 per cent; two samples of African

ginger, 8.2 and 9.036 per cent; one sample of male fern, 10.33 per cent,

(p. 129.)

- — 1910

Extr actum Filicis.

Caesar and Loretz, Jahres-Ber., Sept. 1910, p. 90.

Fromme ’s method for the estimation of crude filicin is given.

- 1910

Cubebs.

Southall Bros. & Barclay, Lab. Rep., 17, p. 11.

Eight samples of cubebs, when extracted with petroleum spirits, yielded

from 3.88 to 18.08 per cent, of extractive matter. The same samples on

subsequent extraction with alcohol (90 per cent.) yielded from 3.4 to 5.66

per cent, of extractive matter.

- 1910

Capsicum.

Southall Bros. & Barclay, Lab. Rep., 17, p. 8.

Two samples of capsicum (B. P. C.) yielded 15.4 and 14.0 per cent.,

respectively, of extract to benzol.

Dohme and Engelhardt 1910

The new Hungarian Pharmacopoeia.

Proc. Am. Pharm. Assoc., 58, p. 1168.

The extraction of male fern with ether, as directed in the Ph. Hung. Ill ,

instead of acetone as in the 77. S. P., VIII, is thought to be desirable since

the latter is liable to extract substances which might produce injurious

after etfects (p. 1179.)

It is further stated that the yield of ether extract as given in the Hun¬

garian Pharmacopoeia is 8 per cent. (p. 1184.)

1176 Wisconsin Academy of Sciences, Arts, and Letters.

Eldred, F. R. 1910

Some data obtained in the examination of official substances.

Proc. A. Ph. A., 58, p. 889.

Forty-eight lots of capsicum were examined. The yield of ether-soluble

oleoresin, when the latter was dried for one hour on a water bath, was

found to vary from 11 to 26 per cent., the average 18 per cent, (p.891.)

Gane, E. H. 1910

Pharmaeopceial notes and comments.

Drug Topics, 25, p. 212.

It is stated that a good sample of cubebs should yield 20 per cent, of

ether-soluble extract.

Gane and Webster 1910

Pharmacopoeial notes and comments.

Drug Topics, 25, p.

Aspidium is stated to be one of the most useful of drugs when carefully

collected and preserved, but that much of the rhizome is inert and is ob¬

tained from any old species of fern. It is said to be falling into disuse

on this account. It is thought that the observance of more care in the

collection of the drug and the preparation of the oleoresin would restore

its popularity as an anthelmintic.

La Wall, C. H. 1910

Some suggested standards and changes, for the U. S. P.

Am. Journ. Pharm., 82, p. 21.

The author asserts that a test for capsicum should be included , in the

U. S. P. requirements for the oleoresin of ginger as many commercial

samples used in making ginger ale extracts contain oleoresin of capsicum

and these occasionally find their way into the pharmaceutical trade.

A method for the detection of capsicum in the oleoresin of ginger based

on the neutralization of the pungent principle of the ginger with potassium

hydroxide is described (p. 25.)

Vanderkleed, C. E. 1910

Report of the Committee on Adulterations.

Proc. Penna. Pharm. Assoc., 33, p. 131.

Seven samples of capsicum yielded from 15.10 to 22.27 per cent, of

oleoresin; one sample of African ginger 10.12 per cent; two samples of

Jamaica ginger 5.636 and 6.316 per cent., respectively (p. 147.)

Du Mez — The Galenical Oleoresins.

1177

- - - - 1911

Extractum Filicis.

Caesar and Loretz Jahres.-Ber., Aug. 1911, pp. 76 and 105.

Regret is expressed in that the Ph. Germ. V. has not included an assay

for oleoresin of aspidium. The crude filicin content is thought to be a

satisfactory indication of the value of this preparation. A filicin con¬

tent of 27 per cent, is guaranteed by the firm for the new lot of the ex¬

tract prepared by them (p. 76.)

Frpmme’s method of estimating the crude filicin is given (p. 105.)

1911

Male fern extract.

Evans Sons Lescher & Webb, Analyt. Notes, 6, p. 48.

Five samples of male fern extract were tested. Two were found to

be adulterated with castor oil (55 to 70 per cent.)

The Kraft and the Swiss pharmacopoeial methods for evaluating the

extracts are discussed and the results obtained in each case, along with other

physical and chemical constants, are tabulated.

- 1911

Cubebs.

Southall Bros. & Barclay Lab. Rep., 19, p. 9.

Five samples of cubebs yielded from 4.66 to 8.78 per cent, of extract

to petroleum spirit, the average being 6.95 per cent.

- 1911

Insect Powder.

Southall Bros. & Barclay, Lab. Rep., 19, p. 10.

Two samples of insect powder yielded 8.28 and 7.57 per cent, of oleo*-

resin when tested by Durant’s method.

One sample of Japanese insect flowers yielded 13.98 per cent, of oleo¬

resin of an orange brown color.

- 1911

Oil of male fern.

Brit. & Col. Drugg., 60, p. 388.

In this article, it is stated that parcels of the extract of male fern are

being condemned in London as they have been found to contain large

quantities of castor oil.

Suspicion was first aroused through the low selling price of some

1178 Wisconsin Academy of Sciences , Arts, and Letters.

of the extracts. The adulterated extract was being sold for 4s per

pound while reliable manufacturers would not quote prices below 5 s 6 d

per pound.

- - 1911

Ext. Filicis maris.

Chem. & Drugg., 79, p. 749 and 798.

This editorial commenting on Parry’s observation, that extract of male

fern is commonly adulterated with castor oil, calls attention to the testis

given in the Netherlands and Swiss pharmacopoeias.

Bernegau, L. H. 1911

Report of the Committee on Adulterations.

Proc. Penna. Pharm. Assoc. 34, p. 117.

Three lots of lupulin tested 58.9, 57.7 and 62.1 per cent, soluble in

ether (p. 125.)

Beythien, Hemple & Others 1911

Kurze Mitteilungen aus der Praxis des Chemischen Unter-

suchungsamtes der Stadt Dresden.

Zeitschr. Unters. Nahr. u. Genussm., 21, p. 666.

A table is presented showing the ash content and extract content of a

number of samples of ginger (p. 668.)

According to Reich the volatile ether extract content varied from 0.80

to 4.02 per cent., the non volatile from 1.66 to 6.93 per cent; the alcoholic

extract from 1.33 to 4.08 per cent; the petroleum ether extract from 1.14

to 4.49 per cent; and the methyl alcohol extract from 4.40 to 12.53 per

cent.

Deane, Harold 1911

Oleoresina Capsici, B. P. C.

Pharm. Journ., 87, p. 804.

The author criticises the British Pharmaceutical Codex with respect to

the title Oleoresina Capsici. He is of the opinion that the preparation

has no right to the name oleoresin, as it corresponds more closely to the

product sold as capsicin or soluble capsicin for the use of pill makers

and mineral water manufacturers.

Francis, J. M. 1911

Report of the Committee on Adulterations.

Proc. Penna. Pharm. Assoc., 34, p. 117.

Only one of eight lots of lupulin examined failed to exceed the required

60 per cent, of ether-soluble matter (p. 125.)

Du Mez — The Galenical Oleoresins.

1179

Gluecksmann, G. 1911

Ueber eine neue Identitaetsreaktion des Extractum Cube-

barnm.

Pbarm. Praxis, 1911, p. 98. [Apoth.-Ztg., 27, p. 334.]

A test in which hydrochloric acid is used for producing a color reaction

is described in detail.

Parry, E. J. 1911

Extract of male fern.

Pharm. Journ. 87, p. 778. [Chem. & Drugg., 79, p. 860;

Am. Journ. Pharm., 84, p. 136; Apoth-Ztg., 26, p. 1046.]

The author reports on the examination of commercial extracts of male

fern and finds that the greater part are undoubtedly adulterated with from

30 to 60 per cent, of castor oil. The physical and chemical constants

of the commercial samples and of genuine extracts are tabulated for com¬

parison.

Pearson, W. A. 1911

Report of the Committee on Adulterations.

Proc. Penna. Pharm. Assoc., 34, p. 126. [Bull. A. Ph. A.,

6, p. 346.]

The author reports that two lots of oleoresin of aspidium were rejected

because they were not green in color.

Rosendahl, H. V. 1911

Fern rhizomes, yield of extract and relative activity of.

Year-Book of Pharm., 48, p. 286. [Apoth.-Ztg., 26, p. 588 ;

Svensk. farmac. Tidsk., 1911, p. 85.]

The yield of ethereal extract obtained from various species of fern

harvested during different months of the year was found to be as follows:

Two grams of the extract of Dryopteris dilatata are stated to be thera¬

peutically equivalent to 8 to 10 grams of the extract of Aspidium filix mas

or four grams of the extract of Dryopteris spinulosa.

1180 Wisconsin Academy of Sciences , Arts , and Letters .

Vanderkleed, C. E. 1911

Report of the Committee on Adulterations.

Proc. Penna. Pharm. Assoc., 34, p. 117.

Two samples of capsicum are reported to have yielded 14.7 to 17.93 per

cent., respectively, of oleoresin; one sample of subebs, 22.14 per cent;

eleven samples of African ginger, 7.128 to 9.484 per cent; and eight

samples of Jamaica ginger, 3.4 to 6.6 per cent. (p. 132.)

- 1912

Extr actum Filicis.

Caesar and Loretz, Jahres-Ber., Sept. 1912, p. 128.

The firm’s method for estimating the crude filicin is given.

- 1912

Capsicine.

Evans Sons Lescher & Webb, Anaylt. Notes, 7, p. 18.

Five samples of capsicine examined were all entirely soluble in 10 vol¬

umes of 90 per cent, alcohol.

- 1912

Male fern extract.

Evans Sons Lescher & Webb, Analyt. Notes, 7, p. 51.

Sixteen samples of male fern extract examined in 1912 were free from

castor oil and of satisfactory purity. They showed a refractive index of

1.507 to 1.509 at 15°C, and gave a filicin content of 22.9 to 26.3 per cent.,

when assayed according to the method given in the Swiss Pharmacopoeia.

- 1912

Capsicum.

Johnson & Johnson, Lab. Notes, 1912, p. 14.

The yield of ether extract obtained from capsicum is reported to have

varied from 16 to 19 per cent.

- — 1912

Cheap extract of male fern found badly adulterated.

Merck’s Report, 21, p. 29 [Apothecary, 24, p. 14.]

a. sample of cheap extract of male fern examined by Merck was found

to be adulterated with 25 per cent, of castor oil, and to contain only 8 per

cent, of crude filicin.

Du Mez — The Galenical Oleoresins.

1181

_ _ 1912

Male fern extract.

Southall Bros., & Barclay, Lab. Rep., 20, p. 15.

The statement of Parry that much of the male fern extract is adulterated

is confirmed. The physical and chemical constants obtained in the ex¬

amination of six commercial extracts are tabulated.

/

Dohme and Engelhardt 1912

Drug quality during the period 1906-1911.

Journ. A. Ph. A., 1, p. 99.

It is stated that there was hardly any variation in the percentage of

oleoresin in the samples of cubebs examined during the last six years,

(p. 101.)

Goris and1 Yoisin 1912

The determination of the ether extract of male fern, and the

unification of the methods of analysis.

Bull. Sci. Pharmacolog., 19, p. 705, [Pharm. Ztg., 58, p.

129; Joum. 90, p. 81; Year-Book of Pharm., 50, p. 337.]

It is stated that the method of the Swiss Codex gives values for crude

filicin which are about 30 per cent, too high owing to the solubility of

the ether solution in the solution of barium hydroxide. If the ether be

driven off by heating to 50 °C before filtering, the results will be com¬

parable with those obtained by the magnesia methods.

Hooper, D. 1912

Notes on Indian drugs.

Pharm. Journ. 89, p. 391.

The examination of the rhizomes of Indian ginger, with reference to de¬

termining the relationship between maturity and oleoresin content, showed

that young rhizomes develop oleoresin as they are allowed to grow. Those

gathered in December yielded 6.4 per cent, of extract to alcohol (90 per

cent.), while those gathered in February gave 8.3 per cent. Upon washing

the extracts with water, the remaining insoluble residue amounted to 3.0

per cent, and 3.5 per cent., respectively. Some of the more mature rhizomes

gave as high as 11.8 per cent, of alcoholic extract or 8.1 per cent, of

washed resin.

Patch, E. L. 1912

Report of the Committee on Drug Market.

Journ. A. Ph. A., 1, p. 499.

Eight samples of Jamaica ginger gave from 3.3 to 6.0 per cent, of alco¬

holic extract (p. 500.)

1182 Wisconsin Academy of Sciences , Arts, and Letters.

Vanderkleed, C. E. 1912

Report of Committee on Drag Market.

Proc. Penna. Pharm. Assoc., 35, p. 165.

The assay of 4 samples of capsicum showed the oleoresin content to be

from 14.41 to 16.7 per cent; five samples of cubebs yielded 1.735 to 24.49

per cent, of oleoresin; seventeen samples of Jamaica ginger, 3.444 to 6.640

per cent; ten samples of African ginger, 6.85 to 11.10 per cent (p. 179.)

- 1913

Miscellaneous Inquiries.

Chem. & Drugg., 82, p. 470.

Gingerin is stated to be the extract obtained upon evaporating the tinc¬

ture of ginger. It is said to vary with the variety of ginger used in the

preparation of the tincture.

Capsicin is stated to be commercially indefinite. It may be a strong alco¬

holic extract, an ethereal, a chloroformie or an acetone preparation. The

accepted capsicin of commerce, however, is the oleoresin prepared with

ether.

0

- 1913

Die Methoden zur Wertbestimmung des Filixextrakts.

Pharm. Ztg., 58, p. 129.

The methods of Goris and Yoisin, and E. Schmidt for the evaluation of

the extract of male fern are discussed.

- - 1913

Extractum Filicis.

Caesar and Loretz, Jahres.-Ber., Sept. 1913, pp. 98 and 106.

Four samples of extract of male fern prepared by the firm showed a

crude filicin content of 32.64, 23.7, 28.15 and 30.4 per cent., respectively,

(p. 98.)

The firm guarantees the filicin content of their extract to be 27 per

cent.

- 1913

Male fern extract.

Evans Sons Lescher & Webb, Analyt. Notes, 8, p. 44. [Year-

Book of Pharm., 51, p. 244.]

Seven samples of extract of male fern examined during the year showed

a filicin content of 21.3 to 25.3 per cent, and a refractive index of 1.5 to 1.51.

Three samples were impure or suspicious. They showed a refractive

index of 1.495, 1,497 and 1.499, and a filicin content of 15.6, 19.6 and

19.7 per cent., respectively.

Du Mez — The Galenical Oleoresins.

1183

_ _ 1913

Male fern extract.

Southall Bros., & Barclay, Lab. Rep., 21, p. 14.

The analytical data obtained in the examination of two commercial

samples of the extract of male fern are given.

Bohrisch, P. 1913

Ueber Extractum Filicis.

Pharm. Ztg., 58, p. 601. [Chem. Abs. 8, p. 206.]

A comprehensive review of the constituents and the methods of evaluat¬

ing the extract of male fern is given.

Four samples of commercial extracts in bulk were examined for density

and crude filicin content. The findings for density were 0.9888, 0.9842,

0.9836 and 1.0109; for crude filicin 14.85; 15.42, 16.00 and 24.00 per cent.

The same tests for five samples of the extract in capsules showed: density,

0.9824, not determined, 1.0135, 1.0255 and 0.9910; crude filicin, 15.02,

23.42, 26.77, 27.72 and 14.45 per cent.

Dohme and Engelhardt 1913

Cubebs.

Oil, Paint and Drug Rep., 83, p. 55.

The quantities of oleoresin obtained from cubebs ranged between 16

and 22 per cent.

DuMez, A. G. 1913

The physical and chemical properties of the oleoresin of As-

pidium with respect to the detection of adulterations.

Philippine Journ. of Sc., 8, Sec. B., p. 523.

The methods of adulterating the oleoresin are discussed in detail The

physical and chemical constants of samples prepared in the laboratory and

those obtained from various commercial sources are presented with the

idea of indicating to what extent they may be relied upon in detecting

a deteriorated or adulterated product.

Engelhardt, H. 1913

Purity of chemicals and drugs.

Journ. A. Ph. A., 2, p. 163.

Four samples of black pepper are reported to have yielded 10.6, 12.5,

9.2 and 11 per cent., respectively, of oleoresin; six samples of capsicum,

13.1, 41.8, 15.26, 15.8, 11.3 and 11 per cent; cubebs from 18 to 25 per

cent; Jamaica ginger from 2.81 to 5.24 per cent; lupulin, eight samples

out of twelve, less than 60 per cent; three samples of parsley seed. 14.7,

11.4 and 13.04 per cent. (pp. 164 and 165.)

1184 Wisconsin Academy of Sciences, Arts, and Letters.

Gane, E. H. 1913

Report of Committee on Drug Market, August, 1912.

Journ. A. Ph. A., 2, p. 677.

Four lots of lupulin gave 44.94 to 65.5 per cent, of ether-soluble material,

(p. 681.)

Harrison and Sell 1913

Analytical constants of extract of male fern.

Chem. & Drugg. 83, p. 182. [ Year-Book of Pharm., 50, p.

494; Pharm. Journ. 91, p. 128; Pharm. Ztg., 58, p. 643.]

The analytical constants of genuine and commercial extracts of male

fern are tabulated. The authors do not approve of the standards sug¬

gested by Parry.-

Hill, C. A. 1913

Analytical notes on extract of male fern.

Chem. & Drugg., 83, p. 181. [Pharm. Ztg., 58, p. 643.]

The analytical constants of 23 samples of extract of male fern are

discussed and tabulated. The chemical and physical constants of the oily

portion are also given for comparison with those of castor oil. One com¬

mercial sample is reported to have contained 59 per cent, of the latter.

Osborne, Oliver F. 1913

A last plea for a useful Pharmacopoeia.

Journ. Am. Med. Assoc., 60, p. 1427.

Among the “ useless” preparations adopted by the Committee of Re¬

vision, the author includes the oleoresins of lupulin and parsley seed,

(p. 1429.)

Parry, E. J. 1913

Extract of male fern.

Chem. & Drugg., 83, p. 231.

The author confirms the results which he published in an earlier paper.

Patch, E. L. 1913

Report of the Committee on Drug Market.

Journ. A. Ph. A., 2, p. 1081.

The percentage of alcoholic extract obtained from the drugs tested is

reported as follows:

Du Mez — The Galenical Oleoresins.

1185

Capsicum, four samples, 19 to 24 per cent; ginger, nine samples, 5.2,

5.7, 4.2, 4.0, 4.5, 4.9, 3.5, 4.8 and 4.3 per cent. pp. 1088 and 1094.

The yield of ether extract reported by Kebler is as follows:

Fifty-three samples, lupulin, 63.96 to 77. .82 per cent; black pepper

three lots, 10.04, 10.87 and 12.88 per cent; red pepper, eight samples,

13.0, 10.6, 14.7, 18.91, 13.12, 10.4, 13.25 and 14.7 per cent. The iodine

values for the same were 132, 138, 123.4, 107, 127.3, 25.2 and 137.3.

Seventeen other samples yielded from 11.22 to 20.77 per cent. The iodine

value of these varied from 110 to 145.7 (pp. 1098 and 1101.)

Umney, J. C. 1913

What is capsicin ?

Pharm. Journ., 91, p. 594.

Capsicin is stated to be a synonym for Oleo-Besin of Capsicum of the

B . P. Codex, and, is made by extracting capsicum with 60 per cent, alcohol

and subsequently evaporating off the solvent. It should not be con¬

fused with the preparations made with strong alcohol (90 per cent.),

ether or acetone.

Vanderkleed, C. E. 1913

Report of the Committee on Drug Market.

Proc. Penna. Pharm. Assoc., 36, p. 77.

Thirty-seven samples of Jamaica ginger are reported to have yielded

3.10 to 5.75 per cent, of oleoresin; seventeen samples of African ginger,

6.85 to 9.92 per cent; seven samples of capsicum, 13.1 to 18.1 per cent;

one sample of cubebs, 21.8 per cent.

Yagi, S. 1913

Physiologische Wertbestimmung von Filixsubstanzen und

Filixextrakten.

Zeitschr, f. d. ges. exp. Med., 3, p. 64. [Therap. Monatsch.,

1914, p. 443; Apoth-Ztg., 29, p. 544.]

A method in which earth worms are used for the purpose of testing the

relative activity of extract of male fern and its constituents is described.

- - 1914

Untersuchung der offizinellen vegetablischen Drogen.

Riedel’s Ber. 58, p. 29.

The samples of cubebs examined are reported as having yielded 11.1 to

14.7 per cent, of extract soluble in ether 1 part and alcohol 1 part (p. 31.)

The alcohol extract obtained from capsicum varied from 31.9 to 35.3

per cent. (p. 32.)

