Gorli oil, by Emile Andre and Daniel Jonatto.

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1:' ;r*

Contribution under Investigation of Chaulmoogra Oil.

Researches on Gorli Oil.

By Emile Andre and Daniel Jonatto,
Bull. Soo. Chim., 1928, IV, 43, 347.

An enmpirical observation was made long ago by the people of
S almost all the tropical regions of the world, on the use of the oil

from the seeds of different grains as a cure for skin diseases, and

particularly in the treatment of leprosy. In India, the virtues of

chaulmoogra oil, which was taken from the seeds of the Taraktogenus

Hurzii, was long know; in Indo-China and halaysia, the use of the oil

prepared from the different seeds of Hydnooarpus and well known under

the names of Kanti, the Krabao of Lubrako, Mamoty, Kavatel, DTdu, etc.;
I n South American in the Anmacon basin, the natives extracted in an

effective way the oils furnished by the seeds of several plants belonging

to the genii Carpotroche, Lindackeria and Irna; ia Occidental Africa,

finally, the heroes produced from the powdered seeds of the Onooba

echinata (Oliver) or Gorli, preparations for local application, the

curaive effect of which was incontestable.
Little by little the botanists arrived at the identification

of the plants or shrubs which furnished these precious drugs. It was

verified, not without surprise, in spite of their different geographic

origin, all thE seeds which furnished the anti-leprosy oil, camn from

the same small family, that of the Flacourtiaoees.
On their side, the chemists discovered that the anti-leprosy

oils possessed in common, a large number of characteristics of great

importance. They turned the plane of polarized light strongly to the

right. They owed that property to the presence of the mixture of





1A 1 -2-
glycerides of which they were composed, particularly of the acids

belonging to the Oloopentene group, which were isolated and represented

by their formulas.

Ohaulmoogric acid CH CH
CHO CH -
CH8 CH / ______ ) -_00_
Hydnocarpic acid CH U- NH
I \On (CH O COOH
>Ha OH-/
CHs CH~
They were discovered in 1904 and. 1905 by Power and Gornall,

and Power and Barrowoliff.


Power and Gornall. The constituents of chaulmoo.rio seeds.
J,of Chem. Soc., 1904 (85)0 838-51.

Power and Barrowoliff. The constituents of the' seeds of Hydnocarpuw
Wightiana and of Hydnooarpua anthelmlntica. Isolation of a homologue
of chaulmoogric acid. J. Chem. Soc., 1905 (87), 884-96.

All the oils of the seeds of the Flacourtiacees do not contain

the acids of this grcup, but it is a fact worthy of note, that the

latter have not been found in the seeds of any other family. One does

not know how few exarmnples of a chemical character are also limited so

that they belong exclusively to one botanical eroup,

The family of Flacourtiacees is subdivided into two tribes, the

Hydnocarpees and the Oncobees, While the representatives of the first

belong to the flora of Asia and Oceania, those of the second grow in

South America and Afrlia, The genii Taraktogenos, Hydnocarpus and

S Asteriastigma b*ng to the tribe of Hydnocarpees, The genus Oncoba,

S Carpatroche, Lindackeria and MAyna belong to that of the Oncobees.

There exists other geAii of the two tribes, but they do not furnish

anti-leprosy oil. Thuvs tar, the genua Oncoba alone was found in the

African flora, especially in the Onooba echinataiOliver), and urnisbes

an oil rich in bchaulmooric acid. It iS found in the forests of Guinea,







Ivory Coast, Sierra-Loone and Nigeria.

Thanks to the kindness of Professor Perrot, we have at our

disposal for sampling a more or leoS abundant quantity of anti-leprosy

seeds of Flacoourtiacees. 'UIth a preliminary note (.1ndre, Contribution

to the study of the oils of the Chaulmsoogric group. C. iR. 1925 (181),

1089), the physical and chemical properties of a certain number of oils

extracted from these seeds were determined. The studies were all made

in a profound manner. The examination of Gorli seeds were well worthy

of attention. They are the only anti-leprosy grains in the African

flora, and leprosy makes important ravages in Occidental and Equatorial

Africa. On the other hand, one is not able to receive from the regions

where one finds fOorlit od, any mixture of chaulmoogice seeds coming

from related species. This happy agreement of circumstances gaarartees

a purity of origin repardim- which it is meM difficult to depend on

when one bee.inrL the study of many Hjdnecarpus seeds of Asia and Oceania.