The samples of aspidium examined gave 9.4 to 9.7 per cent, of ether-

soluble extract.

*

75 — S. A. L.

1186 Wisconsin Academy of Sciences, Arts, and Letters .

- 1914

Ueber Gelatinkapsel-Fabrikate.

Riedel’s Ber. 58, p. 45. [Apoth.-Ztg., 29, p. 310.]

Capsules from only two manufacturers contained extract of male fern

of which the crude filicin content was higher than 20 per cent. The ex¬

tract of male fern in capsules from four other sources showed a filicin

content of from 8.57 to 16.02 per cent. (p. 48.)

- 1914

Extractum Filieis.

Caesar and Loretz, Jahres-Ber., Oct., pp. 23, 37, and 96.

The method of S. Yagi for the physiological standardization of the extract

of male fern is stated to be too cumbersome for practical use. (p. 23.)

Extracts prepared in the laboratory showed the following crude filicin

content, 25.48, 24.85, 29.7, 26.04, 26.0, 35.58, 27.35 and 33.79 per cent,

(p. 37.)

It is further stated that the yield of ether extract, after evaporating on

a water bath at 60 °C to constant weight and drying in a desiccator for

half an hour, should be about 15 to 18 per cent. (p. 96.)

- 1914

United States Pharmacopoeia Ninth Revision. Abstracts of

proposed changes with new standards and descriptions.

Journ. A. Ph. A., 3, pp. 524 and 1573. [Year-Book of

Pharm., 52, p. 324.]

It is stated that the former solvent, acetone, is to be changed to ether

in the following: Oleoresina Aspidii, Oleoresina Capsici, Oleoresina

Zingiberis and Oleoresina Piperis. (p. 551.)

Directions are also given for the preparation of Oleoresina Petroselini

(p. 573.)

Bohrisch, P. 1914

Ueber verschiedene verbesserungbeduerftige Artikel des

Dentschen Arzneibnches Y.

Apoth.-Ztg., 29, p. 901.

It is stated that a large portion of the extract of male fern made in Ger¬

many shows a crude filicin content of less than 15 per cent., while the Swiss

Pharmacopoeia requires a content of 26 to 28 per cent. The author,

therefore, thinks it desirable that a method for the estimation of the crude

filicin in this preparation be given in the German Pharmacopoeia.

Du Mez — The Galenical Oleoresins.

1187

E\ve, G. E. 1914

Report of Committee on Drug Market.

Proc. Penna. Pharm. Assoc., 37, p. 125.

The author reports as follows on the oleoresins examined:

Four samples of oleoresin of capsicum were found to be pungent in

dilutions of 1 to 150,000, the arbitrary standard of H. K. Mulford

Company.

Seven samples of oleoresin of ginger were pungent to the taste in

ailutions of 1 to 20,000, the arbitrary standard of H. K. Mulford Company.

On<e lot of oleoresin of cubeb contained the waxy deposit which the U.

S. P. directs should be rejected.

One lot of oleoresin of say palmetto, “IT. S. P. ’ ’ contained 15 per cent,

of water which separated on standing. It also contained a large amount

of insoluble matter (p. 152.)

Linke, H. 1914

Ergebnisse, Beobachtungen und Betrachtungen bei der

Untersuchung unserer Arzneimittel.

Apoth'.-Ztg., 30, pp. 606 and 628.

The results obtained in the examination of extract of male fern, in bulk

and in capsules, obtained from various sources are tabulated. Especially

the extract marketed in capsules was found to be low in filicin content.

Patch, E. L. 1914

Report of Committee on Quality of Medicinal Products.

Journ. A. Ph. A., 3, p. 1283.

A sample of oleoresin of capsicum examined is reported as having been

found to be insoluble in ether, only slightly soluble in alcohol and almost

completely soluble in water (p. 1298.)

Rippetoe, J. R. 1914

The examination of some drugs with special reference to

the anhydrous alcohol and ether extracts, and ash.

Am. Journ. Pharm., 86, p. 435.

Four samples of capsicum are reported as having yielded 17.02 to 24.46

per cent, of extract to alcohol, and 16.49 to 17.88 per cent to ether, (p. 437.)

Six samples of cubebs gave 8.87 to 11.04 per cent, of alcoholic extract,

and 7.68 to 9.80 per cent, of ethereal extract, (p. 438.)

Two samples of Jamaica ginger yielded 4.98 to 5.5 per cent, of extractive

matter to alcohol, and 2.79 to 4.97 per cent, to ether. Two samples of

African ginger yielded 6.20 to 6.23 per cent, to alcohol, and 5.3 to 5.45

per cent, to ether, (p. 439.)

Three samples of lupulin yielded 32.49, 55.18 and 57.06 per cent.,

respectively, of ethereal extract, (p. 440.)

1188 Wisconsin Academy of Sciences , Arts, and Letters.

Seoville, W. L. 1914

Report of Committee on Quality of Medicinal Products.

Joum. A. Ph. A., 3, p. 1283.

It is stated that the samples of cubebs examined during the year gave

from 18.1 to 22 per cent, of oleoresin, (p. 1287.)

Vanderkleed, C. E. 1914

Report of Committees on Drug Market.

Proc. Penna. Pharm. Assoc., 37, p. 125.

On page 160, analytical data obtained from the laboratory of H. K.

Mulford Company are reported showing the following yield of oleoresin

for capsicum, cubebs and ginger :

The filicin content of five samples of extract of male fern examined is

reported as having varied from, 20.4 to 27.7 per cent., the specific gravity

from 0.9885 to 1.030.

Glickman, L. H. 1915

Report of Committee on Drug Market.

Proc. Penna. Pharm. Assoc., 38, p. 138.

Ten lots of lupulin examined are reported to have yielded the following

percentages of ether-soluble matter : 55.5, 55.0, 57.1, 58.6, 54.7, 55.3, 44.2,

69.2, and 68.2, (p. 149.)

Vanderkleed, C. E. 1915

Report of Committee on Drug Market.

Proc. Penna. Pharm. Assoc., 38, p. 138.

On page 155, the following data concerning the yield of oleoresin are

The reasons for some of the changes in the formulas of galeni¬

cals made in the ninth revision of the United States Pharma¬

copoeia.

Journ. A. Ph. A., vol. 5, No. 12, p. 1390.

It is stated that acetone was the menstruum directed to be used in the

preparation of the oleoresins by U. S. P., eighth revision, on account of

cheapness. It is further stated that, since permission has been obtained

to use denatured alcohol in the manufacture of ether, the cost of the latter

has been reduced to such an extent that it has again become advantageous

to use it in place of acetone. Hence, its use in the new Pharmacopoeia.

1190 Wisconsin Academy of Sciences , Arts , and Letters .

INDEX TO BIBLIOGRAPHY

Oleoresin of Aspidium

1824. Geiger, Ph. L.

1824. Morin

1826. Buchner, A.

1826. Von Esenbeck, Nees

1826. Pesckier, Ch.

1827. Batso, V.

1827. Brandes, R.

1827. Buchner, A.

1827. Van Dyk

1827. Geiger, Ph. L.

1827. Tilloy

1827. Zeller

1828. Meylink

1828. Peschier, Ch.

1828. Winkler, F. L.

1829. Allard

1829. Haendesa

1829. Voget

1844. Hornung

1845. Luck

1851. Bock

1851. Luck, E.

1852. von der Marck

1859. Procter, Win., Jr.

1861. Pavesi

1871. Hager

1875. Patterson, J.

1876. Kruse

1878. Cressler, C. H.

1878. Rohn, E.

1879. Kennedy

1881. Bowman, J.

1881. Seifert, O.

1883. Maish, J. M.

1884. Kramer

1886. Berenger-Feraud

1887. Kremel, A.

1888. Keefer, C. D.

1888. Trimble, H.

1889. Greenwalt, W. G.

1891. Dieterich

1891. Kuersten, R.

1891. Poulsson, E.

1891. Raymon

1891. Reuter, Ludwig

1892. Beringer, G. M.

1892. Duhourcau

1892. Kobert

1892. Sherrard, C. C.

1892. Weppen & Lueders

1892. Dieterich

1893. Bechurts & Peters

1893. Dieterich

1893. Gehe & Co.

1894. Poulsson, E.

1894. Dieterich

1894. Hell & Co.

1895. Van Aubel

1895. Boehm, R.

1895. Dieterich

1896. Bocchi, I.

1896. Daccomo and Scoccianti

1896. Dieterich

1896. Kraft, F.

1896. Caesar and Loretz

1897. Boehm, R.

1897. Candussio

1897. Lauren, W.

1897. Madsen, H. P.

1897. Caesar and Loretz

1897. Dieterich

1897. Gehe & Co.

1897. Chem. Centralb.

3898. Bellingrodt, Fr.

1898. Dieterich, Karl

1898. Duesterbehn, F.

1898. Katz, Julius

1898. Lefils

1898. Miehle, Feodor

1898. Plzak, F.

1898. Caesar & Loretz

1898. Gehe & Co.

1898. Pharm. Centralh.

Du Mez — -The Galenical Oleoresins,

1191

Oleoresin of Aspidium. — Con.

1912. Caesar & Loretz

1912. Evans Sons Leseher & Webb

1912. Merck’s Rep.

1912. Southall Bros. & Barclay

1913. Bohrisch, P.

1913. Du Mez, A. G.

1913. Goris & Voisin

1913. Harrison and Self

1913. Hill, C. A.

1913. Parry, E. J.

1913. Yagi, E.

1913. Caesar and Loretz

1913. Evans Sons Leseher & Webb

1913. Southall Bros. & Barclay

1914. Bohrisch, P.

1914. Linke, H.

1914. Vanderkleed, C. E.

1914. Caesar & Loretz

1914. Journ. A. Ph. A.

1914. Riedel’s Ber.

1915. Sherman, H. B.

1915. Southall Bros. & Barclay.

Oleoresin of Capsicum

1849. Procter, Wm. Jr.

1853. Bakes, W. C.

1864. Parrish, E.

1872. Maish, J. M.

1873. Bucheim

1888. Trimble, H.

1892. Sherrad, C. C.

1898. Winton, Ogden and Mitchell.

1903. Beythien

1903. Southall Bros. & Barclay

1905. Vanderkleed, C. E.

1905. Am. Drugg. & Pharm. Ree.

1907. Patch, E. L.

1908. Patch, E. L.

1908. Vanderkleed, C. E.

1909. Vanderkleed, C. E.

1910. Brown, L. A.

1910. Eldred, E. R.

1910. Southall Bros. & Barclay

1910. Vanderkleed, C. E.

1911. Deane; Harold

1911. Vanderkleed, C. E.

1912. Vanderkleed, C. E.

1192 Wisconsin Academy of Sciences, Arts, and Letters ,

Oleoresin of Capsicum. — Con.

1913. Cliem. & Drugg.

1913. Engelhard!, H.

1913. Patch, E. L.

1912. Evans Sons Lescher & Webb

1912. Johnson & Johnson

1913. Umney, J. C.

1913. Vanderkleed, C. E.

1914. Patch, E. L.

1914. Eippetoe, J. E.

1914. Vanderkleed, C. E.

1914. Journ. A. Ph. A.

1914. Eiedel ’s Ber.

1915. Vanderkleed, C. E.

Oleoresin of Cubeb

Oleoresin of Cubeb. — Con.

1907. Blome, W. H.

1907. Smith, A. W.

1907. Evans Sons Lescher & Webb

1908. Vanderkleed, C. E.

1909. Vanderkleed, C. E.

1909. Chem. & Drugg.

1910. Gane, E. H.

1910. Vanderkleed, C. E.

1910. Southall Bros. & Barclay

1911. Southall Bros. & Barclay

1911. Vanderkleed, C. E.

1912. Dohme & Engelhardt

1912. Gluecksmann, G.

1912. Vanderkleed, C. E.

1913. Dohme & Engelhardt

1913. Vanderkleed, C. E.

1914. Maines and Gardner

1914. Eippetoe, J. E.

1914. Seoville, W. L.

1914. Vanderkleed, C. E.

1914. Journ. A. Ph. A.

1914. Eiedel ’s Ber.

Oleoresin of Ginger

1834. Beral

1849. Procter, Wm., Jr.

1859. Procter, Wm., Jr.

1866. Eittenhouse, H. N.

1867. Pile

1872. Maish, J. M.

1877. Wolff, L.

1879. Thresh

1886. Jones, E. W.

1888. Trimble, H.

1891. Eiegel, S. J.

1892. Sherrard, C. C.

1893. Dyer and Gilbard

1895. Davis, E. G.

1896. Liverseege

1897. Glass and Thresh

1901. Bennet

1903. Ballard

1903. Southall Bros. & Barclay

1905. Helfenberger Ann.

1908. Spaeth, Eduard

1908. Vanderkleed, C. E.

1909. Pateh, E. L.

Du Mez — The Galenical Oleoresins .

1193

Oleoresin of Ginger — Con.

1909. Vanderkleed, C. E.

1910. La Wall, C. H.

1910. Vanderkleed, C. E.

1911. Beythien, Hemple & Others

1911. Vanderkleed, C. E.

1912. Hooper, D.

1912. Patch, E. L.

1912. Vanderkleed, C. E.

1913. Engelhardt, H.

1913. Patch, E. L.

1913. Vanderkleed, C. E.

1913. Chem. & Drugg.

1914. Rippetoe, J. R.

1914. Vanderkleed, C. E.

1914. Journ. A. Ph. A.

1915. Vanderkleed, C. E.

Oleoresin of Lupulin

1823. Blanche

1853. Livermore

1859. Procter, Wm. Jr.

1869. Rump, C.

1888. Trimble, H.

1892. Sherrard, C. G.

1907. Van der Harst, J. G.

1908. Dohme & Engelhardt

1909. Bernegau, L. H.

1909. Dohme & Engelhardt

1909. Parson, W. A.

1911. Bernegan, L. H.

1911. Francis, J. H.

1913. Gane, E. H.

1913. Engelhardt, H.

1913. Osborne, O. F.

1913. Patch, E. L.

1914. Rippetoe, J. R.

1915. Glickman, L. H.

Oleoresin of Parsley Fruit

1877. Wolff, L.

1892. Beringer, G. M.

1906. Merck ’s Ann. Rep.

1909. Evans Sons, Lescher & Webb

1913. Engelhardt, H.

1913. Osborne, O. F.

1914. Journ. A. Ph. A.

Oleoresin of Pepper

1825. Meli

1829. Carpenter, G. W.

1859. Procter, Wm. Jr.

1877. Wolff, L.

1888. Trimble, H. .

1892. Sherrard, C. C.

1903. Ballard

1913. La Wall, O. H.

1913. Engelhardt, H.

1913. Patch, E. L.

1914. Journ. A. Ph. A.

Oleoresin of Allcanet Boot

1892. Gehe & Co.

Oleoresin of Annatto

1895. Gehe & Co.

Oleoresin of Cardamom Seed

1849. Procter, Wm., Jr.

1859. “ <* “

Oleoresin of Chenopodi/um

1849. Procter, Wm., Jr.

1877. Wolff, L.

Oleoresin of Clove

1849. Procter, Wm., Jr.

Oleoresin of Conium Leaves

1870. Lefort, M. J.

Oleoresin of Pepo

3890. Minner, L. A.

Oleoresin of Pyrethrum

1849. Procter, Wm., Jr.

1859. “ “ “

1902. Southall Bros, and Barclay

1911. “ “ “ "

Oleoresin of Santonica

1830. Sehuppmann

1849. Procter, Wm., Jr.

1877. Wolff, L.

1194 Wisconsin Academy of Sciences, Arts, and Letters.

Oleoresin of Savine

1849. Procter, Win., Jr.

Oleoresin of Saw Palmetto

1914. E ’we, G. E.

Oleoresin of Xanthoxylum

1849. Procter, Wm., Jr.

0 leoresins ( General )

1869. Squibb, E.

1873. Bemington, J. P.

1887. Lippincott, C. P.

1900. Maish, H. C.

1905. Francis, J. M.

1905. Drug Topics

1916. Beringer, G. M.

Keene — Studies in Zygospore Formation.

1195

STUDIES OF ZYGOSPORE FORMATION IN

PHYCOMYCES NITENS KUNZE

Mary Lucille Keene

The problem of sexuality in the Mucorineae offers an ex¬

tremely interesting field of investigation for the physiologist.

Great differences have been found to exist with regard to the

production of zygospores and sporangia and considerable ex¬

perimentation has been carried on to determine the conditions

influencing asexual and sexual reproduction.

The cytological features are very incompletely known. Nu¬

merous studies have been made upon Sporodinia grandis, a homo-

thallic form, with more or less conflicting results. They have

served, however, to give us some insight into the internal

changes which occur when zygospore formation takes place.

With the heterothallic forms, on the other hand, there has been

little done and the field open here offers many interesting pos¬

sibilities.

Conjugation in the Mucorineae was first described by Ehren-

berg (1820) in a form ^he termed Syzygites megalocarpus

(Sporodinia grandis). De Bary (1864) described the process

of conjugation and zygospore formation in both Sporodinia

grandis and Rhizopus nigricans. Following this work of de

Bary, various workers undertook to study and explain the con¬

ditions responsible for the production of zygospores.

Van Tieghem (1876) believed the impoverishment of the

medium to be responsible for the production of the zygospores.

Cornu (1876) attributed it to desiccation. Brefeld (1872) in

an early paper cited cold as an agent but later (1900) he de¬

cided that zygospore formation is undoubtedly due primarily

to some unknown internal cause. Bainier (1883 a and b, 1884)

1196 Wisconsin Academy of Sciences , Arts, and Letters.

concluded that the production of zygospores is influenced by

the medium on which they are grown. Zopf (1888) attributed

their formation to the invasion of parasites which caused a

decrease in the number of sporangia produced. Klebs (1898,

1902) attributed the immediate cause of sporangial formation

to transpiration, the stimulus for zygospore production being

concerned with decreased transpiration. Falck (1901) claimed

that zygospores would form only when the concentration of the

medium is high and that the relative humidity is of slight, if

any, importance.

Blakeslee (1904) confirmed Klebs’ results showing that in¬

creased moisture favors the formation of zygospores. He also

showed that the concentration of the medium is unimportant.

Blakeslee came to the conclusion, however, that these various

physical factors were but secondary influences and that pure

sexual strains existed upon which zygospore production was

primarily dependent. He obtained cultures of Rhizopus nig¬

ricans from mycelia which had developed from the suspensors

of a zygospore and succeeded in isolating two pure strains

which, when grown alone through numerous generations, gave

rise to sporangial growth only. If they were ‘ ‘ contrasted, ’ 7

that is, grown side by side, or in mixed cultures, they readily

produced zygospores. Thus the heterothallic nature of

Rhizopus nigricans was established. Later he extended his work

to include Absidia caerulea, Phycomyces nitens, Mucor mucedo,

and several undetermined Mucors, among the heterothallic

forms.

Blakeslee ’s results have not been extensively tested by other in¬

vestigators. Hamaker (1906) claimed that zygospores of

Rhizopus nigricans could be produced unfailingly upon proper

media. Namyslowski (1906) also believed that the nutrients

were responsible for zygospore production.

The writer (1914) in an earlier paper reviewed rather com¬

pletely the literature relevant to the cytology of conjugation in

the Mucorineae.

The results of studies upon Sporodinia grandis published by

the writer (1914) vary but little from those published by

Dangeard (1906) in his later paper. Fusions in pairs appear

to take place between the nuclei of the fusing gametes. Cer¬

tain plastid-like bodies apparently concerned with the produc-

Keene — Studies in Zygospore Formation. 1197

tion of an oily reserve substance are described. These bodies

are small and numerous in partially mature zygospores but

later become reduced to one or two large plasmatic bodies sat¬

urated with oil. A nuclear disorganization takes place. All of

the nuclei do not disorganize and, even in the mature zygospore,

many of the normal but slightly larger nuclei are present.

The mature zygospore contains a large amount of an irreg¬

ularly knotted or densely granular, red-staining substance

which the writer was unable to explain. It reacted to the

triple stain much as the mucorin crystals do, but appeared to

arise from the disorganized nuclei.

Burgeff (1915) describes briefly the internal changes which

take place at the time of conjugation and of the formation and

germination of the zygospores of Phycomyces nitens . At the

time of conjugation the nuclei become collected at the places of

contact of the gametes, a large vacuole becomes evident, the’

wall is resorbed and the zygospore is established. The nuclei

are equally distributed throughout the zygospore. No nuclear

fusions are to be noted. Vacuoles containing oil appear, to¬

gether with granular masses which are protein-like reserve sub¬

stances. Later the oil vacuoles flow together into a few large

globules. At two to four months after formation, one central

oil globule is present. The nuclei lie in the outer layer of

the non-granular, weakly staining, hollow, cytoplasmic sphere

which surrounds the oil globule. The nuclei are homogeneous,

without a membrane and are surrounded by a clear zone.