For e-cornple, experience has shown us that, between the soads itich

arrived at .tihort intervals from Indip or Indo-China under one and the

same desig-nation, marked differences soimetires eisat. In fact, according

to two Enrlish authors, Gorli oil was said to contain 87.5 per cent of

its weight of ohaulnoogric acid free from hydnocarpic acid, it would

therefore be a fine raw material for extractirnC chau.luoogric acid.

Gorli Seed. The Oncoba echinata {Oliver), called Corli or Katoupo,

is a shrub which Crows about four to six meters in height a;nd v'hose fruits

resemble the cheatnut; their thorny outer casing bursts on maturity and the

seeds are exposed, a few very large grains have a leatherlike teguinent.

They weigh about .05 g. and are smaller than the chawlmoogra seeds, The

fruit has a pulp of medium thickqpas and the sugar is difficult to

.


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separate completely if the maturity is nat complete. The kernel consists

of & white albumwin-like oil which lodges in two foliaceous cotyledons.

At first the gorli oil gives off a sweet and agreeable odor, then after-

ward an acrid flavor; the yield of oil is variable. Certain samples,

when extracted with ether in a Soxhiet apparatus, give 52 per cent of

oil and others S9 per cent according to the difference in maturity.

Gorli Oil. Separation of the jlycerides which it contains. In

our climates Gorli seed oil is solid. Its principle properties are

as follows !

Melting point 40 42*
Density at 20 31 0.9286
Index of refraction (NL ) 1.4740
Rotatory power +560 10'
Saponification number 184.5 7
Iodine number (Hanus) 98

'Ae have begun the studj of the separation of the various

constituents without using any operation which would alter their nature.

If, according to Golding and Akers, the acids contain 87 per cent of

chaulmoogrie acid, it should be easy to extract trichaulnoogrine from

Gorli seed oil by simple crystallization. These results were not

obtained according to our expectation, .

On using alternatively acetone and petroleum ether a large number

of times, we have crystallized the solid Alycerides of Gorli seed oil,

an imperfect separation for a first operation. After long and laborious

manipulations, we have obtained a substance of resinous consistency

which crystallizes in mammillary masses which melt sharply at 51We

After 18 or 20 crystallizations about the fusion point, iS rotatory

power and iodine nuuier remains reasonably constant, The substance was






then considered in a fairly pure state* It possessed the following

physical and chemical constants:

Melting point I51
Saponifi cation inumbor 194
Iodine number 72.5
Specific rotation +49 20'

The theoretical iodine number for trichaulmooerine is about

86.8,and the saponification number about 191.3.

Energetic chilling of the mother liquors of the product enabled

us to obtain a mixture of glycerides having a pasty consistency.

Finally, on removing the solvent by distillation, we have obtained an

oily liquid, rather mobile, yellow in color and possessing a verj

pronounced odor. The principal physical and chemical constants were

as follows;

Density at 16* 0.9482
Index of refraction 1.4828
Specific rotation +46" "25'
Iodine number 108
Saponification nuniber 194

The mixture of liquid glycerides had a high rotator power which

is of great interest concerningr Gorli seed oil. we see that a very long

study will be necessary to isolate a new acid belonging to the group

of chaulmoogric and hldnocarpic acids Vich is not strongly saturated

with its two congeners.

The Fat Aeids of Gorli Seed Oil. By using solvents, we have

been able to separate Gorli seed oil into three parts: crystalline

glyoerides, 40 per cent; pasty glycerides, 40 per cent; glycerides

having a high rotator power# 20 per cent. On continuing a series of

crystallizationsof the pasty part, nothing of much importance was found.

We have found by a long and laborious method, and have furnished what




-6-


information we can, and have continued the study of that group which is

Obtained by saponification with alcoholic soda. We have used

1l Fractional cryatallizatlon (usually from alcohol),

2, Fractional distillation of the ethyl esters under reduced

pressure.

3. Fractional precipitation of the alcoholic solution of the

acids with magnesium acetate and barium acetate (i.,ethod of Heins).

We have not gone into these operations in detail, but have only

given those examples from the experimental part in the memorandum.