Burgeff finds that, at the time of germination of the

zygospores of one variety, the nuclei are arranged in pairs in the

periphery. A varying number of the nuclei appear to fuse in

pairs. In another variety the conjugation of the nuclei ap¬

pears to take place before germination. The oil globules be¬

come reduced and the cytoplasm becomes vacuolate. As the

germ tube pushes out, the nuclei undergo mitotic division.

The single chromatin grain of the nucleus forms simple, small

chromosomes. The approximate number, determined by count

and estimation, is twenty-four. They appear to separate into

groups of twelve and become surrounded by a membrane.

The present piece of work was undertaken in the hope that

some further facts concerning these internal phenomena might

be offered. Furthermore, in view of the work done by Blakeslee

1198 Wisconsin Academy of Sciences , Arts , and Letters.

and of the very interesting field opened up by his explanation

of the sexuality of the Mucorineae, it was thought possible that

some internal differences might be found which could be cor¬

related with the apparent inherent difference between the two

strains, or to bring the problem to the point where some such

correlation might be possible when the more general cytological

features were known.

The previous work was carried out on Sporodinia grandis ,

a homothallic form, in which it is a very simple matter to ob¬

tain zygospores in abundance with the simplest cultural

methods. The present work, however, has been done on

Phycomyces nitens, a heterothallic form, in which certain sec¬

ondary factors are relevant to zygospore production.

I am indebted for my cultures to Dr. R. A. Harper, who

kindly supplied me with zygosporic plates in which the two

strains had been contrasted and a line of zygospores had re¬

sulted in the characteristic fashion where the mycelia of the

two strains had come together. Isolations were made from

these plates and the pure plus and minus strains resolved.

Mixed cultures were also obtained which produced zygospores

profusely.

I am also indebted to Dr. L. 0. Kunkel for pure plus and

minus cultures of Phycomyces nitens which were, I believe, ofi

the same stock as those furnished in plate form by Dr. Harper.

METHODS

Stock cultures of the pure plus and minus strains of

Phycomyces nitens have been kept on various media. Rice or

rye bread has been used for the most part because of the ease

of manipulation. Small Erlenmeyer flasks are very satisfac¬

tory containers for culture work because there is less surface

exposed for evaporation and they are less subject to contam¬

ination than the wider-mouthed culture dishes that are ordin¬

arily employed. The cotton plugs may be covered with tin

foil so that all the moisture is conserved.

At intervals the strains have been inoculated side by side

on the various kinds of media and in almost every case a line

of zygospores has been evident by the end of a week. Trans¬

fers of individual sporangia have been made, one from each

strain, with the same marked results when grown together.

Keene — Studies in Zygospore Formation. 1199

Mixed cultures have been kept growing, and here also the

zygospore production has been profuse.

For cytological studies, material ranging from three days

to six months in age was fixed. Various fixing reagents were

employed: Flemming’s solution of various strengths, chrom-

acetic, Bouin’s, and Gilson’s. The younger stages were fixed

directly on the agar and small portions of the agar were car¬

ried through the various stages of washing, dehydrating, and

infiltration with paraffin. Because the young gametophores are

much convoluted and stand erect from the surface of the sub¬

stratum, it is difficult to obtain satisfactory sections.

The same difficulties of technic were encountered here which

were met with in Sporodinia grandis, but in even a more serious

form. The older zygospores are extremely brittle because of

the heavy walls and the large amount of reserve material con¬

tained within the zygospore. The most satisfactory serial sec¬

tions were obtained from material that was fixed in Flemming’s

solution, thoroughly washed and treated with hydrofluoric acid

while in 95 per cent alcohol. That the resulting structures are

normal and not the result of this treatment is evident from the

fact that in material treated in the usual ways, the same struc¬

tures have been found but it is almost impossible to obtain them

in serial form because of their torn condition.

For infiltration with paraffin, both the xylol and the cedar

oil methods have been employed with equal success. The cedar

oil method is probably better for the older stages.

The younger zygospores were cut into sections of from 5 to

10 microns while the older ones were cut into thicker sections

ranging from 10 to 60 microns. Owing to the size of the zygospore

inclusions found at maturity, the thick sections were more satis¬

factory for all but the nuclear studies. For affixing the sec¬

tions to the slides both the albumen-glycerin and the fish-glue

fixatives were used.

The Flemming’s triple stain was given the preference al¬

though anilin-safranin alone was used in many cases. The

nuclei stand out quite clearly in such preparations. Gram’s

anilin-gentian-violet and iodine stain gave some very beautiful

preparations. They closely resemble preparations made with

Heidenhain’s iron-alum-haematoxylin combination but are very

much more quickly made.

^ 1200 Wisconsin Academy of Sciences , Arts, and Letters.

Stained preparations of the germinating pins and minns

spores were made as follows : the spores were germinated either

in weak sugar solution or in agar. Bouillon is to be avoided be¬

cause of precipitation in the subsequent treatment. The spores,

germinated in sugar solution, were flooded onto a slide, which

had been previously covered with fish-glue fixative, and allowed

to stand. When almost dry, the preparation was covered with

the fixing solution, either Flemming’s or chrom-acetic. The

latter is the more satisfactory because subsequent bleaching is

not necessary. After an exposure for ten minutes, the fix¬

ing agent was drawn off by means of filter paper and the slide

was washed carefully in water. Many of the spores washed

off but enough remained to give very satisfactory preparations.

It was found best to use alcoholic stains if possible because the

less the preparations are washed in water the better they are

in the end.

The spores germinated in agar were also fixed and carried

through to paraffin in the usual ways. These preparations are

not as good because the agar is granular and takes the stain

and because in sectioning the germ tubes are cut at various

angles.

The pure strains of the sporangial cultures were grown on

rye bread in large flat dishes. The sporangia were collected

at various stages and fixed as previously described. The studies

of the sporangia in fixed material were restricted to the large

sporangia which are produced in older cultures.

LIFE HISTORY AND DEVELOPMENT

Under natural conditions Phycomyces nitens is found grow¬

ing most commonly in fresh manure. In the majority of texts

and general descriptions it is described as preferring an oily

substratum, but there seems to be little evidence to support

this statement. It is possible to obtain a luxuriant growth on

any of the ordinary media used in the laboratory for such pur¬

poses, e. g., bread, rice, sugar, and vegetable agars. It requires

considerable moisture and medium temperatures (18° to 28 °C.)

to produce the best vegetative growth.

The spores, are small elliptical bodies with resistant walls.

They possess from four to twelve nuclei each, typically eight.

Keene — Studies in Zygospore Formation. 1201

The spores germinate readily in water or various weak sugar

solutions and broths. They enlarge somewhat and one or two

germ tubes push out (Pl. II, fig. 8). These grow for some dis¬

tance during which time the number of nuclei present increases.

Careful studies have revealed no differences between the spores

of the two strains. The germ tube branches and sub-branches

forming the hyphal network over and through the substratum.

At intervals characteristic enlargements occur and occasionally

from these, rhizoid-like branches grow out. In other cases,

however, these enlargements appear merely as swellings and

what they are functionally remains a question. Internally they

appear much as any other portion of the mycelium ; sometimes

there occurs a clustering of the nuclei in this region. The small

sporangia which are formed first and are produced close to

the substratum appear to be typical in formation and produc¬

tion of spores. The aerial branches which are destined to form

the large sporangia appear yellowish with a blackening toward

the base. The yellow color is due to the presence of a large

amount of oil, as shown by tests, which exudes in droplets when

the sporangiophores are crushed. As the sporangiophores

elongate they exhibit an extreme sensitiveness to light, the ter¬

minal portions bending toward the source of illumination. If

grown in the dark, they elongate to a greater extent than when

grown in the light.

The history of the formation of the sporangia and of the

origin of the spores has been worked out by Swingle (1903).

The young sporangiophores are densely crowded with cytoplasm

and nuclei. The tip swells out into a small rounded structure.

The contents of this are evenly distributed at first but later a

zonation appears with the denser portion of the protoplasm

toward the periphery and the vacuolate portion at the center.

There occurs a marked streaming of the protoplasm into the

sporangium at this stage and the rounded vacuoles of the cen¬

tral portion move out to the periphery. They become filled

with stainable contents which appear bluish when the triple

stain is used. The nuclei are at first evenly distributed through

the outer zone, few occurring in the central region. A layer

of vacuoles having stainable contents becomes arranged in a

dome-shape in the denser portion. The vacuoles flatten, fuse

edge to edge and form a continuous cleft which is filled with

the same material that filled the vacuoles.

76— S. A. L.

1202 Wisconsin Academy of Sciences, Arts, and Letters.

The spore differentiation begins at this time. The vacuoles

lose their rounded form and become angular. As the edges or

points of the vacuoles come in contact, they unite, forming

clefts in the plasm. Furrows cut into the sporeplasm from the

columella. These unite with the clefts formed by the vacuoles

and cut the plasm into irregular masses. The spores vary in

size and in the number of nuclei. The nuclei remain in the

resting stage throughout this process; no cases of nuclear di¬

visions were observed by Swingle.

All the cytoplasm and the nuclei are included in the spores

themselves. Between the spores there occurs the intersporal

slime which has originated in the vacuoles and which Swingle

believes arises as a secretion from the vacuolar membrane. It

is homogeneous when the spores are formed, stains a bluish

brown with the triple stain, and contains no nuclei or other in¬

clusions.

The columella wall begins to form while the spore cleavage

is going on and continues to thicken until the spores are ripe.

Thus it has been shown in this form, as well as by Harper

(1899) for Pilobolus and Sporodinia, that the columella wall

arises as a dome-shaped structure from the very first and not

as a straight wall which later arches up, as has been so erron¬

eously described in many places. The spores finally become

invested with a refringent cell wall which is very resistant to

stains.

Studies of the plus and minus sporangia were made in order

to determine whether or not any morphological differences exist

between the two strains. The sporangia of the two strains

are structurally alike as far as it has been possible to determine.

The young sporangiophores of both show a marked increase in

the number of nuclei. The nuclei, to all appearances, are sim¬

ilar. The subsequent changes that take place in the formation

of the columella and production of spores proceed alike in the

two strains.

The character of the growth of the plus and minus strains

is unlike, and when cultures of each are grown side by side it

is possible to distinguish between them. The mycelium in the

minus strain grows somewhat more slowly and less vigorously

and the sporangia appear to be fewer and later in appearance.

Keene — Studies in Zygospore Formation.

1203

Zygospore Production

Van Tieghem and Le Monnier (1873) were the first to report

the zygospores of Phycomyces nitens and in their drawings in¬

dicate it as a homothallic form, as a result of which de Bary

placed Phycomyces with Sporodinia. Van Tieghem ’s first

cultures were obtained from cochineal. He lost these but later

obtained others from horse dung and again from cochineal.

He failed to obtain zygospores when cultures were made from

a single sporangium. Bainier (1883a) described the zygospores

on horse dung mixed with flax-seed flour or soaked with flour,

but he also realized the uncertainty of securing them. Later

he found that if, during February or March, he started fresh

cultures of horse dung he almost always obtained the zygospores

within a short time. Zygospores have been reported in

Phycomyces microsporus by Van Tieghem (1876) and in

Phycomyces pirrotianus by Morini (1896).

Until Blakeslee (1904) worked with Phycomyces nitens , the

zygospores had not been reported in this country except in one

case in which Thaxter, according to Blakeslee, described them

in rabbit dung obtained from Daytona, Florida.

The general facts of the morphology of conjugation in this

form have been described by de Bary (1864), to whose ac¬

count Blakeslee (1904) has added a few points of interest. The

majority of writers in describing the origin of the progametes

say that the club-shaped progametes develop from the.hyphae,

increase in size, come in contract and fuse. Blakeslee, how¬

ever, believes that the stimulus to development comes from con¬

tact; that they are “ zygotactic ’ ’ and that the progametes are

normally adherent from the first. Blakeslee has devised an

ingenious experiment to determine whether the origin of the

progametes is dependent upon contact or upon chemical stimuli.

The experiment has been repeated by the writer. A small bat¬

tery jar was lined with filter paper. Suspended by means of

wire in the jar, one and one-fourth inches apart, were two

small cheese cloth bags containing rye bread. Blakeslee soaked

these with orange juice but the author found moistening well

with water to be sufficient. An inch of water was put in the

bottom of the jar and paper was tied over the top. This was

then sterilized in the autoclave at 8 lbs. for 15 minutes. When

cool one bag was inoculated with the plus strain and the other

1204 Wisconsin Academy of Sciences, Arts , and Letters.

with the minus strain. The paper cover was replaced, tin foil

was spread over the top to reduce evaporation, and the appara¬

tus was set into the ice box where evaporation would be slow

and light effects negligible. At the end of six days a line of

zygospores had formed midway between the two bread bags.

Thus, as Blakeslee has pointed out, any influence upon the

origin or direction of growth of the gametophores was not the

result of any chemical attraction due to the medium or to con¬

tact of the mycelial masses, but must have been confined to the

aerial portions and is, in all probability, restricted to the hyphae

affected.

Blakeslee describes the more general morphological aspects

of conjugation and zygospore formation. In a later paper

(1906), he describes the germination of the zygospores of

Phycomyces as well as of several other forms. Germination is

said to take place after a long period of rest and it is difficult

to bring the zygospores to germination in the laboratory. In

the process of germination the outer wall is ruptured and a

germ tube forms which produces a rudimentary mycelium on

which are borne sporangia and spores. The spores in turn

give rise to the next vegetative generation. Presumably it is

at the time of the formation of the spores in the germ sporangia

that sex segregation occurs. According to Blakeslee, three

kinds of spores may be produced in a single germ sporangium :

the plus, the minus and the neutral, which upon germination

give rise to the corresponding mycelia.

The effects of external conditions, as secondary influences

related to the formation of zygospores in this form, have not

been carefully investigated by Blakeslee. He secured zygo¬

spores on all the substrata tested, which fact disproves the idea

that oily substances are essential. He obtained them sparsely

on potato agar but plentifully on potato agar acidulated with

orange juice. He finds that the zygospores are produced much

less abundantly in the warm oven, 26°-28°C., than at room

temperature.

The writer has verified these results. In securing zygo¬

spores, the following media have been used successfully: car¬

rots, carrot agar, bean dextrose agar, condensed milk agar,

potato agar, potato dextrose agar, prune agar, dextrose bouil¬

lon agar acidulated with orange juice, bread (both wheat and

Keene — Studies in Zygospore Formation. 1205

rye) and rice. In every case zygospores have been secured

when the medium was inoculated with spores from both strains,

while at no time and on none of the above-mentioned media,

have zygospores been obtained with the pure strains.

No difficulty whatever was experienced in any inoculations

in securing a plentiful production of zygospores when the two

strains were inoculated into the same medium. The matter

of humidity seems to be a very important secondary condition

and the best results are invariably obtained if the cultures are

kept in a cool, humid place. As soon as the medium begins

to dry out, zygospore production ceases and there occurs a

marked increase in vegetative development. Considerable dif¬

ficulty was experienced at first in bringing the zygospores to

maturity, but later it was discovered that moisture conditions

were responsible. If Petri dishes were used it was essential

that a very heavy layer of agar be supplied, and the softer agars

with high moisture content were more satisfactory.

This substantiates the work done by Klebs (1898, 1902) in

which he pointed out the relation of transpiration to spore

formation in Sporodinia grandis , and corroborates the results

obtained by Blakeslee (1904) on Rhizopus nigricans. There

seems to be no evidence in Phycomyces, at least, that zygospore

formation is affected by the concentration of the medium.

Cytology of the Zygospore

When the two branches from sexually different strains of

Phycomyces nitens come together there occur a branching and

lobing which tend to interlock the hyphae (PI. I, figs. 1 and 2).

Previous to contact it is impossible to tell the gametophoric

hyphae from any of the other parts of the mycelium. The

nuclear conditions at this stage are the same as in the resting

mycelium, as far as it has been possible to determine. There is

no evidence of any excessive streaming or increase in the num¬

ber of nuclei. As the branches increase in length, they become

erect, the terminal portions elongate, their inner surfaces lying

parallel and appressed (fig. 3). The gametophores at this time

are usually characterized by a yellow color which is due to the

presence of oil as shown by tests. As the progametes continue

1206 Wisconsin Academy of Sciences , Arts , and Letters.

to enlarge (fig. 4), the cytoplasm becomes somewhat vacuolate,

lines of streaming may be discerned and there occurs a marked

increase in the number of nuclei. Although these stages have

been studied with great care, it is not possible to say with cer¬

tainty that nuclear divisions take place. Certain suggestive

conditions are found, as indicated in the accompanying figures

(PI. II, figs. 9, 9 a, 96), but to any one who has attempted a

study of the nuclei of these forms it will be evident why a final

decision cannot be rendered. The nuclei are so small that only

the most conspicuous changes are apparent. It seems highly

probable that nuclear divisions do occur at this time, however,

as the increase in the number of nuclei in the progametes is

greater than can be readily explained through nuclear migration

from adjacent parts. Furthermore, these peculiar nuclear condi¬

tions are apparent at only four stages : in the progametes ; in the

suspensors prior to formation of the appendages; in the young

sporangiophores ; and in the germinating spores. The accom¬

panying figures (9a, 96, 10a, 106) illustrate the appearance of

the nuclei at this time. The resting nucleus is a small, dense,

globular to ovoid body possessing a conspicuous, red-staining

granule, probably the nucleolus. The chromatin consists of

very small granules scattered through the nuclear cavity. The

nuclear membrane is fairly well defined in most of the nuclei.

At the time of these apparent divisions, there are present from

one to three of these red-staining masses and some of the nuclei

appear somewhat elongated. In what is evidently a polar view

three of these red-staining bodies can be seen, one of which is

usually slightly larger than the other two. In edge view, there

are usually two of these bodies apparent, sometimes of equal

size but often unequal. As far as it has been possible to de¬

termine, the larger of these three bodies is the nucleolus and

the other two represent the chromatic masses. If they were

all nucleoli they would be expected to be visible at other stages.

Furthermore, the granular chromatin which is present in the

resting nucleus is not found in the nuclei showing this condi¬

tion. This would suggest that it had become concentrated into

these small, deep-staining masses.

The tips of the gametophores remain in contact throughout,

but as the gametophores increase in length they also increase in

diameter and the portions back of the tip are gradually forced

Keene — Studies in Zygospore Formation.

1207

apart from each other and round out. At this time, a large

central vacuole becomes apparent in each and the cytoplasm

at the point of contact of the two gametophores is very dense.

This is evident in fresh material and is particularly well brought

out in stained preparations (figs. 9 and 10). There are few,

if any, small vacuoles and the nuclei are very closely placed.

The time of dissolution of the contiguous walls varies here

as in Sporodinia. Sometimes the gametes are cut off from the

suspensors before the protoplasmic masses come into contact,

but in other cases, the intervening wall is resorbed before the

new delimiting walls are established. This condition has

been checked carefully in living material. Figure 10 shows a

section through the gametophores before the formation of the

cross walls. This formation, however, is a matter of a very

short space of time, both being accomplished within an hour.

The formation of the delimiting walls proceeds as it does in

Sporodinia. The new wall forms first at the surface and closes

in gradually in the form of a diaphragm which finally severs

the intervening strand of protoplasm. The same papilla-like

structures found in Sporodinia characterize these walls.

The intervening wall separating the two gametes is usually

dissolved first at the center but may be resorbed in several

places at once. (fig. 10). The protoplasm of one gamete

pushes its way into the protoplasm of the other. Here again,

as in Sporodinia , the author is not inclined to ascribe any sig¬

nificance to this act as due to a sexual differentiation. It ap¬

pears rather to occur as the result of turgescence. If the in¬

ternal pressures are not at an equilibrium, which is hardly to

be expected, when the wall weakens at one spot, the gamete

/ possessing the greater osmotic pressure is released and surges

into the other. Ultimately, the separating wall disappears and

the two gametes appear as one mass (fig. 11). Occasionally

fragments of this wall may be discerned in the zygospore.

An interesting and somewhat perplexing condition arises in

the appearance of the nuclei at this time. As the young zygo¬

spore is delimited and the protoplasm of the two gametes be¬

gins to mix, there occurs a characteristic grouping of the nuclei.

There appear to be from twelve to sixteen nuclei aggregated

in a group (fig. 11). It is impossible to state with certainty

that in each group there are nuclei from each gamete, as there

1208 Wisconsin Academy of Sciences, Arts, and Letters.

is no possible way of distinguishing between the nuclei of the

two branches. In fact the nuclei from the two gametes are

apparently similar in size and content. It seems highly prob¬

able, however, that nuclei from each gamete are aggregated

because nuclei in each group fuse in pairs. This is evidenced

by the fact that the nuclei show an increase in size and a de¬

crease in number prior to any process of nuclear disorganization.

Prior to fusion, the nucleus is dense and granular and possesses

a conspicuous nucleolus. After the fusions take place, the

nuclear plasm appears vacuolate and the nucleolus is much

larger. As indicated in the figures, within one zygospore (fig.

11c) there may be found groups of nuclei in which there occur

from twelve to sixteen small nuclei and other groups in which

there are five large nuclei and two to four smaller ones. There

seems little doubt as to the significance of this condition, since

no marked differences in the size of the nuclei are evident at

any earlier stage.

There are certain large, round, red-staining bodies found

within the zygospore at all stages which must not be confused

with the nuclei. They are far more conspicuous than the

nuclei and are larger. They tak^ffie^saf^^iti:" in the same

way that the nucleolus does and have undoubtedly been in¬

terpreted by some workers as nuclei. They a;re usually con¬

tained within a clear zone and very often eabh possesses a

small secondary body (fig. IleZ). Their appearance suggests

very strongly the crystalloids and globoids of the higher plants.

These bodies are characteristic of many of the Mucorineae and

have been described by various workers. The author has been

able to demonstrate their occurrence at all stages in tHe life

history of both Sporodinia grandis and Phycomyces nitens.

They undoubtedly constitute a form of reserve substance, prob¬

ably protein in nature. In addition to these, there also occur

red-staining angular crystals (fig. lie).

The new wall surrounding the zygospore is established' just

previous to the nuclear fusions. It is laid down inside of the

old gametophore wall (fig. 11). It is more or less roughened

and is probably formed in the same way as in Sporodinia, which

has been described by Yuillemin (1904).

Following the nuclear fusions, there occur nuclear disorgan¬

izations. The cytoplasm of the zygospore becomes finely vacuo-

Keene ■ — Studies in Zygospore Formation.

1209

late. The nuclear disorganizations do not appear to be re¬

stricted to any particular region but occur throughout the

whole zygospore. Some of the nuclei in each group appar¬

ently undergo disintegration. This disorganization appears

to be restricted to the smaller nuclei or presumably to those

which have failed to fuse. During the process of nuclear dis¬

organization the red-staining nucleolus enlarges, stains unevenly

and appears as if being dissolved. The margin takes the stain

but the central portion stains faintly and may even appear

brownish. As disorganization proceeds, and it does so on a

large scale, the resulting masses appear to run together or

coalesce forming irregular or knotted masses. Plate II, fig¬

ure 126 and Plate III, figures 146, 14c illustrate the various

stages in the appearance of this substance. The same sub¬

stance was evident in the zygospores of Sporodinia , but both its

origin and fate were not interpreted. Here, however, there

seems to be little, if any, doubt on these points. As this sub¬

stance increases in volume it becomes concentrated into one or

more central masses. It is without special structure. While

it is alveolar in part, it as of a homogeneous texture and in no

way resembles living cytoplasm. The oil that is contained

within the zygospore sometimes appears as small droplets in

this;;substance but does not mix with it. When fresh zygospores

■•'Ite. are^rushed, gas bubbles may be seen to escape and disappear.

itMeif . of these conditions may explain the alveolar nature of

%tliis mass.

~s. When .'fresh mature zygospores are crushed, the substance in

:• -Bi^^fe]fe^udes as a semi-transparent amorphous mass. It is

nffinM# In water. The oil which is pressed out with it is

honey-colored and rounds up into distinct globules which react

typically to ; Sudan III and osmic acid. The oil is soluble in

xytolr and chloroform. The amorphous material, however, is

pot. Affected by Ahese reagents. The alcohol in the Sudan III

^ _?^ftiay- cag|e a s®§fht precipitation but the mass is not stained.

;.Whcjp h^pfrite' iJlhhol is added, there remains a semi-trans-

pai’Orit substance rv'^lhlfeh becomes brownish upon standing.

AV'^l^ee the stained sections indicated that this substance might

have its origin in the disorganizing nuclei, an attempt was

made to test it for proteins. Because of the small amount of

material that was available, only rather crude microscopical

1210 Wisconsin Academy of Sciences, Arts , and Letters.

tests could be employed. The zygospores were dissected from

their black coats, mounted in water and crushed under a cover-

glass. The oil exuded in the form of yellow globules, while

the amorphous substance was forced out more slowly and in a

more or less irregular mass. Sudan III was then added ; some¬

times the zygospores were mounted directly an this reagent and

then crushed. The oil became a brilliant red while the other

substance remained clear. If the Sudan III were followed by

chloroform, the oil globules immediately disappeared leaving

the amorphous mass behind. The addition of ammonia water

caused the latter to disappear at once. Sodium hydrate had

much the same effect but acted more slowly. The xantho-proteic

test was applied to other crushed zygospores and this mass took

on a decided orange color. Millon’s reagent failed to give the

color changes. Zygospores were crushed in alkaline phenol-

phthalein and apparently gave an acid reaction, since the por¬

tion of the reagent through which the zygospore content was

forced lost its color. The significance of this, however, is not

great, because the reaction of the rest of the cytoplasm may

have been acid. On the other hand, the cytoplasm and nuclei

at this time are reduced to a thin parietal layer, as shown in

sections (PL III, fig. 17), so the acid reaction was probably

caused by these amorphous inclusions. Since it was impracti¬

cable to attempt to isolate this substance in question, the con¬

clusions based upon these tests can only be of the most tenta¬

tive nature but the reactions appear to be those of the nucleo-

proteins. These tests have served merely to separate this type

of reserve material from the oil which is present and to aid in

the interpretation of a rather perplexing condition existing in the

mature zygospore.

At the time that the nuclear disorganizations begin, there

appears a marked zonation in the zygospore (PI. II, fig. 12).

The inner coat of the zygospore, which is semi-transparent, is

produced at this time. It is very thick and resistant. It is

laid down within the brown, roughened wall previously formed.

Thus the mature zygospore is invested with two thick coats

(PI. Ill, fig. 14) and parts of the original gametophore walls

may still be found on the outside in many places. Toward the

margin of the zygospore there appear bluish-staining areas. In

the earlier conditions they appear merely as vacuoles in which

Keene — Studies in Zygospore Formation. 1211

there are stainable contents. When fixed with Flemming’s

solution these areas are blackened by the osmic acid and require

considerable bleaching before they are clear. They are responsible

for the zonate appearance of the zygospore at this time (fig. 13).

The zygospore becomes more and more vacuolate, the groups

of nuclei become separated, and the disorganizing nuclei may be

found distributed throughout the zygospore (PI. II, fig. 12).

As the vacuolate condition increases the center of the zygospore

becomes quite sponge-like in appearance. The bluish-staining

bodies enlarge and begin to appear more or less reticulate (PI.

Ill, fig. 15). They are identical with the bodies described by

the writer in Sporodinia grandis and are undoubtedly associated

with the formation of oil. They do not seem to play as prom¬

inent a part in the maturation processes in PJiycomyces as they

do in Sporodinia. It may be that the protein material just de¬

scribed replaces to some extent, as reserve material in Phycomy-

ces , the oil that is so plentiful in Sporodinia.

The literature referring to the possible relationship between

these structures associated with oil production in the Mucorineae

and the elaioplasts described by many workers, has been reviewed

by the witer in a previous paper (1914). The elaioplasts or

oil plastids, according to these various investigators, are bodies

set aside by the protoplasm for the secretion of oil.

In Sporodinia the oil plastids arise as very small globular

bodies. When first formed they appear as vacuoles with stained

contents but careful study of them under high powers of mag¬

nification shows a coarse reticulation with a more or less homo¬

geneous center. As they increase in size, their reticulate nature

becomes more and more apparent. A coalescence between them

takes place, apparently as the result of crowding, and in the

mature zygospore there may occur from one to three of these

plastids but usually only one large one is present

In PJiycomyces these reticulated bodies, as already described,

appear to originate at various places through the zygospore,

being most apparent toward the margin. Oil is associated with

them from their earliest appearance. As the zygospore matures

these plastid-like bodies become vacuolate, enlarge and assume

the appearance of definite cell structures. In the older zygo¬

spores studied, numerous small 'plastids were still to be found

toward the periphery, but, as indicated in the accompanying

1212 Wisconsin Academy of Sciences , Arts , and Letters.

figures (15 and 16), a single large mass is often found. This

plastid in Phycomyces does not resemble very closely the large

plastid found in the mature zygospores of Sporodinia, but it un¬

doubtedly functions in the same way. In Sporodinia the large

plastid is finely granular and appears delicately reticulate.

In PJiycomyces its protoplasmic nature is not as evident. It is

coarsely reticulate and even alveolate. It appears as if the

protoplasm, when once saturated with oil, loses its granular ap¬

pearance and may even deliquesce.

The large protein masses do not resemble the oil plastids

either in color or in consistency in the prepared sections. In

figure 16, the disorganized nuclei have not as yet become co¬

alesced as they do somewhat later, as shown in figure 17. The

amount of oil apparently becomes somewhat reduced in the older

zygospores. The proportional amount of each substance varies

in different zygospores.

Nuclei of the original typical form can be found throughout

all the different stages described above. They stain somewhat

differently, depending on the age of the zygospores. They are

much reduced in number in the older zygospores but are still

plentiful enough to be evident in many places.

There are several points which emphasize the fact that nuclear

disorganizations take place. The one just mentioned, namely,

that there is a marked reduction in the number of nuclei pres¬

ent in the mature zygospore, is the most important; secondly,

the nuclear disorganization exactly parallels in appearance the

conditions found in the suspensors, where there is no question

concerning the occurrence of both nuclear and cytoplasmic dis¬

integration. Swingle (1903) has described nuclear disorgani¬

zations in the sporangia of both RJiizopus nigricans and PJiy¬

comyces nitens as follows: The first sign of disintegration is

tJie appearance of a red-staining mass on one side. As tJie pro¬

cess goes on, tJie wJiole nucleus comes to appear as a slightly

shrunken, homogeneous mass, often irregular in shape, and

staining the same shade of red as the crystalloids. It might be

argued that these red-staining bodies are crystalloids whose sub¬

stance is being dissolved but I have very good evidence that such

is not the case. * # * There are all stages of disintegration

between the almost perfect nuclei and the most shrunken ones.

Aside from these facts, on any conception of a nuclear-

Keene — Studies in Zygospore Formation. 1213

cytoplasmic balance, it seems improbable that the immense num¬

ber of nuclei which are present in the zygospore following the

fusion of the two gametes, should persist in such a comparatively

small structure, and nuclear disorganizations might normally be

expected to occur.

There occurs an interesting change in the development which

is of importance from a secondary standpoint only. Following

the formation of the delimiting walls in the gametophores, there

appear slight protuberances from the walls of the suspensors

(PL I, fig. 6). These grow rather rapidly and give rise to the

peculiar, dichotomously-branched appendages which grow out

and surround the zygospore givling to it a very characteristic ap¬

pearance (fig. 7). These appendages first appear on the same

suspensor in which septation first occurred. This, however,

does not appear to be due to any inherent difference between the

two strains. Internally the changes are interesting.

Nuclear divisions appear to follow the cutting off of the ter¬

minal portions, or the nuclear divisions inaugurated in the

progametes continue, and there results an increase in the num¬

ber of nuclei in the suspensors. In a cross section of the sus¬

pensors there appear peculiar deep-staining areas opposite the

places from which the appendages grow. The nuclei in these

areas appear as if caught in a current and even show elongation

in the direction of the current. The appendages as they elong¬

ate become filled with protoplasm and later appear vacuolate

with only a thin lining layer of protoplasm in which the nuclei

are distributed in about the same proportion as in the vegetative

mycelium. All the protoplasm and nuclei disappear in the

older stages and the appendages and suspensors appear empty

(PI. Ill, fig. 14). Occasionally dense, red-staining bodies may

be found in the suspensors. They resemble closely the protein

masses found in the partly mature zygospore and are probably

of similar origin.

Zygospore germinations were secured in only one small lot of

material so it has not been possible to carry the history of the

internal changes to completion. It will be interesting to know

what is the fate of these various substances in germination and

what are the nuclear behaviors which complete the cycle.

Thus it will be seen that fundamentally, the changes which

take place when sexual reproduction occurs in Phycomyces

1214 Wisconsin Academy of Sciences, Arts , and Letters.

nitens are essentially the same as those that occur in Sporodinia

grandis . The conditions of nuclear fusions and subsequent dis¬

integrations are the same. There appear, in both forms, cer¬

tain plastid-like bodies which are associated with the oil which

occurs as a reserve substance. In Sporodinia the disintegration

of the nuclei results in the formation of an irregular knotted

mass of material which in Phycomyces appears as a mass of

what is probably either nucleic acid or nucleo-protein substance.

Careful cytological studies of the plus and minus strains of

germinating spores, young sporangiophores, sporangia and

progametes have revealed nothing in the nature of a morpholo¬

gical sexual differentiation. The author is satisfied that if any

such means of differentiation between the two strains is to be

found, it must be looked for in the germ sporangia where se¬

gregation undoubtedly occurs or more likely in physiological

conditions. Perhaps microchemical tests will reveal a differ¬

ence in the materials present in the two strains, especially in the

progametes.

Many workers have described coenocentra in the Phycomy-

cetes and McCormick (1912) has described the presence of a

coenoeentrum in the zygospores of Rhizopus nigricans but in

Phycomyces nitens nothing has been encountered which answers

the descriptions of a coenoeentrum. While aggregations of

nuclei occur, they are entirely independent of any coenocentra-

like structures.

Young and partially mature zygospores have been studied in

Rhizopus nigricans, another heterothallic form, and much the

same set of conditions has been found as described in the pres¬

ent paper. The nuclei show the same clustered condition and

subsequent nuclear disintegrations occur. The nature of the

reserve substances in the mature zygospores has not been de¬

termined as yet. Work on Zygorhynchus moelleri was aban¬

doned temporarily because of the very small size of the zygo¬

spores and the accompanying difficulties of technic. But, in

view of the present work, there remains open an interesting

problem in connection with such forms as show a morphological

differentiation between the two sexual branches. It is interest¬

ing to note, as Blakeslee has pointed out, that in the heterothallic

forms where we should expect to find an inequality of the

gametes none occurs uniformly, while in Zygorhynchus and

Keene— Studies in Zygospore Formation. 1215

Dicranophora , homothallic forms, the morphological differen¬

tiation is marked and constant.

Summary

1. There are no morphological differences to be found in the

germinating spores of the plus and minus strains of Phycomyces

nitens. They both germinate by means of one or two germ

tubes which branch and produce, the vegetative mycelium.

2. The vegetative mycelium of the minus strain grows some¬

what less vigorously than that of the plus strain and the spor¬

angia appear later.

3. The sporangia of the plus and minus strains are similar

in all respects.

4. The two strains — the plus and the minus — are necessary

in order to secure zygospores.

5. Zygospores were secured on various kinds of media and

their production does not seem to be in any way dependent

upon the concentration of the medium. Humidity, however,

appears to be an important secondary factor.

6. Interlocking of lobes occurs when certain hyphal branches

of the plus and minus strains come in contact. This appears

to be the result of contact and not of chemical stimulation.

7. The terminal portions of these branches elongate forming

the progametes. There is no difference morphologically be¬

tween the two progametes.

8. The progametes show an increase in the number of nuclei

as they increase in size and round out from each other. This

increase in the number of nuclei is undoubtedly due to nuclear

divisions.

9. Delimiting walls are formed which cut off the terminal

portions, resorption of the contiguous walls occurs, the two

gametes come in contact, and a mixing of the protoplasm takes

place.

1216 Wisconsin Academy of Sciences, Arts , and Letters.

10. Grouping of the nuclei follows. There occur from 12 to

16 nuclei in each group.

11. Nuclear fusions in pairs follow, resulting in the reduction

in the number of nuclei and in an increase in the size of the

nuclei.

12. Deep-staining, crystal-like bodies are to be found at all

stages. They resemble the crystalloids and globoids of the

higher plants and undoubtedly constitute a form of reserve sub¬

stance.

13. Zonations within the zygospore take place at the time

of the formation of the second wall which invests the zygospore,

and at the time of the appearance of the oil masses.

14. Disorganization of some of the nuclei follows and re¬

sults in the formation of a large amount of irregular to globular

masses of a deep-staining substance.

15. The oil plastids enlarge, show reduction in number and

appear as definite reticulate bodies.

16. In the mature zygospore there are found two different

types of reserve material.

a. A large amorphous mass of what is probably nucleo-

protein substance.

b. A considerable amount of oil.

17. Nuclei of the typical form are found in much reduced

numbers in zygospores six months old. The protoplasm is re¬

duced to a thin parietal layer.

This work has been done under the direction of Professor G.

M. Reed of the University of Missouri and I am greatly in¬

debted to him for his unfailing interest and valuable sugges¬

tions.

Madison, Wisconsin.

Keene — Studies in Zygospore Formation.

1217

LITERATURE CITED

Bainier, G. 1883 a Sur les zygospores des Mucorinees. Ann. des Sci. nat.

Bot. Ser. 6, 15 : 342-356.

- - 1883 b Observations sur les Mucorinees. Ann. des Sei. nat. Bot.

Ser. 6, 15: 70-104.

- 1884 Nouvelles observations sur les zygospores des Mucorinees

Ann. des Sci. nat. Bot. Ser. 6, 19: 200-216.

Bary, de A. 1864 Syzygites megalocarpus. Beitrage zur Morphologie

und Physiologic der Pilze 1: 74-78.

Blake slee, A. F. 1904 Sexual reproduction in the Mucorineae. Proc.

Amer. Acad. Arts and Sei. 40: 205-319.

- 1906 Zygospore germinations in the Mucorineae. Annales Mycol-

ogici 4: 1-28.

Brefeld, O. 1872 Zygomyceten. Botanische Untersuchungen iiber

Sehimmelpilze. Leipzig. 1: 1-64.

- 1901 iiber die geschlechtlichen und ungeschlechtlichen Fruchtformen

bei copulirenden Piben. Jahresber. Sehles. Ges. f. vaterl. Kultur 78:

71-84.

Burgeff, H. 1915 Untersuchungen iiber Yarabilitat, Sexualitat und Erb-

lichkeit bei Thycomyces nitens. Flora 108: 353-448.

Cornu, M. 1876 Note. Bull. Soc. Bot. de Fr. 23: 13-14.

Dangeard, P. A. 1906 La fecundation nueleaire chez les Mucorinees.

Compt. rend. Acad. Sci. [Paris] 142: 645-646.

Ehrenberg, C. F. 1820 Syzygites eine neue Schimmelpil z ga ttung nebst

Beobaehtungen iiber sichtbare Bewegung in Schimmeln. Yerhandl.

der Gesellsch. nat. Freunde. Berlin. 1.

Falck, R. 1901 Die Bedingungen und Bedeutung der Zygotenbildung bei

Sporodinia grandis. Cohn ’s Beitrage zur Biologic der P Hanzen 8:

213-306.

Hamaker, J. T. 1906 A culture medium for the zygospores of Mucor

stolonifer. Science n. s. 23: 710.

Harper, R. A. 1899 Cell division in sporangia and asci. Ann. Bot. 13:

467-524.

77— S. A. L.

1218 Wisconsin Academy of Sciences , Arts, and Letters.

Keene, M. L. 1914 Cytologieal studies of the zygospores of Sporodinia

grandis. Ann. Bot. 28: 455-470.

Klebs, G. 1898 Zur Physiologie der Fortpflanzung einiger Pilze. Jahrb.

fur wiss. Bot. 32: 1-70.

- 1902 fiber Sporodinia grandis. Bot. Zeit. 60: 178-199.

McCormick, F. 1912 Development of the zygospores of Rhizopus nigri¬

cans. Bot. Gaz. 53: 61.

Morini, F. 1896 Note Mieologiche. Malpighia 10: 72-99.

Namyslowski, B. 1906 Rhizopus nigricans et les conditions de la for¬

mation de ses zygospores. Bull. Internat. de l’Acad. des Sci. de

Cracovie. Math, et Natur. pp. 676-692.

Swingle, D. B. 1903 Formation of the spores in the sporangia of

Rhizopus nigricans and Phy corny ces nitens. Bull. Bur. PI. Ind. 37 :

1-40.

Van Tieghem, P., and Le Monnier, G. 1873 Becherches sur les Mucoriiiees.

Ann. des Sci. nat. Bot. Ser. 5, 17: 261.

Van Tieghem, P. 1876 Troisieme memoire sur les Mucorinees. Ann.

des Sci. nat. Bot. Ser. 6, 4: 312-398.

Vuillemin,*’ P. 1904 Becherches morphologiques et morphogenique sur

la membrane des zygospores. Ann. Mycol. 2: 485-506.

Zopf, W. 1888 Zur Kenntniss, der Infectionskrankheiten niederer Thiere

und Pflanzen. Nova Acta Acad. Caes. Leop. Carol 52: 352-358.

4

Keene — Studies in Zygospore Formation. 1219

EXPLANATION OF FIGUEES IN PLATES.

All figures were drawn with the aid of the camera lueida and with the

Zeiss apochromatic objectives and compensating oculars. Figures 8a; 9 a, b, c;

10 a, b; 11a, b, c, d, e; 12 a, b; 14 a, b, c; 17 a, b, were drawn with objective

1.5 mm. and ocular 12. Figure 8 was drawn with objective 1.5 mm. and

ocular 8. Objective 16 mm. and ocular 12 were used with the remaining

figures.., j

Plate I.