In combining the methods which we have shown, we have determined

approximately the conmoaition of each group Of glycerides of Gorli seed

oil, The crystallizable glycerides contain 85 per cent chaulmoogric acid

and 15 per cent palmitic acid. The pasty glycerides contain 80 per cent

of chaulmoogric acid, The rest consists of almost equal quantities of

palmitic acid and a new liquid acid possessing rotatory power, which we

call Gorlic acid. The liquid glycerides contain 70 per cent chaulmoogric

acid, 10 per cent palmitic acid end 20 per cont Gorlic acid.

Chaulmoogric Acid. Gorli seed oil contains about 80 per cent, which

we have satisfactorily extracted in very good yield. Dean and I.reashall

('ractionation of Uliaulmoo-ra Oil* JT Amesr Chem. Soo,, 19?0, (2), 42,

p. 2626-45) have studied in 1920, the preparation oi chaulmoogric acid
/'
and hydnocarpic acid, taken from the seeds oi' the Ti'araktogenoua 1urzii,

King, and have prepared after very laborious operations (fractional

distillations of the ethyl esters, and repeated crystallizationsof the

different acid fractiomns) from 1 kg. starting material, 100 g. of

chaulmoogric acid,and 50 g. hydnocarpio acid* Gorli oil does not contain




-7-


hydnoarpie acid, and gives five to six times as much chaulmoogrie

acid. The experimental part shows the best method of preparation,

In poassession of an important quantity of pure cheaulmoogric acid,

we have effected a preparation of trichaulmoogrine by a synthetic

process, which we have asaceeded in extracting directly from Gorli

oil. Chsulmoogric acid has been known more than 20 years; however,

trichaulnoogrine has never yet been described, Its preparation does

not present great difficulty. We have applied, point by point, the

g-neral methods indicated by the Dutch chemist Shei.j in 1899. It

consists of esterifyine pure glycerine with a large excess of fatty

acid at about 100' at a pressure of about k0-25 mm. of mercury.

After several crystallizations from acetic, trichIulmoogrine is

obtained in the form of colorless, odorless crystals, possessing the

following physical and chemical characteristics

Melting point 456
Index of refraction HN 1.4764
Density D0 0.9437
Specific rotation +540 50#
Saponification number 190.6
Iodine number 87,3

It is worthy of note that the melting point of tricbaulnoogrine is

remarkably low (450) compared with that of chaulmoogric acid, 66'. In

general, the glycerides of the solid fatty acids of this series generally

have a higher melting point than the acids from which they are derived.

Palmitic Acid. The presence of this acid in Gorli oil has been

shown by Goulding and Akefrs. We have, however, also found it in the

three groups of glycerides which we have separated at the beginning of

the work. We have shown its presence in the examination of the product

as proved by the fractional distillation of the ethyl esters. Their

rotator power is notably inferior to that of those fractions, the iodine








number I# weaker and the saponification number higher. On redistilling

these fractions several times we have isolated a certain quantity of an

ethereal salt having only a weak rotatory power. We have extracted the

fatty acids by saponification, the latter then recrWstallized several

times from alcohol, and finally furnished a product which melted

sharply at 62.5'* When mixed with palmitlc acid the m. p. does not

change. To verify that it was not accompanied by any homologue, it was

dissolved in alcohol and fractionally precipitated by successive additions

of an alcoholic solution of magnesium acetate. The several fractio.as

melted &t 62.5%, which proves conclusively that palmitic acid alone was

present.

Gorlic Acid. We have isolated. from the liquid elycerides of Gorli

oil a new acid, which is liquid at ordinary temperatures and whose physical

and chemical properties we are bringing to a conclusion, which does not

belong to the linear series, but to the cjolic series of the same family

with chaulmoogric and hydnocarpic acids. The iodine number shows that it

has an ethylene linking, more so than these two acids. The molecular

weight was determined and the formula C18H320 attributed to it. 4e have

obtained this in the free state and have cnaracterised it and given it

the name of Gorlic acid.

The purest product which we have obtained has an iodire number of

170 the theoretical being 181. It was impossible to attain the figure,

either because the product contained a little chaulmoogrie acid, or also

because the ethylene bond did not fix the theoretical quantity of halogen.

These two explanations exclude all but one other. We appeal for a second

only for the needs of our cause; we have discovered a method for obtaining




-9-

the maximum value for the iodine number of Gorlic acid. It is

necessary to take a large excess of an acetic acid solution of bromine

iodine (Method of Haua). If the theoretical quantity of halogen

only is employed, the ethylene group is not completely saturated.

It takes from 3 1/2 to 4 times the quantity to arrive at the value

170. It is probable that under these conditions the reaction is

incomplete. It is not the first time that the ethylene group showed

the same reaction.

We have prepared several salts of Gorlio acid, gorlates of Li,

lg, Ba and Ou, The last these salts were obtained in the form of an

amorphous mass, more or less viscous, the salt of Gu notably had the

form of a very brilliant and translucent gua. The salt of Li is solid

at the ordinary temperature. It had the form of a soap, but was not

crystalline. It melts at 1630 to a lump, according to Maquenne and

decomposes. Heating on an oil bath turns it yellow. It changes and

softens about 150*.

We have tried to obtain several organic derivatives of Gorlic

acid in the hope that certain of thorn would be crystalline. .Ae have

prepared the hydroxylamide, the diethyamide atid the amide of Gorlic acid.

The last one alone was obtained crystalline and melted at 950. The

determination of nitrogen by the Kjeldahl method gave

N found 4,88 Cale. 5.05

Gorli acid,which is a liquid fatty acid, is difficult to obtain

pure. we believe, nevertheless, that we have clearly identified that new

immediate principle, the lack of starting material having prevented further

study of the subject.

We have called attention to a fact which we have discovered in the




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course of our researches on the work of two Americans, Dean and

Wrenihall (U, S. Public Health Service Bull. No. 124, p. 12-23, 1924),
Chem. Abs., 1925 (2), 19, p. 2476.
who obtained in 1924, from the mother liquors from the crystallization

of chaulmoogric and hydnocarpic acids from commercial chaulmoogra oil, a

liquid acid having a rotation of *650, nd an iodine number of 164, which

they did not give any name. It seems to be identical with our Gorlic acid.

SUnfortunately, the starting material was obtained from an uncertain

botanical origin. In fact, on selling commercially under the name of

chaulmoogra oil, there IS usually meant the oil of Chaulmoogra Taraktogenos

Iurzii, which is an oil obtained from the seeds of various Hydnocarpi. h.e

have had very great difficulties in referring to the writings of Dean and

Wrenshall, which were not in the form of scientific periodicals,but in

the form of a bundle ofi reprints for the attention of the officials of

the Public Hygiene Siervice of the Uaited States.

Experimental Part.

Without entering into great detail, we describe all the operations

which we have used to establish the principle results for this study.

Preparation of Chaulmoogric Acid from Qorli Oil.

Corli seed oil is saponified by an excess of alcoholic aoda.

Yor example.

100 g. oil
100 g. alcohol of 90 per cent
50 g. NaOH, 36 per cent
Reflux 1/Z hour

The mixture of soaps obtained is dissolved in HaO, decomposed by an excess

of HC1 in a separatory funnel. The fattj acid liberated is repeatedly

extracted by shaking with ether, The ethereal solution is washed with

HaO as long an the washinge are acid and then dried with NaaSO4. The




-11-

other Is distilled and the last traces of solvent driven off by

heating on water bath in sA stream of COm under reduced pressure.

There iS thus obtained 95 g. of total acids which solidify immediately.

This purified by dissolving in 4 parts of 95 per cent hot alcohol

and allowed to crystallize. It is filtered by suction. The save

operation is repeated three times and finally gives a fairly pure

ohaulimoogrio acid. Its purity is. verified by means of its m p.,

iodine number and rotation. However, from industrially extracted

oils the crystals thus obtained are still colored. On distillation

under reduced pressure, the last traces of Ipurity are removed. It

is very inconvenient. At 235" the acid comes over under a pressure

of 14 1/2 am. We prefer to distill in the form of the ethyl enter

which comes over at a much lower temperature.