Figs 1 and 2. Young gametophores of plus and minus strains showing

lobing and interlocking.

Fig. 3. Young gametophores showing elongation of terminal portions. It

is at this stage that the gametophores appear as erect yellow

columns.

Fig. 4. Enlargement of gametophores.

Fig. 5. Formation of the delimiting walls.

Fig. 6. Showing the origin of the spine-like appendages.

Fig. 7. Mature zygospore with blackened wall and invested with appen¬

dages.

Plate II.

Fig. 8. Germinating spore of plus strain.

Fig. 8a. Nuclei from germinating spore under higher magnification.

Fig. 9. Section through progametes prior to septation or resorption.

Figs. 9a and b. Nuclei from respective progametes. These may illus¬

trate phases of nuclear divisions.

Fig. 9c. Crystalloids.

Fig. 10. Young conjugating branches at the time of resorption of the

separating wall.

Figs. 10a and b. Nuclei from respective suspensors.

Fig. 11. Young zygospore, showing characteristic grouping of the nuclei

following fusion of the protoplasmic masses.

Fig. 11a and b. Nuclei of the suspensors at time of formation of ap¬

pendages.

1220 Wisconsin Academy of Sciences , Arts, and Letters.

Fig. lie. Groups of nuclei showing conditions before and after nuclear

fusions.

Figs. 11 d and e. Crystalloids.

Fig. 12. Zonation at time of formation of second zygospore wall.

Fig. 12a. Nuclei at this stage.

Fig. 12b. Disorganizing nuclei.

Plate III.

*.

Fig. 13. Zonation at time of formation of oil bodies.

Fig. 14. Showing disorganizing nuclei and aggregation of irregular

masses resulting. Shows also the two walls of the zygospore and

a small portion of the old gametophore wall.

Figs. 14a, b. Appearance of nuclei and disorganizing nuclei at this stage.

Fig. 14c. Irregular masses formed by coalescence of disorganizing nuclei.

Fig. 15. Appearance of reticulated oil plastids.

Fig. 16. Large oil plastid and deep-staining area of disorganizing nuclei.

Fig. 17. Mature zygospore showing large alveolated nucleo-protein mass

which results from the disorganized nuclei.

Fig. 17a. Appearance of a portion of the nucleo-protein mass under

higher magnification.

Fig. 17 b. Nuclei of the mature zygospore, much reduced in number.

Trans, wis. acad. vol. xix

PLATE XVI

KEENE — ZYGOSPORE FORMATION IN PHYCOMYCETES

COCKAYNE BOSTON

*0

m 9c-

i

TRANS. WIS. ACAD. VOL. XIX

PLATE XVIII

KEENE — ZYGOSPORE FORMATION IN PHYCOI\

KEENE — ZYGOSPORE FORMATION IN PHYCOMYCETES

COCKAYNE BOSTON

Proceedings of the Academy.

1221

PROCEEDINGS OF THE ACADEMY,

1917 AND 1918

FORTY-SEVENTH ANNUAL MEETING, 1917.

The forty-seventh annual meeting of the Wisconsin Academy

of Sciences, Arts, and Letters, in joint meeting with the Wiscon¬

sin Archeological Society, was held at Milwaukee, on Thursday

and Friday, April 12 and 13, 1917, in the Trustees’ Room of the

Milwaukee Public Museum.

First Session, Thursday, April 12, 3 p. m.

President H. L. Ward called the meeting to order. The com¬

mittee to audit the Treasurer’s accounts was appointed, George

Wagner and Samuel A. Barrett being named. The reports of

the Secretary and Treasurer were read.

The following programme of papers was presented:

1. The Pompeius Strabo Inscription in the Palazzo dei Conservatori.

M. iS. Slaughter. By title.

2. The influence of French Farce on the Towneley Cycle of Mystery

Plays. Louis Wann. By title.

3. Lumberjack Songs and Legends in the North West. K. Bernice

Stewart. Twenty minutes.

4. An Ethnological Trip to Labrador and Hudson Bay. E. W.

Hawkes. Twenty minutes. Illustrated.

5. Ethical Tales of the Eskimo. E. W. Hawkes. Twenty minutes.

Illustrated.

6. The Cotton-tail in Paiute Mythology. ;S. A. Barrett. Fifteen

minutes.

7. The Anthropological Groups of the Milwaukee Public Museum.

iS. A. Barrett. Ten minutes. Illustrated.

8. The New System of Taxidermy for Large Animals. Henry L.

Ward. Five minutes.

1222 Wisconsin Academy of Sciences , Arts , and Letters.

9. A Museum Exhibit on Bird (Protection. Henry, L. Ward. Five

minutes.

10. The Eradication of Insect Pests in Collections. T. E. B. Pope.

Ten minutes.

I

Second Session, Friday, April 13, 9 :30 a. m.

The second session was presided over by President H. L. Ward.

The following programme of papers was presented:

11. The Prehistoric Argillite Culture of New Jersey. E. W. Hawkes-

Ten minutes. Illustrated.

12. The Washo Indian. S. A. Barrett. Twenty minutes. Illus¬

trated.

13. The Creation of the Yosemite Valley as told in Miwak Mythology.

S. A. Barrett. Fifteen minutes. Illustrated.

14. Building Laws of the Greeks and Romans. Alfred C. Clas.

Twenty minutes.

15. The Discovery of Fluorite in the Ordovician Limestones of Wis¬

consin. Rufus M. Bagg. Ten minutes.

16. The Members of the Niagara Formation in New York and their

Western Extension. Ira M. Edwards. Ten minutes.

17. An Instance of the Uncertainty of Calculating the Thickness of

Rock Formations by Measuring the Dip. Ira M. Edwards.

Ten minutes.

18. A New Method for the Estimation of Alum and Benzoate of Soda

in Foods. A. F. Gilman. Ten minutes.,

19. Some Practical (Studies in Food Values. A. F. Gilman. Twenty

minutes.

20. Notes on Parasitic Fungi in Wisconsin. V. J. J. Davis. Ten

minutes.

21. A Biochemical Study of the Plankton of Lake Mendota. Henry

A. Schuette. By title.

22. jSpecies of Lentinus in the Region of the Great Lakes. Edward

T. Harper. By title.

23. A Review of the Plover, Genus Ochthodromus Reichenbach, and

its\ Nearest Allies. Henry C. Oberholser. By title.

24. Pigments of Flowering Plants. Nellie A. Wakeman. By title.

25. The Commercial History of Ginseng of the United (States. W. O.

Richtmann. By title.

26. A Survey of the Commerce of Camphor. W. O. Richtmann. By

title.

27. Further Studies on the Tremellineae of Wisconsin. E. M. Gil¬

bert. By title.

28. Notes on the Fungal Flora of Lake Mendota. E. M. Gilbert.

Five minutes.

Proceedings of the Academy .

1223

29. Studies of Zygospore Formation in Phycomyces nitens Kunze.

Mary Lucille Keene. By title.

Paper 19 was discussed by Dr. J. J. Davis.

Third Session, Friday, April 13, 2 :30 p. m.

Professor Rufus M. Bagg called the meeting to order, after

which the following programme of papers was presented :

30. Proposed Changes in the Culture Area Map of North America.

E. W. Hawkes. Five minues. Illustrated.

31. An Adaptation of the Dewey System to Anthropological Litera¬

ture. ig. A. Barrett. Ten minutes. Illustrated.

32. The Great Basin Culture Area. S. A. Barrett. Twenty minutes.

Illustrated.

33. On the Crystalline Style of the Lamellibranchs. T. C. Nelson.

Ten minutes. (Presented by George Wagner.)

34. On a Remarkable Occurrence of Warblers. George Wagner. Five

minutes.

35. Vertebrates of Northern Michigan. A. R. Cahn. By title.

36. New American Water Mites of the Genus Neumania. Ruth

Marshall. By title.

37. Studies on Myxosporidia from the Urinary Bladders of Wiscon¬

sin Fishes. J. W. Mavor and W. Strasser. By title.

38. Wisconsin and State Rights. Louise B. Kellogg. Fifteen min¬

utes.

39. Routes of Primitive Commerce. W. A. Titus. By title.

40. Beloit Mound Groups. Ira M. Buell. Fifteen minutes.

41. Indian Remains in Sheboygan County. A. Gerend. By title.

42. The Conchordal Fracture in the Flaking of Flint Implements.

H. L. Skavlem. Twenty minutes.

43. Mounds and Sites of Green Lake. C. E. Brown. Fifteen min¬

utes.

44. Indian Earthworks of the Lake Chetek Region. C. E. Brown and

R. H. Becker. By title.

45. The Milwaukee Museum School Loan 'Study Set on Forestry.

Huron H. Smith. Ten minutes. Illustrated.

46. Museum Exhibition of the Fungi. Huron H. Smith. Ten min¬

utes. Illustrated.

47. Botanical Exhibitions in the Public Museum. Huron H. Smith.

Ten minutes.

48. A Native Tree Exhibit for Wisconsin. Huron H. Smith. Ten

minutes.

49. Plans for a State Flora. Huron iH. Smith. Ten minutes.

1224 Wisconsin Academy of Sciences , Arts , and Letters.

On motion, the Secretary was instructed to cast the ballot for

the following candidates for membership :

James Percy Bennett, Madison.

Mabel Mary Brown, Madison-

Ira M. Buell, Beloit.

A. B. Cahn, Madison.

Sylvester J. Carter, Milwaukee.

Ira Edwards, Milwaukee.

Ernest William Hawkes, Milwaukee.

William 0. Johnson, Milwaukee.

George W. Keitt, Madison.

Charles Edward McLenegan, Milwaukee.

Maude Miller, Madison.

Thomas Edmund Burt Pope, Milwaukee.

C. Audrey Bichards, Madison.

Henry A. Schuette, Madison.

Huron Herbert Smith, Milwaukee.

J. Charles Walker, Madison.

Louis Wann, Appleton.

Fred Werner, Milwaukee.

Clyde M. Woodworth, Madison.

Fourth Session, Friday, April 13, 7 :30 p. m.

The annual dinner was held in the Bepublican House, Presi¬

dent H. L. Ward presiding. An informal programme and dis¬

cussion was carried out. At the close of the dinner the Academy

was declared adjourned, to meet in 1918 in Madison.

Arthur Beatty,

Secretary.

Proceedings of the Academy. 1225

REPORT OF THE SECRETARY FOR THE YEAR 1916.

Honorary Members . . . . . 6

Life Members . . . . . . 11

Corresponding Members . . 41

Active Members ....... . 210

Total. . . 268

Changes Since Last Report.

Of the 14 applicants for memberhip at the last annual meet¬

ing, 13 have been enrolled, one not having completed the re¬

quirements by the payment of dues.

Active Members reported in April, 1916. . . . . . 216

New Members enrolled . . . . . . 13

229

Deaths . . . . . . . . . . . . . . 2

Resignations . . . . . . . 3

Dropped for non-payment of dues . . . . . 15

20 20

209

Transferred from Corresponding to Active Membership . . 1

Present Active Membership . . . . . . . 210

New Applications for Membership . . . . . . . . . . 19

Membership Accounts — April 11, 1917.

Memberships paid to end of 1918 or later. . . . . 3

“ “ “ “ “ 1917 16

“ “ “ “ " 1916 152

“ “ “ “ “ 1915 21

“ " “ “ “ 1912, 1913, or 1914. . . 18

210

1226 Wisconsin Academy of Sciences, Arts, and Letters.

I regret to report the loss of two active members by death —

H. S. Hippensteel, Stevens Point, who died April 25, 1916 ; and

W. J. Brinckley, Milwaukee, who died May 1, 1916.

Arthur Beatty,

Secretary.

REPORT OF THE TREASURER FOR THE YEAR 1916.

Receipts.

Received from dues and initiations . $213.04

Received from sale of transactions . . 2.45

Received from interest on bonds . 153.00

$368.49

Balance on band April 8, 1916 . . 29.92

$398.41

Disbursements.

Secretary^ ^Treasurer’s Allowance . $200.00

Safety Deposit Box Rent . 3.00

1 Bond purchased April 2, 1917 . 100.00

$303.00

Balance on hand April 11, 1917 . . . $95.41

Arthur Beatty,

Treasurer.

Milwaukee, April 12, 1917.

Your auditing committee has compared the report of the

treasurer with the books and vouchers, and find that the report

is correct.

GrEORGE WAGNER,

Samuel A. Barrett.

Proceedings of the Academy.

1227

FORTY-EIGHTH ANNUAL MEETING, 1918.

The forty-eighth annual meeting of the Wisconsin Academy of

Sciences, Arts, and Letters, in joint meeting with the Wisconsin

Archeological Society, was held at Madison on Thursday and

Friday, April 11 and 12, 1918, in the Auditorium of the State

Historical Museum.

First Session, Thursday, April 11, 3 :00 p. m.

The meeting was called to order by Professor C. E. Allen,

Vice-President for Sciences, as President Henry L. Ward was

unable td be present on account of sickness. Dean Birge drew

attention to the absence of President Ward in appropriate re¬

marks, and moved that the Secretary send a suitable letter of

condolence to President Ward- This letter was sent at once.

As this was the year for the election of officers, the chairman

named the following nominating committee: Charles R. Van

Hise, J. J. Davis/ Charles S. Slichter.

The chairman also appointed Albert S. Flint and Charles E.

Brown as members of the committee to audit the Treasurer’s

report.

The following programme of papers was presented :

1. Additional Wisconsin Peace Medals. Charles E. Brown. Ten

minutes.

2. Votive Offerings of Indian Pottery from Colombia, S. A. George A.

Collie. Twenty-five minutes.

3. The Stratigraphic Structure of Wisconsin Indian Mounds. Samuel

A. Barrett. Twenty-five minutes. Illustrated. (Read in syn¬

opsis by the Secretary.)

4. Effigy Mounds in Iowa. Charles E. Brown. Ten minutes.

5. The State Collection of War Posters. Ruth O. Roberts. Fifteen

minutes/

1228 Wisconsin Academy of Sciences , Arts , and Letters.

Second Session, Friday, April 12, 9 :30 a. m.

The session was called to order by Vice President Frank G.

Hubbard, who called for the report of the nominating commit¬

tee. The report was as follows :

The committee on nominations beg leave to report the follow¬

ing nominations for officers for the ensuing term :

President , E. A. Birge, Madison.

Vice President, Sciences, Eratus G. Smith Beloit.

Vice President , Arts, A. C. Clas, Milwaukee.

Vice President, Letters, F. L. Paxson, Madison.

Secretary , Arthur Beatty, Madison.

Treasurer, Arthur Beatty, Madison.

Curator, C. E. Brown, Madison.

Librarian, Walter M. Smith, Madison.

Committee on Publication.

The Secretary,

The President,

C. E. Allen, Madison.

Committee on Library.

The Librarian, ex officio,

George Wagner, Madison.

Paul H. Dernehl, Milwaukee.

Rufus M. Bragg, Appleton.

Albert G. Gilman, Rip on.

Committee on Membership.

The Secretary,

L. J. Cole, Madison.

S. A. Barrett, Milwaukee.

A. F. McLeod, Beloit.

E. M. Gilbert, Madison.

Respectfully,

Chas. R. Van Hise,

John J. Davis,

Chas. S. Slighter,

Committee on Nominations.

Proceedings of the Academy.

1229

On motion of the chairman, the Secretary cast the ballot for

the candidates named.

President-elect Birge was then called to the chair.

The reports of the Secretary and of the Treasurer were read,

and the auditing committee vouched for the correctness of the

Treasurer’s accounts.

The reading of papers was then proceeded with, as follows:

6. The Work of the Wisconsin War History Commission. J. W.

Oliver. Ten minutes.

7. The Passing of a Historic Waterway. F. E. Williams. Twenty

minutes.

8. The Literary Precursors of Wagner’s Meister singer. Edwin C.

Roedder. Twenty minutes.

9. A Teacher of William Wordsworth: Joseph Fawcett and The Art

of War. Arthur Beatty. Twenty minutes.

10. The Habits of the Fishes in Wisconsin. A. S. Pearse. Twenty

minutes. Illustrated.

11. Experiments on Rabbits with Immune Serum. M. F. Guyer.

Thirty minutes.

12. The Relation of Age of Dam to the Production of Twins in Cattle.

iSarah V. H. Jones. Ten minutes.

13. Selection for Chemical Characters in Soy Beans and Jimson-weeds.

C. M. Woodworth. Fifteen minutes.

14. The Bottom Fauna in the Deeper Water of Lake Mendota. C.

Juday. Ten minutes.

15. Recent Observations on the Chrysopidae of Milwaukee. Roger C.

Smith. Eight minutes.

16. Chemistry of the Heptane Solution. Edward Kremers. By title.

17. The Hydrohalogens. Leander Sherk. By title.

18. Terpenes as Oxygen Conveyors. E. V. Lynn. By title.

Third Session, Friday, April 12, 2:30 p. m.

President Birge called the afternoon session to order. On the

initiative of the Treasurer the question was raised as to whether

the Academy’s balance should be invested in City of Madison

Bonds as usual, or in securities which pay a higher rate of in¬

terest. After some discussion the Treasurer was advised to con¬

tinue his usual practice.

The presentation of papers was proceeded with, as follows :

19. Housing Problems of the War. L. S. Smith. Thirty minutes.

Illustrated.

1230 Wisconsin Academy of Sciences , Arts , and Letters.

20. The Status of Chlorine in Plant Nutrition. W. E. Tottingham.

Ten minutes.

21. Physiological Balance of Nutrient Solutions, with Reference to

the Theory of Electrolytic Dissociation. W. E. Tottingham.

Ten minutes.

22. Preliminary Notes on the Fungi Found in the Waters of Madison

and Vicinity. E. M. Gilbert. Fifteen minutes.

28. Apospory in Pteris sulcata . W. N. Steil. Fifteen minutes.

24. The Effect of Neutral Salts upon the Toxicity of Acidified Culture

Solutions toward Aspergillus nigier. J. P. Bennett. Ten

minutes.

25. The Relation of Certain Mineral Nutrients to the Composition of

the Oat Plant. J. G. Dickson. Ten minutes.

26. Sex Determination in a Liverwort. C. E. Allen. Ten minutes.

27. Notes on the Summer Birds of Door Peninsula. Wisconsin, and

Adjacent Islands. Hartley H. T. Jackson. By title.

28. The Relation of Vegetation to Bird Life in Texas. Harry C.

Oberholser. By title.

29. Notes on Parasitic Fungi in Wisconsin, VI. J. J. Davis. By title.

At the close of the programme the Secretary presented the

following applications for membership. On motion, the Secre¬

tary was instructed to cast the ballot in their favor :

Melvin H. Brannon, Beloit.

Frederic Doerfler, Madison.

P. H. Hawkins, Madison.

Sarah V. H. Jones, Madison.

Sterling E. Price, Madison.

W. E. Tottingham, Madison.

Charles H. Vilas, Madison.

The Secretary presented the name of Mrs. Lucius Fairchild,

presented by the council for election as an Honorary member.

On motion the Secretary was instructed to cast the ballot in her

favor. This was done, and Mrs. Fairchild was declared an Hon¬

orary Member of the Academy.

On the completion of this item of business the Academy was

declared adjourned.

Arthur Beatty,

Secretary.

Proceedings of the Academy. 1231

\

REPORT OF THE SECRETARY FOR THE YEAR 1917.

Honorary Members . . . 6

Life Members . 11

Corresponding Members . 41

Active Members . 208

Total . 266

Changes Since Last Report in April, 1917.

Of the 19 Applicants for membership at the last Annual Meet¬

ing, all have been enrolled.

Active Members reported in April, 1917 . 210

New Members enrolled since April, 1917 . 19

229

Deaths . 4

Resignations . 6

Dropped for nonpayment of dues . 11

- 21

Present Active Membership . 208

New Applications for Membership to be acted upon at this meeting 7.

Membership Accounts, as Shown April 1, 1918.

Accounts paid to end of 1921 . 2

“ “ “ “ “ 1918 8

“ “ “ “ 1917 . 15 5

“ “ “ “ “ 1916 34

“ “ “ “ “ 1915 7

“ “ “ “ “ 1914 2

208

I regret to have to report the loss of 4 Active Members by

death, since the last Annual meeting. Rev. Dr. Eugene Grover

Updike, of Madison, died Dec. 24, 1917 ; he had been a member

of the Academy since 1892. Professor William Porter of Beloit

1232 Wisconsin Academy of Sciences , Arts , and Letters.

College, a member since 1894, died October, 1917. In October,

1917, William H. Ellsworth, of the Ellsworth-Thayer Mfg. Co.

of Milwaukee, died, his membership dating back to 1905. Mr.

George Bowman Ferry, Architect, of Milwaukee, died in Janu¬

ary, 1918 ; he had been a member since 1896.