The acid is heated 5-hoursat least,to boiling, under reflux

with equal arts of 96 per cent alcohol and 5 per cent of its weight

of pure HaSO4. The two layers are separated, the ethyl ester, insoluble

in the alcohol, forms the lower layer. This is decanted, dissolved

in ether and washed several times, first with salt water, then with

ordinary water to remove all traces of HBSO4. On distilling the ether,

the residue remaining is ethyl chaulm.oograte and is brown in color.

This is purified by distillation under reduced pressure. The major

part passes over at 218-201 at a pressure of 1 rmam. of mercury. The

pure ethyl chaulmoograte is obtained absolutely colorless. On

saponifying by the ordinary method and extracting the solution with

ether after acidifying, the acid is obtained. After evaporating off

the ether, the chaulmoogrlc acid is finally crystallized from alcohol.




-12-


It separates out in very brilliant colorless laminae, without any odor.

This acid had the following characteristics

Melting point 08
Saturation number 198,6
Iodine number 90.7
Rotation +61* 50'

Tha ma p. and rotation are the Game as found by Pocwer and Barrovwcliff.

The theoretical saturation number is 198.9 and iodine number is 90.6.

Synthetic Preparation of Trichaulmoogrine. Wile have already shown

that we have used the general method for preparing the glycerides as

described by Soheij, which consists in heating at 1000 uider partial

vacuum S large excess of fatty acid with pure glycerine. Passing in

dry CO. gas serves both the purpose of stirring up the mass and carrying

off the HaO formed during the esterlilcation.

"e have used pure glycerine of commerce which we have rectified

by distillation under reduced pressure. '.ee have rejected the first and

last fractions. The glycerine which we used passed over at 180" at a

pressure of 16 as. The chsnlmoogric acid was a pure product which we

prepared.

1'e have heated the mixture of chaulmoogric acid and glycerine

during eight days at the rateof 6 to 7 hours per day, We have stopped

when we saw no further change in the aspect of the mass end no more

droplets of HsO formed on the sides of the flask. Vte have thus Obtained

a astrupy product without any odor. Since we have used a large excess of

chaulmoogric acid, the crude product was washed with several portions of

warm alcohol to remove the last traces of free asoid, After several

recrystallizatiens from alcohol, the trichaulnoogrine formed colorless,

odorless crystals, dry to the touch, melting at 45%, and remaining melted

for a long time and taking on a stiff, scaly, translucent, vitreous




4-1S

appearance. We have given the principle chemical and physical properties.

The Extraction of Palmitic Acid from the Solid Glycerides. The

alcoholic mother liquors coming from the extraction of chaulmoogric

acid from the solid glycerides is concentrated, allowed to crlystallize,

and gives a different product with a lower melting point. We have thus

obtained, for example,one per cent of crystals, melting at 56%, having

a rotation of *290 and an iodine number of 48,4; two per cent of a

product melting at 41*, with a rotation of 115* 40' and an iodine

number of 45.2. The fact that the rotatory power is notably lower

shows that a solid fatty acid with a normal chain is present. By

fractional distillation of the ethyl eaters, and by crystallization

of the acids coming from them, the fractions show a weak rotatory power,

the whole of which we successfully extracted.

The acids obtained by the concentration of the mother liquors

of the chaulmoogric acid and esterifyinr with ethyl alcohol in the

presence of sulfuric acid was fractionally distilled under reduced

pressure in a current of COM.

First Distillation.

Pressure 12-13 nmn. of mercury.

Temp. Wt. of fractions Rotatory Power

(1) 209-15# 14 (solid at 00) *22"-10
(2) 215-170 29 (solid at 00) +291-0t
() 218-190 15 (liquid) +59-09
(4) 219-21 ( ) +42"-20O
(6) 221-23* ) +450 o-,0
(6) 223-27- 4 + ) *440-09

Then isolating the inactive fatty acid, and distilling the first

products again.




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Second Distillation.

Pressure lZ mm. of mercury.

Taiap. wt.%

(1) 202.9 3
(2) 209-12" 26
(3) P2_12414 20
(4) 214417 11
(5) 217-200 19
(6) 220-23 2

Residue pyrogenous.

On extracting the fatty acids from fractions 2, 3 and 4,
ing
and crjtallizing these from alcohol and determine/ their rotatory power.

Acid 2 +240 50'
"3 +38 54'
4 *54* 0'

The acids obtained from the second fraction, melt at 590, have a

saturation number of 209 and an iodine number of 31.8. On recrystallizing

from alcohol and determining the rotatory power afterwards.