Arthur Beatty,

Secretary.

April 12, 1918.

REPORT OF THE TREASURER FOR THE YEAR 1917.

Receipts.

Received from dues and initiations . . . $214.00

Received from sale of transactions . 5.40

Received from interest on bonds . 158.00

Received from 3 bonds matured April 1, 1918 . 300.00

677.40

Balance on hand April 11, 1917 . 95.41

762.81

Disbursements.

Secretary-Treasurer’s Allowance . $200.00

Safety-lDeposit Box Rent . 3.00

Expenses of meeting, 1917 . 10.48

$213.48

Balance on hand April 12, 1918 . $549.33

Present Permanent Investment consists of 25 City of Madi¬

son Bonds.

Arthur Beatty.

Madison, April 12, 1918.

Your committee, appointed to audit the Treasurer’s accounts,

have compared his report with the books, vouchers, and the

bonds in the safety deposit box, and find that the report is cor¬

rect.

Albert S. Flint,

Charles E. Brown.

List of Officers

1233

LIST OF OFFICERS AND MEMBERS

CORRECTED TO SEPTEMBER 1, 1918.

Officers.

President, Edward A. Birge, Madison.

Vice-President, Sciences, Erastus G. Smith, Beloit.

Vice-President , Arts, A. C. Clas, Milwaukee.

Vice-President , Letters, F. L. Paxson, Madison.

Secretary, Arthur Beatty, Madison.

Treasurer, Arthur Beatty, Madison.

Curator, C. E. Brown, Madison.

Librarian, Walter M. Smith, Madison.

Committee on Publication.

The President, ex officio,

The Secretary, ex officio,

C. E. Allen, Madison.

Council.

The President, Vice-Presidents, Secretary, Treasurer, Librarian

and Past Presidents retaining their residence in Wisconsin.

Committee on Library.

The Librarian, ex officio,

George Wagner, Madison.

Paul H. Dernehl, Milwaukee.

Albert G. Gilman, Rip on.

Committee on Membership.

The Secretary, ex officio,

L. J. Cole, Madison.

S. A. Barrett, Milwaukee.

A. F. McLeod, Beloit.

E. M. Gilbert, Madison

78— S. A. L.

1234 Wisconsin Academy of Sciences , Arts, and Letters .

Past Presidents.

Honorable John W. Hoyt, M. D., LL. D.,# Washington, D. C.,

1870-75.

Dr. P. R. Hoy, M. D. ,* 1876-78.

President A. L. Chapin, D. D.,# 1879-81.

Professor Ronald D. Irving, Ph. D.,# 1882-84.

Professor Thomas C. Chamberlain, Ph. D., Sc. D., LL. D.,

Chicago, Ill., 1885-87.

Professor William F. Allen,! 1888-89.

Professor Edward A. Birge, Ph. D., Sc. D., LL. D., Madison,

1889-90.

Librarian George W. Peckham, LL. D., Milwaukee, 189 1-93. *

President Charles R. Yan Hise, Ph. D., LL. D., Madison,

1894-96.

Professor C. Dwight Marsh, A. M., Ph. D., Washington, D. C.,

1897-99.

Professor Charles S. Slighter, M. S., Madison, 1900-1902.

Dr. John J. Davi^, M. D., Racine, 1903-1905.

Professor Louis Kahlenberg, Ph. D., Madison, 1906-1909.

President Samuel Plantz, Ph. D., D. D., LL. D., Lawrence

College, Appleton, 1910-1912.

Professor Dana C. Munro, A. B., A. M., Princeton, New Jer¬

sey, 1913-1915.

Director Henry L. Ward, Milwaukee, 1915-1918.

HONORARY MEMBERS.

Chamberlain, Thomas Chrowder, Hyde Park Hotel, Chicago,

Ill.

A. B. (Beloit) ; Ph. D. (Wisconsin, Michigan) ; LL. D. (Michigan, Beloit,

Columbia, Wisconsin) ; Sc. D. (Illinois). Head of Geological De¬

partment and Director of Walker Museum, University of Chicago,

Consulting Geologist U. S. Geological Survey ; Consulting

Geologist, Wisconsin Natural History Survey ; Geological

Commissioner, Illinois Geological Survey ;

Editor, Journal of Geology.

Fairchild, Mrs. Lucius, 302 Monona Avenue, Madison, Wis¬

consin.

* Deceased, f Deceased December 9, 1889. Professor Birge elected to fill

unexpired term.

List of Members,

1235

Garland, Hamlin, New York, N. Y.

Vice-President, International Institute of Arts and Letters. Chairman of

Cliff-Dwellers, of Chicago.

Jordan, David Starr,

President Emeritus of Stanford University, Stanford Uni¬

versity, Cal.

M. S., Cornell University, 1872; M. D., Indiana Medical College, 1875;

Ph. D., Butler College, 1878; DD. D., Cornell University, 1886, Johns

Hopkins University, 1902, Illinois College, 1903 ; Instructor in Botany,

Cornell University, 1871-72 ; Professor of Natural History, Lombard

University, 1872-73 ; Principal of Appleton (Wis.) Collegiate In¬

stitute, 1873-74; Lecturer in Marine Botany at Penikese,

1873-74; Teacher of Natural History, Indianapolis High

School, 1874-75; Professor of Biology, Butler College,

1875-79 ; Instructor in Botany, Harvard Summer School,

Cumberland Gap, 1875-76 Assistant to U. S. Fish Com¬

missioner, 1877-81 ; Professor of Zoology, Indiana

University, 1879-85 ; President of Indiana Univer¬

sity, 1885-91 ; President of the California Acad¬

emy of Sciences, 1891-98, 1901-03, 1908 ; U. S.

Commissioner in charge of Fur Setl. Inves¬

tigations, 1896-98 ; of Salmon Investiga¬

tions, 1904 ; International Commissioner

of Fisheries, since 1908; President of

the American Association for the

Advancement of Science, 1903-09.

Trelease, William,

Urbana, Ill.

B. S. (Cornell) ; S. D. (Harvard) ; LL. D. (Wisconsin, Missouri, Washington

University) ; Professor of Botany University of Wisconsin, 1883-5 ;

Professor of Botany Washington University 1885-19*3 ; Director

Missouri Botanical Garden, 1889-1912 ; Professor of Botany

University of Illinois, 1913-1918 ; Vice-President Associa¬

tion Internationale des Botanistes and Chairman

American Board of Editors, Botaniches

Centralblatt.

Wheeler, W. M.,

Forest Hills, Boston, Mass.

Ph. D. Professor of Economic Entomology, Harvard University.

1236 Wisconsin Academy of Sciences, Arts , and Letters ,

LIFE MEMBERS

Birge, Edward Asahel, 744 Langdon St., Madison

A. B., A. M. (Williams) ; Ph. D. (Harvard) ; Sc. D. (Western University

of Pennsylvania) ; LL. D. (Williams). Professor of Zoology and

Dean of the College of Letters and Science, University of Wis¬

consin ; Secretary of Commissioners of Fisheries, Wiscon¬

sin ; Director and Superintendent, Wisconsin Geological

and Natural History Survey ; Member, Wisconsin

State Board of Forestry ; Wisconsin Conserva¬

tion Commission, Vice-President, Phi Beta

Kappa

Davis, John Jefferson, 629 Mendota Court, Madison

B. S. (Illinois) ; M. D. (Hahnemann). Physician. Curator of Her¬

barium, University of Wisconsin.

Flint, Albert Stowell, 450 Charter St., Madison

A. B. (Hard) ; A. M. (Cincinnati). Astronomer, Washburn Observa¬

tory, University of Wisconsin.

Hobbs, William Herbert,

820 Oxford Road, Ann Arbor, Mich.

B. S. (Worcester Polytechnic Institute) ; A. M., Ph. D. (Johns Hop¬

kins). Professor of Geology, University of Michigan.

Hoyt, John Wesley, Washington, D. C.

A. M. (Ohio Wesleyan) ; M. D. (Cincinnati) ; LL. D. (Missouri).

Chairman of the National Committee of Four Hundred to

Promote the Establishment of the University of

the United States.

Marsh, Charles Dwight,

3430 Brown St., N. W., Washington, D. C.

A. B., A. M. (Amherst) ; Ph. D. (Chicago). Physiologist in Bureau

of Plant Industry, United States Department of Agriculture.

Plantz, Samuel, 545 Union St., Appleton

A. M. (Lawrence) ; Ph. D. (Boston) ; D. D. (Albion) ; LL. D. (Baker).

President, Lawrence College.

Sharp, Frank Chapman, 27 Mendota Court, Madison

A. B. (Amherst) ; Ph. D. (Berlin). Professor of Philosophy,

University of Wisconsin.

Skinner, Ernest Brown, 210 Lathrop St., Madison

A. B. (Ohio) ; Ph. D. (Chicago) ; Associate Professor of Mathe¬

matics, University of Wisconsin.

List of Members.

1237

Slighter, Charles Sumner, 636 Frances St., Madison

B. S., M. S. (Northwestern). Professor of Applied Mathematics,

University of Wisconsin ; Consulting Engineer.

Van Cleef, Frank Louis,

39 For Green Place, Brooklyn, N. Y.

A. B. (Oberlin, Harvard) ; Ph. D. (Bonn). Chief of Sixth Division

and Translator in Office of Commissioner of Records,

Kings County.

Van Hise, Charles Richard, 772 Langdon St., Madison

B. Met. E., B. S., M. S., Ph. D. (Wisconsin) ; LB. D. (Chicago, Yale,

Harvard, Williams, Dartmouth). President, University of Wis¬

consin ; Consulting Geologist, Wisconsin Geological Survey ;

President, Board of Commissioners, Wisconsin Geologi¬

cal and Natural History Survey ; President, Wis¬

consin State Board of Forestry.

ACTIVE MEMBERS

Allen, Bennett Mills, Lawrence, Kansas

Ph. B. (De Pauw) ; Ph. D. (Chicago). Professor of Zoology Uni¬

versity of Kansas.

Allen, Charles Elmer, 2014 Chamberlin Ave., Madison

B. S., Ph. D. (Wisconsin). Professor of Botany, University of

Wisconsin.

Arzberger, Emil Godfrey, Washington, D. C.

Ph. B. (Wisconsin). Bureau of Plant Industry.

Bagg, Rufus M. Jr., 7 Brokaw Place, Appleton

Professor of Geology and Mineralogy, Curator of Museum,

Lawrence College.

Baird, Edgar A., 3207 Stevens Ave., Minneapolis, Minn.

B. A., M. A., University of Wisconsin.

Barber, W. Harley, 120 Thorn St., Ripon, Wis.

A. B. (University of Wisconsin) ; M. A. (University of Wisconsin).

Registrar and Professor of Physics, Ripon College, Ripon,

Wis. Member of City Council.

Bardeen, Charles Russell, 25 Mendota Court, Madison

A. B. (Harvard) ; M. D. (Johns Hopkins). Professor of Anatomy,

and Dean of the Medical School, University of Wisconsin.

Barrett, S. A., Public Museum, Milwaukee

B. S., M. S., Ph. D. (University of California). Anthropologist;

Curator of Anthropology, Public Museum, Milwaukee.

1238 Wisconsin Academy of Sciences , Arts , and Letters.

Barth, George P., 302 21st St., Milwaukee

Physician.

Bartholomew, Elbert T., 803 State St., Madison

Assistant Professor of Botany, University of Wisconsin.

Bascom, Lelia, 139 W. Gilman St., Madison

Instructor in English, University of Wisconsin.

Beatty, Arthur, 1824 Yilas St., Madison

A. B. (Toronto) ; Ph. D. (Columbia). Assistant Professor of

English, University of Wisconsin.

Bennett, James Percy, 219 W. Gilman St., Madison

Instructor in Botany, University of Wisconsin.

Blackstone, Dodge Pierce, 921 Wisconsin St., Berlin

A. B., a. M., C. E. (Union).

Bleyer, Willard Grosvenor, 625 Langdon St., Madison

B. L., M. L., Ph. D. (Wisconsin). Professor of Journalism,

University of Wisconsin.

Brannon, Melvin H. Beloit

President, Beloit College.

Braun, Adolph R., 832 38th St., Milwaukee

Graduate of National German-American Teachers’ Seminary,

Milwaukee. Teacher of Modern Languages, Milwaukee

High School.

Brown, Charles E., Waban Hill, Nakoma, Madison

Secretary and Curator, Wisconsin Archaeological Society ; Chief

State Historical Museum.

Brown, Charles Newton,

Van Hise Ave. and Roby Road, Madison

LL. B. (Wisconsin). Lawyer.

Brown, Eugene Anson, 2115 Jefferson St., Madison

M. D. (Hahnemann). Physician and Surgeon; Secretary of Board

of Federal Pension Examiners, Madison District.

Brown, Mabel Mary, Madison

Assistant in Botany.

Bryan, G. S., 803 State St., Madison

Instructor in Botany, University of Wisconsin.

Buehler, Henry Andrew, Rolla, Mo.

B. S. (Wisconsin) Geologist; State Geologist of Missouri.

Buell, Ira M., Beloit

Curator of Museum, Beloit College.

I

List of Members .

1239

Bunting, Charles Henry, 2020 Chadbourne Ave., Madison

Professor of Pathology, University of Wisconsin.

Burd, Henry A., 11 S. Warren St., Madison

State Council of Defense, Madison.

Burke, Rush Pearson,

602-4-6 Bell Building, Montgomery, Ala.

M. Sc., M. D. Physician and Surgeon.

Bussewitz, M. A., Milwaukee

Professor, Milwaukee State Normal School.

Cahn, A. R., Madison

Cairns, William B., 2010 Madison St., Madison

A. B., Ph. D. (Wisconsin), Associate Professor of American Litera¬

ture, University of Wisconsin.

Campbell, O.J.,Jr., 15E. Gilman St., Madison

Ph. D. (Harvard). Assistant Professor of English, University of

Wisconsin.

Carr, Muriel B., Montreal, Canada

B. A. (McGill). Instructor in English, McGill University,

Montreal, Canada.

Carter, Sylvester J., 850 Newhall St., Milwaukee, Wis.

B. A., B. L. S. Reference Library, Milwaukee Public Library.

Chandler, Elwyn Francis, University, N. D.

A. B., A. M. (Ripon). Professor of Mathematics, University of North

Dakota ; Assistant Engineer, United States Geological Survey.

Chase, Wayland J., 141 Summit Ave., Madison

A. B., A. M. (Brown). Associate Professor of History, University of

Wisconsin.

Clas, Alfred Charles,

Flat 2, St. James Ct., 815 Grand Ave., Milwaukee

Architect (Perry & Clas), 419 Broadway, Milwaukee; Member,

Board of Park Commissioners.

Clawson, Arthur Brooks,

1884 Monroe St., N. W., Washington, D. C.

A. B. (Michigan). Department of Agriculture, Washington.

Cole, Leon J., 1915 Keyes Ave., Madison

A. B. (Michigan) ; A. M. (Harvard) ; Ph. D. (Wisconsin). Associate

Professor of Experimental Breeding, University of Wisconsin.

Conklin, G. H., 1204 Tower Ave., Superior

Practicing Physician.

1240 Wisconsin Academy of Sciences, Arts, and Letters.

Cool, Charles Dean, 1607 Adams St., Madison

A. B. (Michigan) ; A. M. (Harvard) ; Ph. D. (Wisconsin). Assistant

Professor of Romance Languages, University of Wisconsin.

Culver, Garry Eugene, 1103 Main St., Stevens Point

A. M. (Denison). Professor of Physical Science, State Normal

School.

D aland, William Clifton, Milton

M. A., D. D. President and Professor of the English Language and

of Biblical Literature, Milton College.

Dean, Alletta F., Mansfield, Mass.

Ph. B., Ph. M. (Wisconsin).

Dennis, Alfred Lewis Pinneo,

518 Wisconsin Ave., Madison

A. B. (Princeton) ; Ph. D. (Columbia). Professor of European

History, University of Wisconsin.

Denniston, Rollin Henry, Science Hall, Madison

Ph. G., B. S., Ph. D. (Wisconsin). Assistant Professor of Botany,

University of Wisconsin.

Dernehl, Paul Herman,

717 — 718 Majestic Building, Milwaukee

B. S. (Wisconsin) ; M. D. (Johns Hopkins). Physician.

Dodge, B. 0., New York, N. Y.

Ph. B. (Wisconsin) ; Ph. D. (Columbia). Instructor in Botany,

Secretary-Treasurer Torrey Botanical Club. Depart¬

ment of Botany, Columbia University.

Dodge, Robert Elkin Neil, 15 W. Gorham St., Madison

A. B., A. M. (Harvard). Assistant Professor of English, University

of Wisconsin.

Doerfler, Frederic, 1309 W. Dayton St., Madison

Student at University of Wisconsin.

Dowling, Linnaeus Wayland, 2 Roby Road, .Madison

Ph. D. (Clark). Associate Professor of Mathematics, University of

Wisconsin.

Downes, Robert Hugh, 2434 Jefferson Ave., Norwood, Ohio

B. L. (Wisconsin). General Manager, Norwood Sash and Door

Manufacturing Company.

Du Mez, Andrew Grover,

25th and East Streets, N. W., Washington, D. C.

Edwards, Ira, Milwaukee

Assistant in Geology, Public Museum, Milwaukee.

List of Members.

1241

Ely, Richard Theodore, 205 Prospect Ave., Madison

A. B., A. M. (Columbia) ; Ph. D. (Heidelberg) ; LL. D, (Hobart).

Professor of Political Economy, University of Wisconsin.

Farley, John Herbert, 482 South St., Appleton

A. M. (Lawrence). Professor of Philosophy, Lawrence College.

Ferry, George Bowman, Woodland Court, Milwaukee

Architect, (Ferry & Clas).

Finger, William, 177 34th St., Milwaukee

Insurance, Loans and Real Estate Broker.

Finkler, Adolph, 612 Commerce St., Milwaukee

Secretary, Albert Trostel and Sons Company ; President, Board of

Trustees, National German- American Teachers’ Seminary ; Presi¬

dent, Board of Trustees, German-English Academy.

Fischer, Richard, 119 East Johnson St., Madison

Ph. C., B. S. (Michigan) ; Ph. D. (Marburg). Professor of Chem¬

istry, University of Wisconsin.

Fish, Carl Russell, 244 Lake Lawn PL, Madison

A. B. (Brown) ; A. M., Ph. D. (Harvard). Professor of American

History, University of Wisconsin.

Fling, Harry R., 601 Jackson St., Oshkosh

A. B. (Bowdoin). Professor of Biology, State Normal School.

Frost, William Dodge, 310 N. Orchard St., Madison

B. S., M. S. (Minnesota) ; Ph. D. (Wisconsin). Professor of Bac¬

teriology, University of Wisconsin.

Gay, Lucy Maria, 216 N. Pinckney St., Madison

B. L. (Wisconsin). Assistant Professor of Romance Languages,

University of Wisconsin.

Gilbert, Edward Martinius, 25 Spooner St., Madison

A. B. (Wisconsin). Assistant Professor of Botany, University of

Wisconsin.

Gilman, Albert G., Rip on, Wis.

Professor of Chemistry, Ripon College.

Gloyer, Walter 0., Geneva, N. Y.

B. A., M. A. (Wisconsin). Associate Botanist, New York Agricul¬

tural Experiment Station.

Graenicher, Sigmund, 116 Harmon St., Milwaukee

Ph. D. (Basel) ; M. S. (Munchen).

Gregory, John Goadby, 717 Jefferson St., Milwaukee

Associate Editor, Evening Wisconsin.

Griggs, Horace William, 2421 Sycamore St., Milwaukee

Roundhouse Foreman, C., M. & St. P. Ry. Co.

1242 Wisconsin Academy of Sciences , Arts , and Letters.

Gutsch, Milton R., Austin, Tex.

Professor of History, University of Texas.

Guyer, Michael F., 138 Prospect Ave., Madison

Professor of Zoology, University of Wisconsin.

Haase, Ewald, 182 Wisconsin St., Milwaukee

Secretary, Milwaukee Gas Light Company.

Haessler, Luise, Park Ave. and 68th St., New York, N. Y.

A. B. (Chicago). Assistant Professor of German, Normal College of

the City of New York.

Hall, Edward Bennington,

747 N. Main St., Springfield, Mo.

B. S. (Drury). Assistant Professor, Geology and Mineralogy, Drury

College, Springfield.

Harper, Edward T., Geneseo, Illinois

Harper, Mrs. Robert Aylmer, New York City

Harper, Robert Aylmer, New York City

Professor of Botany, Columbia University.

Hawkes, Ernest William, Milwaukee

Anthropologist, Public Museum.

Hawkins, Peter H., 1910 Regent St., Madison

Heddle, John R., 1625 Monroe St., Madison

Hohlfeld, Alexander Rudolph,

104 Breese Terrace, Madison

Ph. D. (Leipzig). Professor of German, University of Wisconsin;

President, Modern Language Association of America ; Member

of Board of Administration, National German- American

Teachers' Seminary, Milwaukee.