Rotatory
Power
2d crystalli nation + 22"
3d +1" 3S* 20'
4th +8' 20'
5th 3 0 Ol
6th 0" O'

The inactive acid obtained melted at 62.5* and had a saturation

number of 216". It is identical with palmitic acid, Aiich has a m. p.

of 62,60 and a saturation number of 219*.

The last value is a little higher then that which we obtained.

We have subjected our palmitic acid to a series of fractional

precipitation to make sure of its purity.

One and sixty-five hu:idredths g. of the acid was dissolved

in 35 coo of 95 per cent alcohol and a 5 per cent solution of magnesium




-1-40


acetate in alcohol added corresponding to one-fifth of the molecular

quantity. This operation was repeated five times sLd each fraction

crystallized from a little alcohol. The quantity obtained was sufficient

for determining the suiting point. The five fractions all melte. at

62.5*. T'he palmitic acid used was, therefore, completely free from

homologous fatty acids.

H xtraction of Corlic Acid. The mzjor part of the liquid g-lyoerides

of Gorli oil t"onsists of Corlic acid. This was extracted as follows

The elycerides were saponified with equal weights ol 95 per cent

alcohol and half of their weight of 36 per cent UaOH. The solution

was acidified with 1C1 and the fatty acids extracted with ether. The

ether solution is separated from the water and dried with anhydrous

Nasi304. The ether is distilled off and the acid obtained had a
was
sluggish consistency and/yellow in color. On crystallizing several

times for 90 per cent alcohol, the majorr part ol' the solid acids came out.

The mother liquor were concentrated as much as possible;the residue

is filtered by suction to separate the crude liquid acids. These

represent one-tird of the total acids. this is esterifiled with ethyl

alcohol in the presence of HaSO. The ethyl esters are poured into

ordinary ether, washed with salt water and then ordinary HaO. On

evaporating the ether, it remains in the lorm of a dark brown liquid.

This is rectified by distillation under reduced pressure in a current

of 00C. The products of the first distillation give palmitic acid.

The other fractions which were still slightly fellow in color were

mixed and distilled a second time. Th'e iodine number of each fraction

was taken to deternmine its nichnss in Corlie acild.




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Presurre 15 mm. of Hg.
Ten mperature Weight Iodine number

(1) 212-15 4 108
(2) 215-18 1S 117
(a) 218-20e 26 128
(4) 220-220 57 140
(5) 222-25* 16 149
Residue igneous 4

The theolwtical iodine number of ethyl gorlate is 1661 ihich

shown which distillation products are richest.

Fractions 3, 4, 5 were combined and redistilled.

Temperature Preassure nmm. Weight % Iodine number

(1) 212-18* 14 96
(2) 213-180 13 14 109
(S) 215-20o 13 21 126
(4) 219-21* 13 s0 138
(5) 219" fixed 12 23 150
(6) 219-26 12 5 154
Residue and loss 5




-17-

The ethers, absolutely clear and colorless, have a slightly

aronmatic odor which is not disagreeable, but the iodine number of the

end products not being very high, it seemed superfluous to undertake

new distillations, because each operation involves the loss of an

appreciable quantity of the product by heating. We were satisfied

with saponifying each fraction, extracting the fatty acids, vigorously

cooling them and eliminating the solid products by filtration. We

have thus obtained (1) White, solid acids still contaminated %ith oil,

whose iodine number varies from 120 to 130. Dissolved in alcohol, they

have allowed a mixture of palmitic acid and chaulmoogric acid to

crystallize, the gorlic acid remainirng in the mother liquors;

(2) liquid acids slightly yellow colored made up chiefly of the

gorlic acid, whose iodine number varies from 150 to 170 according to

the fractions from which they come. The theoretical number of a

C18Ho3002 acid, possessing two ethylene bonds, would be 181.

M'e have subjected to distillation under reduced pressure,

different fractions of this acid whose iodine number reached 160,

A gain of 7 to 8 points over this value sometimes caused the loss of

20 per cent of product in the form of tarry residue; we have also been

forced to determine immediately the physical and chemical properties

of the purest garlic acid we have obtained.