• Holmes, Samuel Jackson, Berkeley, California

B. S., M. S. (California) ; Ph. D. (Chicago). Professor of Zoology,

University of California.

Hotchkiss, W. 0., College Hills, Madison

Geologist, State Highway Commission.

Hubbard, Frank Gaylord, 2006 Monroe St., Madison

A. B. (Williams) ; Ph. D. (Johns Hopkins). Professor of English,

University of Wisconsin.

Humphrey, Clarence J., Madison

Pathologist, Forest Products Laboratory.

List of Members.

1243

Ibsen, H. L., Madison

Assistant in Experimental Breeding-, University of Wisconsin.

Ingersoll, Leonard R., 1933 West Lawn Ave., Madison

B. S. (Colorado College) ; Ph. D. (Wisconsin). Associate Professor

of Physics, University of Wisconsin.

Jackson, Hartley H. T., Washington, D. C.

U. S. Biological Survey.

Jana, Ashutosh,

J astro w, Joseph,

Haria, Bengal, India

237 Langdon St., Madison

A. B., A. M. (Pennsylvania) ; Ph. D. (Johns Hopkins). Professor of

Psychology, University of Wisconsin.

Johnson, Aaron Guy, 1910 West Lawn Ave., Madison

Plant Pathologist, University of Wisconsin.

Johnson, James, 131 Lathrop St., Madison

Assistant Professor of Horticulture, University of Wisconsin.

Johnson, William O., 1416 Lee St., Milwaukee

Assistant in Anthropology Public Museum.

J olivette, Hallie D. M., 900 Campus Ave., Pullman, Wash.

Jones, Lewis R.,

1731 Regent St., Madison

Ph. B., Ph. D. (University of Michigan) ; Sc. D. (Honorary, Univer¬

sity of Vermont). Professor of Plant Pathology, University

of Wisconsin.

Jones, Sarah Van Hoosen, Madison

Assistant in Experimental Breeding, University of Wisconsin.

Juday, Chancey, 35 Lathrop St., Madison

A. M. (Indiana). Biologist, Wisconsin Geological and Natural

History Survey.

Keitt, George Wannamaker, Madison

Plant Pathologist. University of Wisconsin.

Kind, John Louis, The Irving, Sterling Court, Madison

A. B., A. M. (Nebraska) ; Ph. D. (Columbia). Associate Professor

of German, University of Wisconsin.

Kremers, Edward, 1720 Yilas St., Madison

Ph. G., B. S. (Wisconsin) ; Ph. D. (Gottingen) ; D. Sc. (Michigan).

Director of Course in Pharmacy and Professor of Pharma¬

ceutical Chemistry, University of Wisconsin.

Kijhl, E. P., Minneapolis, Minn.

University of Minnesota.

1244 Wisconsin Academy of Sciences , Arts , and Letters.

Kutchin, Mrs. Harriet Lehman, Green Lake, Wis.

A. B. (Ripon) ; A. M. (Northwestern). Engaged in zoological

research.

Langenhan, H. August, 1821 West Lawn Ave., Madison

Instructor in Pharmacy, University of Wisconsin.

Lannerd, Willard, 748 Villa St., Racine

B. S. (Purdue). Instructor in Science and Mathematics, Racine High

School.

Leith, Charles Kenneth, 240 Langdon St., Madison

B. S., Ph. D. (Wisconsin). Professor of Geology, University of Wis¬

consin ; Non-resident Professor of Structural and Meta-

morphic Geology, University of Chicago.

Lenher, Victor, 158 Summit Ave., Madison

Ph. D. (Pennsylvania). Professor of Chemistry, University of

Wisconsin.

Leonard, William Ellery, 2015 Adams St., Madison

A. B. (Boston University) ; M. A. (Harvard) ; Ph. D. (Columbia).

Assistant Professor of English, University of Wisconsin.

Lowe, John N., College Station

Instructor in Zoology, A. and M. College, Texas.

McAllister, Fred, Austin, Texas

Department of Botany, University of Texas.

McCaskill, Virgil Ej, Superior

President, State Normal School.

McKenna, Maurice, 152 S. Main St., Fond du Lac

Lawyer ; President Bar Association of Fond du Lac County.

McLenegan, Charles Edward, Milwaukee

Librarian, Public Library.

McLeod, Andrew Fridley, Beloit

Ph. D. (Wisconsin). Associate Professor of Physical Chemistry,

Beloit College.

McMinn, Amelia, 172 21st St., Milwaukee

B. S. (Wisconsin). Instructor in Biology, State Normal School,

Milwaukee.

Marquette, William George, New York, N. Y.

Ph. G. (Northwestern) ; B. S., Ph. D. (Wisconsin). Assistant Pro¬

fessor of Botany, Columbia University.

Marshall, Ruth, 1225 Sedgwick Ave., Chicago

B. Sc., M. S. (Wisconsin) ; Ph. D. (Nebraska). Teacher, Lane

Technical School, Chicago.

List of Members.

1245

Marshall, William Stanley, 139 E. Gilman St., Madison

B. S. (Swarthmore) ; Ph. D. (Leipzig). Associate Professor of

Entomology, University of Wisconsin.

Mason, Max, 1902 Arlington Place, Madison

B. S. (Wisconsin). Professor of Mathematical Physics, University

of Wisconsin.

Maurer, Edward Rose, 167 Prospect Ave., Madison

B. C. E. (Wisconsin). Professor of Mechanics, University of

Wisconsin.

Mayor, J. W., Schenectady, N. Y.

Professor of Zoology, Union College.

Maxson, Mable, Milton

M. A. Instructor in English and Librarian, Milton College.

Meachem, John Goldesbrough, Jr.,

745 College Ave., Racine

M. D. (Rush). Physician.

Mead, Warren J., 922 Yan Bnren St., Madison

Associate Professor of Geology, University of Wisconsin.

Merrill, Mrs. Sherburne S., 3355 Grand Ave., Milwaukee

First Vice-President, Wisconsin Humane Society ; Second Vice-

President, Woman’s Club of Wisconsin ; President, Public

School Art League.

Meyer, Balt as ar, Henry, Washington, D. C.

B. L., Ph. D., LL. D. (Wisconsin). Member Interstate Commerce

Commission.

Miller, Maude, Madison

Assistant in Botany, University of Wisconsin.

Miller, William Snow, 2001 Jefferson St., Madison

M. D. (Yale). Associate Professor of Anatomy, University of

Wisconsin.

Monroe, C. E., 512 Yan Buren St., Milwaukee

A. B. (Oberlin College) ; LL. B. (Michigan University). Lawyer.

Moore, Samuel, Ann Arbor, Mich.

A. B. (Princeton) ; Ph. D. (Harvard). Associate Professor of Eng¬

lish, University of Michigan.

Morris, H. H., 423 N. Lake St., Madison

Assistant in Chemistry, University of Wisconsin.

Morris, William Augustus Pringle,

Howard Place, Madison

A. B. (Hamilton). Lawyer.

1246 Wisconsin Academy of Sciences , Arts , and Letters.

Muttkowski, Richard Antony, Columbia, Mo.

Department of Zoology, University of Missouri.

Nader, John, 991 New York Ave., Rosebank, N. Y.

Architect and Civil Engineer.

Nagler, Mrs. Ellen Torelle,

438 W. Washington Ave., Madison

Naylor, Wilson Samuel, Appleton

Professor, Lawrence College.

Neilson, Walter Hopper, 114 Garfield Ave., Milwaukee

M. D. (Rush). Dean of the Medical Faculty and Professor of the

Principles and Practice of Medicine and Clinical Medicine,

Milwaukee Medical College.

Oberholser, Harry Church, Washington, D. C.

Assistant Ornithrologist, U. S. Biological Survey.

Olin, John Myers, 130 Prospect Ave., Madison

A. B., A. M. (Williams); LL. B. (Wisconsin). Lawyer; Professor

of Law, University of Wisconsin.

O’Shea, M. Vincent, 140 Langdon St., Madison

B. L. (Cornell). Professor of the Science and Art of Education,

University of Wisconsin.

Overton, James Bertram, 512 Wisconsin Ave., Madison

Ph. B. (Michigan) ; Ph. D. (Chicago). Professor of Plant Physi¬

ology, University of Wisconsin.

Owen, Edward Thomas, 614 State St., Madison

A. B., Ph. D. (Yale). Emeritus Professor of French and Linguistics,

University of Wisconsin.

Owen, Ralph W., Eau Claire

Litt. B. (Princeton) ; M. A. (Wisconsin).

Pammel, L. H., Ames, Iowa

Professor of Pathology, General and Systematic Botany, Iowa State

College.

Parker, Fletcher Andrew, 14 W. Gilman St., Madison

Professor Emeritus of Music, University of Wisconsin ; Vice-President,

Music Teachers’ National Association.

Parkinson, John Barber, 516 Wisconsin Ave., Madison

A. B., A. M. (Wisconsin). Vice-President and Professor Emeritus

of Constitutional and International Law, University of

Wisconsin.

Paxson, Frederic L., 629 Frances St., Madison

Ph. D. (Pennsylvania) ; Professor of American History, University

of Wisconsin.

List of Members.

1247

Pearse, A. S., 2240 Rowley Ave., Madison

Associate Professor of Zoology, University of Wisconsin.

Peaslee, Leon D., Milwaukee

Curator of Education, Public Museum.

Peltier, George L., Auburn, Alabama

Illinois Agricultural Station.

Phillips, James David, 1925 West Lawn Ave., Madison

B. S. (Illinois). Professor of Drawing, University of Wisconsin.

Pierson, Merle Pierson, 15 W. Dayton St., Madison

Pitman, Annie, 414 N. Henry St., Madison

B. A., Ph. D. (Wisconsin). Assistant Professor in Latin, University

of Wisconsin.

Pope, Thomas Edmund Burt, Milwaukee

Curator of Invertebrate Zoology, Public Museum.

Price, Sterling E., 312 Prospect Ave., Madison

Scholar in Experimental Breeding, University of Wisconsin.

Reed, George Mathew, 809 Virginia Ave., Columbia, Mo.

A. B. ( Geneva ) ; A. M., Ph. D. (Wisconsin). Assistant Professor of

Botany, University of Missouri.

Rice, Ole S., Madison

B. S. (Wisconsin). Library Clerk, Office of State Superintendent of

Public Instruction.

Richards, C. Audrey, Madison

Assistant in Botany, University of Wicsonsin.

Roedder, E. C. L. C., 1614 Hoyt St., Madison

A. B., A. M., Ph. D. (University of Michigan). Associate Professor

of German Philology, University of Wisconsin.

Rohde, Hugo W., 1275 Stowell PL, East Milwaukee

Chemist, Schlitz Brewing Company.

Rosenberry, Mrs. Lois K., 504 Wisconsin Ave., Madison

Sammis, J. L., 234 Breese Terrace, Madison

Associate Professor of Dairying, University of Wisconsin.

Sanborn, John Bell, Wisconsin Building, Madison

B. L., M. L., Ph. D. (Wisconsin). Lawyer ; Treasurer, Wisconsin

State Bar Association ; Lecturer, University ■ of Wisconsin

Law School ; Member, Wisconsin Council, American

Bar Association.

1248 Wisconsin Academy of Sciences , Arts, and Letters,

Schinner, Augustin, Eight Eeverend,

840 Downer Ave., Milwaukee

D. D. Bishop.

Schlundt, Herman, Columbia, Mo.

Professor of Chemistry, University of Missouri.

Schorger, A. W., 2021 Kendall Ave., Madison

Burgess Laboratories, Madison.

Schuette, Henry A., Madison

Instructor in Chemistry, University of Wisconsin.

Seyboldt, Robert Francis, 419 Sterling Place, Madison

A. M. (Brown), Ph. D. (Columbia). Assistant Professor of Education,

University of Wisconsin.

Showerman, Grant, 410 N. Butler St., Madison

A. B., A. M., Ph. D. (University of Wisconsin). Professor of Latin,

University of Wisconsin.

Sieker, William Christian,

1542 Prospect Place, Milwaukee

B. S. (Wisconsin). Secretary and Treasurer, Manthey-Sieker

Company.

Slaughter, Moses Stephen, 633 Frances St., Madison

A. B., A. M. (De Pauw) ; Ph. D. (Johns Hopkins). Professor of

Latin, University of Wisconsin.

Smith, Cornell Rae, Milwaukee

Assistant Geologist, Public Museum.

Smith, Erastus Gilbert, 649 Harrison Ave., Beloit

A. B., A. M. (Amherst) ; A. M., Ph. D. (Gottingen). Professor of

Chemistry, Beloit College.

Smith, Gilbert Morgan, 1606 Hoyt St., Madison

Instructor in Botany, University of Wisconsin.

Smith, Huron Herbert, Milwaukee

Curator of Botany, Public Museum.

Smith, Walter Me Mynn, 127 Langdon St., Madison

A. B. (Wisconsin). Librarian, University of Wisconsin.

Smythe, Sidney T., Delafield

A. B., A. M. (St. Stephen's) ; B. D. (Nashotah) ; D. D., Ph. D.

(Hobart). President, St. John’s Military Academy;

Member, Committee on Canons, Protestant

Episcopal Church.

Snow, Benjamin Warner, 221 Langdon St., Madison

Ph. D. (Berlin). Professor of Physics, University of Wisconsin.

Spencer, Matthew Lyle, 8 Alton Place, Appleton

A. B., A. M. (Kentucky Wesleyan College) ; A. M. (Northwestern

University) ; Ph. D. (University of Chicago). Professor of

English, Lawrence College.

List of Members.

1249

Squier, George Hull,

Trempealeau

Dairyman.

Starr, William J., 135 Marston Ave., Eau Claire

LL. B. (Columbia). Member, Board of Commissioners of Fisheries,

Wisconsin ; President, Eau Claire Public Library.

Steidtman, E., 2002 Monroe St., Madison

A. B., A. M., Ph. D. (University of Wisconsin). Assistant Professor

of Geology, University of Wisconsin.

Stickney, M. E.,

Granville, 0.

Denison University.

Stout, Arlow Burdette, New York City

A. B. (Wisconsin). New York Botanical Gardens, Bronx Park

Talbert, George A., Rip on

B. S., M. S. (Ohio Wesleyan). Instructor in Biology, Ripon College.

Teller, Edgar Eugene,

228 Elmwood Ave., Buffalo, N. Y.

Thorkelson, Halsten Joseph Berford,

1526 W. Washington Ave., Madison

B. S., M. E. (Wisconsin). Business Manager, University of

Wisconsin.

Thwaites, F. T., Turvillwood, Madison

Curator of Geological Museum, University of Wisconsin.

Titus, W. A.,

54 Oak Ave., Fond du Lac

Manufacturer. Member of Board of Visitors, University of Wisconsin.

Toole, Eben H., Lafayette, Indiana

Assistant Professor of Plant Physiology and Pathology, Purdue

University.

Tottingham, W. E., Madison

Assistant Professor of Agricultural Chemistry, University of

Wisconsin.

Trever, A. A., 368 State St., Appleton

Ph. D., (Chicago). Professor of Greek, Lawrence College.

Turneaure, Frederick Eugene,

166 Prospect Ave., Madison

C. E. (Cornell). Professor of Engineering and Dean of the College

of Engineering, University of Wisconsin.

Van Vleck, Edward Burr, 519 N. Pinckney St., Madison

A. B., A. M. (Wesleyan) ; Ph. D. (Gottingen) ; LL. D. (Clark). Pro¬

fessor of Mathematics, University of Wisconsin ; Editor,

Transactions of the American Mathematical Society.

79— S. A. L.

1250 Wisconsin Academy of Sciences , Arts , and Letters ,

Vaughan, R. E., 1118 W. Johnson St., Madison

Assistant Professor of Plant Pathology, University of Wisconsin.

Vilas, Charles H., Madison

Retired Physician.

Vogel, Mrs. Guido Charles, 409 Terrace Ave., Milwaukee

B. S. (Wisconsin).

Vorhies, Charles Taylor, Salt Lake City, Utah

B. S. (Iowa Wesleyan). Professor of Zoology, University of Arizona.

Voss, Ernest Karl Johnann Heinrich,

175 Nelson Ave., West Lawn Heights

Ph. D. (Leipzig). Professor of German Philology, University of

Wisconsin ; Vice-President, Germanic Museum Association.

Wadmond, Samuel C., Delavan

Vice-President, Jackson and Jackson Company, Delavan ; Secretary of

Board, Aram Public Library, Delavan.

Wagner, George, 1901 Jefferson St., Madison

Ph. C. (Michigan) ; A. B. (Kansas) ; A. M. (Michigan). Assistant

Professor of Zoology, University of Wisconsin ; Ichthyologist,

State Geological and Natural History Survey.

Wakeman, Nellie A., 1814 Ray St., Madison

Instructor in Pharmacy, University of Wisconsin.

Walker, J. Charles, Madison

Plant Pathologist, University of Wisconsin.

Wann, Louis, Appleton

Ph. D. (Wisconsin). Professor of English, Lawrence College.

Ward, Henry Levi, Milwaukee Public Museum, Milwaukee

Director, Milwaukee Public Museum ; Vice-President, Wisconsin

Natural History Society.

Weidman, Samuel, 410 North Henry St., Madison

B. S., Ph. D. (Wisconsin). Geologist, Wisconsin Geological and Natural

History Survey.

Werner, Fred W., 991-16th St., Milwaukee

Instructor in Biology, North Division High School.

West, George A., 97 Wisconsin St., Milwaukee

Lawyer ; President, Board of Trustees, Milwaukee Public Museum.

Whitford, Alfred Edward, Milton

M. A. Professor of Mathematics and Physics, Milton College.

Whitson, Andrew Robinson, R. 7, Madison

B. S. (Chicago). Professor of Soils and Drainage, University of Wis¬

consin ; Field Agent, United States Department of Agriculture.

r

List of Members . 1251

Whyte, William F., 1108 Garfield St., Madison

M. D. Physician. President, State Board of Health of Wisconsin.

Wilson, H. F., 425 Sterling PL, Madison

Professor of Economic Entomology, University of Wisconsin.

Winchell, Alexander N., 200 Prospect Ave., Madison

B. S. and M. S. (University of Minnesota) ; D. Sc. (University Paris)

Professor of Mineralogy and Petrology, University of Wisconsin,

Geologist, Oregon Bureau of Mines and Geology.

Wolfenson, Louis B., 1118 W. Dayton St., Madison

Assistant Professor of Hebrew and Hellenistic Greek, University

of Wisconsin.

Woll, Fritz Wilhelm, Davis, California

B. S., Fh. B. (Christiana) ; M. S., Ph. D. (Wisconsin). Professor in

the California State Agricultural College.

Woodworth, Clyde M., Madison

Assistant in Experimental Breeding, University of Wisconsin.

Wright, Clement Blake Bergin,

284 Martin St., Milwaukee

A. B., A. M. (Toronto) ; B. D. (Nashotah) ; Fh. D. (Kansas City) ;

Clergyman ; Canon, Milwaukee Cathedral ; Secretary, Diocese

of Milwaukee ; Librarian, Diocesan Library.

Young, Karl, 433 Lake St., Madison

A. B. (Michigan) ; A. M. and Ph. D. (Harvard). Professor of Eng¬

lish, University of Wisconsin.

Zdanowicz, Casimir Douglass,

2006 Chadbourne Ave., Madison

Assistant Professor of Romance Languages, University of Wisconsin.

Zimmerman, Oliver Brunner,

International Harvester Corporation, Chicago, Ill.

B S., M. E. (Wisconsin) . International Harvester Corporation.

CORRESPONDING MEMBERS

Abbott, , Charles Conrad, Trenton, N. J.

M. D. (Pennsylvania).

Armsby, Henry Prentiss, State College, Pa.

B. S. (Worcester Polytechnic) ; Ph. B., Ph. D. (Yale) ; LL. D. (Wis¬

consin). Director of Institute of Animal Nutrition ; Expert in

Animal Nutrition, United States Department of Agriculture.

I

1252 Wisconsin Academy of Sciences, Arts , and Letters,

Bennett, Charles Edwin, 1 Grove Place, Ithaca, N. Y.

A. B., Litt. D. (Brown). Professor of Latin Language and Litera¬

ture, Cornell University.

Bridge, Norman, Auditorium Building, Los Angeles, Cal.

A. M. (Lake Forest) ; M. D. (Northwestern, Rush). Emeritus

Professor of Medicine, Rush Medical College. Physician.

Caverno, Charles, Lombard, Ill.

A. B., A. M. (Dartmouth). Professor Emeritus, Ripon College.

Chandler, Charles Henry, New Ipswich, N. H.

A B., A. M. (Dartmouth). LL. D. (Colorado). Clergyman, retired.

Coulter, John Merle, University of Chicago, Chicago, Ill.