Gorlic acid i$ a colorless liquid whichh turns sl ichtljryellow

in contact with air. It has a peculiar c4or and an acrid, burning taste.
1Theoretical value1
Den sit y a t 1 8 3 0 .93 64 -- .. ...... ... .
Index of refraction 1.4783
Rotatory power +50' 18'
Index of saturation 199.5 201
Iodine number (Hanus) 169.6 181.4

1Por 018SHO02 (with two ethylene bonds).




' -18-


Lithium gorlate. We prepared the lithium gorlate by boiling

on the reflux condenser for two hours a solution of gorlic acid in

70 per Cent alcohol in the presence of a quantity of lithium carbonate

corresponding to twice the theoretical quantity. We then separated by

filtration the excess of lithium carbonate. The alcoholic solution

was concentrated by distillation. The very soluble lithium salt was

not deposited. The aolaulon was left i'or several days in a vacuum

veil jar in the presence of sulfuric acid. A *hite, vtrinkled pellicle

was formed with a soaopy, noncryatalline appearance and the entire Msas

gradually solidified.

By checking the evaporation before solidifi'catlon is complete,

a solid part and alcoholic mother liquors may be separated. ie

extracted the fatty acids of the solid part anu those of the soap

still in solution and found that the iodine numbers of each of them

were appreciably the same (168 and 169).

Lithium gorlate is lightly soluble in boiling ether (2 to 3 gi

per hundred), and we tried to utilize this property in order to purify

it, The ethereal solution, concentrated and cooled, allows a %hite,

hard product to deposlto but without any appearance of eryetallization.

The iodine number of the acid of the salt thus purified amounted to

170, a figure already reached.

The attempts to prepare barium gorlate, magnesium gorlate and

copper gorlate gave us results even more unsatisfactory.

Amide of -;orlic acid. Amide of g-orlic acid was prepared by

allowing the chloride of the gorlie acid to pa6P very slowly into




-19-
a concentrated and cooled solution of ammonia.

In order to prepare the acid chloride, we used the method

indicated by H. Mayer (14); it consists of causing thionyl chloride

to react directly on the acid. 'We heated on the water bath for two

hours with the reflux condenser a mixture of 20 g, of garlic acid and

60 g. of thionyl chloride; the quantity of reagent put to work

corresponded to 7 times the theoretical quantity, We maintained the

boiling for two hours. The liquid became very strongly colored. The

excess of thionyl chloride was carefully distilled. The chloride of

the gorlic acid remaining was in the form of a brown oil. "e conveyed

it drop by drop into a saturated, aqueous solution of amrnnia gas at a

temperature of -150 The amide was irrenediately precipitated. It was

crystallized and slightly yellow colored. After having been decanted,

washed with water and dried, we purified it by repeated crystallizations

in acetone. It melts at 95; we then determined the nitrogen there by

the Kjeldahl method (see page ).
9
Resume and Conclusions.

The solid glyoerides of the gorli oil crystallized 16 or 17 times

did not give us the pure trichaulmooerine. But the presence of this

compound in the gorli oil is certain, because chaulmoogric acid

represents nearly 80 per cent ol: the total, fatty acids. The high

melting point of the crystallized glycerides obtained.-by us (510) as

compared with that of the synthetic trichaulmoogrine (45"), indicates

that a palmito-dichaulmoogrine must exist in the oil studied and that

there is probably formed a crystalline combination between this compound

and the trichaulmoogrine.




I Ti
'I


-20-


'J,
)


,.' Owing to the impossibility of extracting this last mentioned

glyceride from the gorli oil, we prepared it synthetically and we

found that its boiling point was considerably lowered with respect to

the acid itself, contrary to that which is produced by the triglyooerides

of the fatty, saturated acids with normal chain.

We clearly distinguished the presence of palmitic acid in the

gorli oil and found that it contained about 10 per cent of it,

We finally extracted from the gorli oil a new, highly

dextrorotatory liquid acid, whose constitution is certainly very

close to that of the chaulmoogric and hydnocarpic acids, we obtained

it in almost a pure state and we give to it the formula 018H3002.

Independently of the pentagonal nucleus which characterizes

the acids of the chaulmoogrio group, its constitution should admit of

two ethylene bonds whiah have not the msae capacity of addition. It

is likely that one of them is bound up in the cyclic part of the molecule

and that the second is located in the lone chain attached to the nucleus.