A. B., A. M., Fh. D. (Hanover) ; Ph. D. (Indiana). Professor of

Botany and Head of Department, University of Chicago.

Crooker, Joseph Henry,

820 South St., Koslindale, Boston, Mass.

D. D. (St. Lawrence, Nashville). Minister, Unitarian Church.

Davis, Floyd,

317 Iowa Loan and Trust Building, Des Ytoines, Iowa

Ph. B., C. E., E. M. (Missouri) ; Ph. D. (Miami). Analytical and

Consulting Chemist.

Eaton, Edward Dwight, Beloit

A. B., a. M. (Beloit) ; B. D. (Yale) ; LL. D. (Wisconsin) ; D. D.

(Northwestern, Yale).

Eckels, William Alexander, Easton, Pa.

A. B., A. M. (Dickinson) ; Ph. D. (Johns Hopkins). Associate

Professor of Greek, Lafayette College.

Fallows, Samuel, 2344 Monroe St., Chicago, Ill.

A. B., A. M., LL. D. (Wisconsin) ; D. D. (Lawrence, Marietta).

Presiding Bishop. Reformed Episcopal Church ; President,

Board of Managers, Illinois State Reformatory.

Hendrickson, George Lincoln,

68 Trumbull St., New Haven, Conn.

A. B. (Johns Hopkins) ; L. H. D. (Western Reserve). Professor of

Latin, Yale University.

Hodge, Clifton Fremont,

3 Charlotte St., Worchester, Mass.

A. B. (Ripon) ; Ph. D. (Johns Hopkins). Professor of Physiology

and Neurology and Professor of Biology in the Collegiate

Department, Clark University.

List of Members.

1253

Holden, Edward Singleton,

United States Military Academy, West Point, N. Y.

B. S., A. M. (Washington) ; Sc. D. (Pacific) ; LL. D. (Wisconsin, Col¬

umbia). Astronomer; Librarian, United States Military Acad¬

emy, West Point.

Hoskins, Leander Miller,

365 Lincoln Ave., Palo Alto, Cal.

M. S., C. E. (Wisconsin). Professor of Applied Mathematics,

Leland Stanford Jr. University.

Iddings, Joseph Paxon, 5730 Woodlawn Ave., Chicago, Ill.

Ph. B. (Tale). Professor of Petrology, University of Chicago,

Geologist, United States Geological Survey.

Kinley, David, Urbana, Ill.

A. B. (Yale) ; Ph. D. (Wisconsin). Dean of the Graduate School

and Professor of Economics, University of Illinois.

Leverett, Frank, 312 N. Thayer St., Ann Arbor, Mich.

B. Sc. (Iowa Agricultural). Geologist, United States Geological

Survey ; Lecturer in Geology, University of Michigan.

Libby, Orin Grant, Grand Forks, N. D.

B. L., M. L. (Wisconsin). Professor of History, University of North

Dakota, State Historical Society of North Dakota.

Lurton, Freeman Ellsworth, Fergus Falls, Minn.

B. S., M. S. (Carleton) ; A. M. (Upper Iowa) ; Ph. D. (Gale). Super¬

intendent of Public Schools ; Member, Board of Directors,

Fergus Falls Public Library.

Luther, George Eimer,

262 South College Ave., Grand Rapids, Mich.

Cashier, People’s Savings Bank ; Treasurer, Historical Society of

Grand Rapids.

Marx, Charles David, Palo Alto, Cal.

B. C. E. (Cornell) ; C. E. (Karlsruhe). Professor of Civil Engineer¬

ing, Leland Stanford Jr. University.

McClumpha, Charles Flint,

56 Church St., Amsterdam, N. Y.

A. B., A. M. (Princeton) ; Ph. D. (Leipzig). Treasurer, McClumpha

Company ; Member, Fort Johnson Club ; Treasurer, Amsterdam

Free Library ; Historian, Montgomery County Historical

Society ; Member, New York State Historical Society.

Moore house, George Wilton,

2069 East 96th St., Cleveland, 0.

B. L., M. L. (Wisconsin) ; M. D. (Harvard). Physician to the

Dispensary of Lakeside Hospital and Western Reserve University.

1254 Wisconsin Academy of Sciences , Arts , and Letters.

Munro, Dana Carleton, Princeton, N. J.

A. B., A. M. (Brown). Professor of History, Princeton University.

Nehrling, Henry,

Palm Cottage Experiment Garden, Gotha, Orange Co., Fla.

Olive, Edgar W., Brooklyn, N. Y.

Curator, Brooklyn Botanic Garden.

Potter, William Bleecker, 1225 Spruce St., St. Louis, Mo,

A. B., A. M., M. E., Sc. D. (Columbia). Mining Engineer and

Metallurgist.

Power, Frederick Belding, 535 Warren St., Hudson, N. Y.

Ph. G. (Philadelphia College of Pharmacy) ; Ph. D. (Strassburg).

Director of Wellcome Chemical Research Laboratories, London,

England.

Salisbury, Rollin D., 5730 Woodlawn Ave., Chicago, Ill-

A. M., LL. D. (Beloit). Professor of Geographic Geology, Head of

the Department of Geography and Dean of the Graduate

School of Science, University of Chicago ; Geologist,

United States Geological Survey and State

Geological Survey of New Jersey.

Sawyer, Wesley Caleb, 725 Asbury St., San Jose, Cal.

A. B., A. M. (Harvard) ; A. M., Ph. D. (Gottingen). Professor of

French and German and Lecturer on Teutonic Mythology,

University of the Pacific.

Stone, Ormond, University Station, Charlottesville, Ya.

A. M. (Chicago). Director of the Leander McCormick Observatory

and Professor of Practical Astronomy, University of Virginia.

Tolman, Albert Harris,

5750 Woodlawn Ave., Chicago, Ill.

A. B. (Williams) ; Ph. D. (Strassburg). Associate Professor of

English Literature, University of Chicago.

Tolman, Herbert Cushing, ' Nashville, Tenn.

A. B., Ph. D. (Yale) ; D. D. (Nashville). Professor of Greek, Van¬

derbilt University ; Canon, All Saints’ Cathedral.

Townley, Sidney Dean, Ukiah, Cal.

B. S., M. S. (Wisconsin) ; Sc. D. (Michigan). Astronomer in Charge

of International Latitude Observatory ; Lecturer in Astronomy,

University of California; Editor of Publications, Astronomi¬

cal Society of the Pacific.

List of Members ,

1255

Turner, Frederick Jackson, Cambridge, Mass.

A. B., A. M. (Wisconsin) ; Ph. D. (Johns Hopkins) ; LL. D. (Illinois) ;

Litt. D. (Harvard). Professor of American History, Harvard

University ; President, American Historical Association ; Mem¬

ber, Massachusetts Historical Association ; American

Amtiquarian Society ; Colonial Society of Massa¬

chusetts ; Wisconsin Historical Society ; Mis¬

sissippi Valley Historical Society, etc.

Van de Warker, Ely, 404 Fayette Park, Syracuse, N. Y.

M. D. (Albany Medical and Union). Surgeon, Central New York

Hospital for Women ; Consulting Physician, St. Ann’s Matern¬

ity Hospital ; Senior Surgeon, Women’s and Children’s

Hospital ; Commissioner of Education, Syracuse.

Verrill, Addison Emery,

86 Whalley Ave., New Haven, Conn.

B. S. (Harvard) ; A. M. (Yale). Professor of Zoology, Yale Uni¬

versity, Curator of Zoology, Yale University Museum ; Presi¬

dent Connecticut Academy of Arts and Sciences.

Winchell, Newton Horace,

501 East River Road, Minneapolis, Minn.

A. M. (Michigan). Geologist and Archaeologist.

Young, Albert Adams,

531 South Claremont Ave., Chicago, Ill.

A. B., A. M. (Dartmouth) ; B. D. (Andover). Clergyman

MEMBERS DECEASED.

Information of whose decease has been received since the issue of

Volume XVIII

Brinckley, William Joshua, Milwaukee

Lecturer, Public Museum.

Deceased May 1, 1916

Ellsworth, William H., Milwaukee

Of The Ellsworth-Thayer Manufacturing Company.

Deceased October 5, 1917

Ferry, George Bowman, Milwaukee

Of Ferry and Clas, Architects.

Deceased January 7, 1918

1256 Wisconsin Academy of Sciences , Arts , and Letters.

Harwood, Mary Corinthia, Ripon

Professor, Ripon College.

Deceased October 19, 1914

Hippensteel, H. S., Stevens Point

Professor of Literature, State Normal School, Stevens Point

Deceased April 25, 1916

Porter, William, Beloit

Professor Emeritus of Latin, Beloit College

Deceased October 14, 1917

Sherman, Dr. Lewis, Milwaukee

Physician and Pharmacist.

Deceased July 2, 1915

Updike, Eugene Grover, Madison

Pastor First Congregational Church, Madison.

Deceased December 24, 1917

Extracts from the Charter.

1257

EXTRACTS FROM THE CHARTER OF

THE ACADEMY

An Act to incorporate the Wisconsin Academy of Sciences, Arts, and

Letters.

The people of the state of Wisconsin , represented in senate and assem¬

bly , do enact as follows:

Section 1. Lucius Fairchild, Nelson Dewey, John W. Hoyt, Increase

A. Lapham, * * ** at present being members and officers of an

association known as “The Wisconsin Academy of (Sciences, Arts, and

Letters,” located at the city of Madison, together with their future

associates and successors forever, are hereby created a body corporate

by the name and style of the “Wisconsin Academy of Sciences, Arts,

and Letters,” and by that name shall have perpetual succession; shall

be capable in law of contracting and being contracted with, of suing

and being sued, of pleading and being impleaded in all courts of com¬

petent jurisdiction; and may do and perform such acts as are usually

performed by like corporate bodies.

Section 2. The general objects of the Academy shall be to encourage

investigation and disseminate correct views in the various departments

of science, literature, and the arts. Among the specific objects of the

Academy shall be embraced the following:

1. Researches and investigations in the various departments of the

material, metaphysical, ethical, ethnological, and social sciences.

2. A progressive and thorough scientific survey of the state with a

view of determining its mineral, agricultural, and other resources.

3. The advancement of the usual arts, through the applications of

science, and by the encouragement of original invention.

4. The encouragement of the fine arts, by means of honors and prizes

awarded to artists for original works of superior merit.

5. The formation of scientific, economic, and art museums.

6. The encouragement of philological and historical research, the

1Here follow the names of forty others. Sections 5, 6, 8 and 9 are omitted

here as of no present interest. For the charter in full see Transactions , vol.

viii, p. xi, or earlier volumes.

1258 Wisconsin Academy of Sciences, Arts, and Letters.

collection and preservation of historic records, and the formation of a

general library.

7. The diffusion of knowledge by the publication of original contri¬

bution to science, literature, and the arts.

Section 3. Said Academy may have a common seal and alter the

same at pleasure; may ordain and enforce such constitution, regula¬

tions, and by-laws as may be necessary, and alter the same at pleasure;

may receive and hold real and personal property, and may use and

dispose of the same at pleasure; provided, that it shall not divert any

donation or bequest from the uses and objects proposed by the donor,

and that none of the property acquired by it shall, in any manner, be

alienated other than in the way of exchange of duplicate specimens,

books, and other effects, with similar institutions and in the manner

specified in the next section of this act, without the consent of the

legislature.

Section 4. It shall be the duty of the said Academy, so far as the

same may be done without detriment to its own collections, to furnish,

at the discretion of its officers, duplicate typical specimens of objects

in natural history to the University of Wisconsin, and to the other

schools and colleges of the state.

Section 7. Any existing society or institution having like objects

embraced by said Academy, may be constituted a department thereof,

or be otherwise connected therewith, on terms mutually satisfactory to

the governing bodies of the said Academy and such other society or

institution.

Approved March 16, 1870.

STATUTES OF 1898.

TRANSACTIONS OF THE ACADEMY.

Section1 ,341. There shall be printed by the state printer biennially

in pamphlet form two thousand copies of the transactions of the Wis¬

consin Academy of (Sciences, Arts, and Letters, uniform in style with

the volumes heretofore printed for said society.

Note. — Under a ruling of the printing commissioners of the state of Wis¬

consin, made in response to a presentation by a committee of the Academy

appointed December 29, 1897, each volume of the Transactions may be

issued in two consecutive parts ; so that a publication may thus be issued

each year covering the papers accepted after the previous annual meeting.

The Academy allows each author one hundred separate reprints of his paper

from the Transactions without expense, except a small charge for printed

covers when desired. Additional copies are charged for at the actual cost

of printing and binding.

OF THE DISTRIBUTION OF PUBLIC DOCUMENTS.

Section 365. The transactions of the Wisconsin Academy of Sciences,

Arts, and Letters shall be distributed as follows: One copy to each

i

Extracts from the Charter.

1259

member of the legislature, one copy to the librarian of each state insti¬

tution; one hundred copies to the State Agricultural Society; one hun¬

dred copies to the State Historical Society; one hundred copies to the

State University, and the remainder to said Academy.

Section 366. In the distribution of books or other packages, if such

packages are too large or would cost too much to be sent by mail, they

shall be sent by express or freight, and the accounts for such express

or freight charges, properly certified to, shall be paid out of the state

treasury.

STATUTES OF 1901.

CHAPTER 447.

BINDING OF EXCHANGES.

Section 1. Section 341 of the revised statutes of 1898 is hereby

amended by adding thereto the following: The secretary of state may

authorize the state printer to bind in suitable binding all periodicals

and other exchanges which the Society shall hereafter receive, at a

cost not exceeding one hundred and fifty dollars per annum. The

secretary of state shall audit the accounts for such binding.

STATUTES OF 1917.

Section 35.32. That part of section 35.32 of the statutes relating to

printing for the Wisconsin Academy of Sciences, Arts, and Letters is

amended to read: “of each number as issued, of the transactions of

the Wisconsin Academy of Sciences, Arts, and Letters, not more than

two thousand copies ♦ * * together with suitable binding at a cost

not exceeding one hundred and fifty dollars per annum of all periodi¬

cals and other exchanges which said academy shall hereafter receive.”

1260 Wisconsin Academy of Sciences , Arts , and Letters.

CONSTITUTION

OF THE WISCONSIN ACADEMY OF SCIENCES, ARTS, AND

LETTERS.

[As amended at various regular meetings.]

Article I. — Name and Location.

This association shall be known as the Wisconsin Academy of

Sciences, Arts, and Letters, and shall be located at the city of Madison.

Article II. — Object.

The object of the Academy shall be the promotion of sciences, arts,

and letters in the state of Wisconsin. Among the special objects shall

be the publication of the results of investigation and the formation of

a library.

Article III. — Membership.

The Academy shall include four classes of members viz.: life mem¬

bers, honorary members, corresponding members, and active members,

to be elected by ballot.

1. Life members shall be elected on account of special services ren¬

dered the Academy. Life membership in the Academy may also be

obtained by the payment of one hundred dollars and election by the

Academy. Life members shall be allowed to vote and to hold office.

2. Honorary members shall be elected by the Academy and shall be

men who have rendered conspicuous services to science, arts, or letters.

3. Corresponding members shall be elected from those who have

been active members of the Academy, but have removed from the state.

By special vote of the Academy men of attainments in science or letters

may be elected corresponding members. They shall have no vote in

the meetings of the Academy.

4. Active members shall be elected by the Academy or the council

and shall enter upon membership on the payment of an initiation fee

of two dollars which shall include the first annual assessment of one

dollar. The annual assessment shall be omitted for the president,

secretary, treasurer, and librarian during their term of office.

Article IV. — Officers.

The officers of the Academy shall be a president, a vice-president for

each of the three departments, sciences, arts and letters, a secretary, a

librarian, a treasurer, and a custodian. These officers shall be chosen

by ballot, on recommendation of the committee on nomination of officers,

Constitution.

1261

by the Academy at an annual meeting and shall hold office for three

years. Their duties shall be those usually performed by officers thus

named in scientific societies. It shall be one of the duties of the presi¬

dent to prepare an address which shall be delivered before the Academy

at the annual meeting at which his term of office expires.

Article Y. — Council.

The council of the Academy shall be entrusted with the management

of its affairs during the intervals between regular meetings, and shall

consist of the president, the three vice-presidents, the secretary, the

treasurer, the librarian, and the past presidents who retain their resi¬

dence in Wisconsin. Three members of the council shall constitute a

quorum for the transaction of business, provided the secretary and one

of the presiding officers be included in the number.

Article YI. — Committees.

The standing committees of the Academy shall be a committee on

publication, a library committee, and a committee on the nomination

of members. These committees shall be elected at the annual meeting

of the Academy in the same manner as the other officers of the

Academy, and shall hold office for the same term.

1. The committee on publication shall consist of the president and

secretary and a third member elected by the Academy. They shall

determine the matter which shall be printed in the publications of the

Academy. They may at their discretion refer papers of a doubtful

character to specialists for their opinion as to scientific value and

relevancy.

2. The library committee shall consist of five members, of which the

librarian shall be ex officio chairman, and of which a majority shall not

be from the same city.

3. The committee on nomination of members shall consist of five

members, one of whom shall be the secretary of the Academy.

Article YII. — Meetings.

The annual meeting of the Academy shall be held at such time and

place as the council may designate; but all regular meetings for the

election of the board of officers shall be held at Madison. Summer

field meetings shall be held at such times and places as the Academy

or the council may decide. Special meetings may be called by the

council.

Article VIII. — Publications.

The regular publication of the Academy shall be known as its Trans¬

actions, and shall include suitable papers, a record of its proceedings.

1262 Wisconsin Academy of Sciences , Arts , and Letters.

and any other matter pertaining to the Academy. This shall be

printed by the state as provided in the statutes of Wisconsin. All mem¬

bers of the Academy shall receive gratis the current issues of its Trans¬

actions.

Article IX. — Amendments.

Amendments to this constitution may be made at any annual meeting

by a vote of three-fourths of all the members present; provided, that

the amendment has been proposed by five members, and that notice has

been sent to all the members at least one month before the meeting.

RESOLUTIONS

REGULATIVE OF THE PROCEEDINGS OF THE ACADEMY.

THE TRANSACTIONS OF THE ACADEMY.

[By the Academy, December 28, 1882.]

2. The secretary of the Academy shall be charged with the special

duty of overseeing and editing the publication of future volumes of

the Transactions.

3. The Transactions of the Academy hereafter published shall con¬

tain: (a) a list of officers and members of the Academy; (b) the

charter, by-laws and constitution of the Academy as amended to date;

(c) the proceedings of the meetings; and (d) such papers as are duly

certified in writing to the secretary as accepted for publication in ac¬

cordance with the following regulations, and no other.

6. In deciding as to the papers to be selected for publication, the

committee shall have special regard to their value as genuine, original

contributions to the knowledge of the subject discussed.

9. The sub-committee on publication shall be charged with insisting

upon the correction of errors in grammar, phraseology, etc., on the

part of authors, and shall call the attention of authors to any other

points in their papers which in their judgment appear to need revision.

[By the Academy, June 2, 1892.]

The secretary was given, authority to allow as much as ten dollars

for the illustrations of a paper when the contribution was of sufficient

value to warrant it. A larger amount than this might be allowed by

the committee on publication.

[By the\ Academy, December 29, 1896.]

The secretary was directed to add to the date of publication as printed

on the outside of author’s separates' the words, “Issued in advance of

general publication.”

Resolutions.

1263

FEES OF LIFE MEMBERS.

[By the Academy, July 19, 1870.]

Resolved, That the fees from members for life be set apart as a per¬

manent endowment fund to be invested in Wisconsin state bonds, or

other equally safe securities, and that the proceeds of said fund, only,

be used for the general purposes of the Academy.

ANNUAL DUES.

[By the Academy, December 29, 1892.]

Resolved, That the secretary and treasurer be instructed to strike

from the list of active members of the Academy the names of all who

are in arrears in the payment of annual dues, except in those cases

where, in their judgment, it is desirable to retain such members for a

longer time.

ARREARS OF ANNUAL DUES.

[By the Council, December 29, 1897.]

Resolved, That the treasurer be requested to send out the notices of

annual dues as soon as possible after each annual meeting and to ex¬

tend the notice to the second or third time within a period of four

months where required.

secretary’s allowance.

[By thb Academy, December 27, 1902.]

Resolved , That the Academy hereby appropriates the sum of seventy*

five dollars per annum as an allowance for secretary’s expenses, for

which a single voucher shall be required.

secretary’s allowance.

[By the Council, April 5, 1912.]

Resolved, That the Academy appropriates the sum of two hundred

dollars per annum for the secretary-treasurer’s allowance.

ELECTION of MRS. LUCIUS FAIRCHILD AS HONORARY MEMBER.

[By the Council, April 12, 1918.]

Resolved, That because of the honorable and leading part that was

played by the late General Fairchild in the founding of this Academy,

his widow, Mrs. Lucius Fairchild, of Madison, be voted an honorary

member of the Wisconsin Academy of Sciences, Arts, and Letters.

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