We are making a study of this acid, of which gorli oil contains from

10 to 20 per cent of its weight.




I/ 1/ f'
Congr_ibution under lnesi.,..ion p_ haiuliuo ., i"
La$ULJ1c353-,,j (; jj hI
,
:" ...ivLie *.idr' e n,. A- -'ieJ. ccrn5tot0

11 4 :. 2 c:t ,1; :I 1V t 1, 5 ; L 2 -.-. r.4] '---
ti] 3.., DOC c i'- Jr!, -- i i ._ j-j ""< *
.. "-U1 ...1 .ro i.... Lt ;,i.:,lvl ion<. ;,o D) t>.'Ol] .

;.r*'..inu'' 1.s."- i Cio;,! O}..);-*** i"' vo .5 "on -,i; Io .._ ""^ ', v,hi.^ ';.
of' :iJ!i0-ot all thC trr:L.vlC;O. r;.ln.. Qof 1he worlalo; the u.:.,:! of
"'.l> oil-i+- t, F C .C .:ia.0 \.ib i-i z :-. Cur or -kJ.i oi
.I Li'LLCla.Ci7 in 1': *rcw ur.xnt 0:L lcprosyXn .izi. tV>
11.ii'.q1' L~~; cl. ;C i. !')O,;* : oiJl U*iUK"'v: w;.:i. ':-'Lcjri j-'roy I ;^' -I) Bxr '
T~*,l'*-*oJ3!.; :
u oe 0 i :i '..Y1 p .'c-p Uj from tLhe I Wr o.." cr'nL ,*'-. -':.*.S. <: --m s^ c\*'J tiC
n v..,i .... LErb.
W~~~~ll~~ ~ ilCI; ."T -*;1 "L;! ";~~;. ";" Li. .i',"!LL !'>O; i~ r' .s- '" .-' ,?i i :-,. -


soty,- n'. e e. -'L,.i& C'i"... t P. "o; -i,. ,'.. X-.... ij-. in Z- L,- -." ..U," C t .1. U *', th,
A 0 .... '',' ADhiO*t -
nau. v.j,; ,y-:t".c *t:,;. in .i; @j. ective \ y tr:. oils .... i :, -- tho
toI' fll '*Q'Q
oo., of :3.'.c'.,.: .,,. ', L-. lo -i.,.. t 'L .. ;es,. *f..'W.";'2.'_ .-". ";-Li-
.'ii t ,.:t'l ':, Ie .. ;'...; ,'i. ... ,:-.. t c' if3 .'-
-....:2 ,''Ci'< too ^O k. Y e. I.;. ( '! .c .. .....t.....' J ..*3i V;L') oJI
* ,:oli,,ir;- .1' :t1O: 1r .... for ,oc:. .I i">ijlc, i'on~ t''.; cur. tiv." ,;'rLeet on"
';.. c,,j *i, .. *. "k?.O01tt.2.:JtL. 'AGi,


1'*v zk -l
Lit l.% ... by litt.ie ti L- It .4...'. i... JO ,-L.--L at tnj i.,ci,,iflc
Uion o L-.3 + ,. ..,.ni..:- o.:" she .-t. '..P.h i'e i -u .L.;.+ Gc..: ,.
... 7.. It \;< v'-J t-sr, 0 ....'. .. .t ;... i r s,.ite ,. thoe .' ,--
-'- i o .;t .; .. "i\.,.'ilc -;"; .t1 *iJ:.A. 's eed ,..hic .,,- '';! ijL. ." '.l "
V.,.,. > oj,./ 11 ; ,:C f..-..c I.r'o .. vlii:: ,S-., :.>,.-' ,. i'.:,.....3 if i-_.: y, i"i';:'.t ci &v,-' .L.c." -..


i' UV.''kl
t i.: "" LsJ',.L "i :'" t .. ..

...r 'r.:y ui J hu cw'--.'c, 'u..,:C in co' ..,.,,". a ]s r ;,. nj.Ui :: of vh...ot '.L. -l.,,S
21ti*. r'y C !i; ;'.,i .z. "fg i..u" )**.C'"- t.I N ..& **,-iJ r c -.". to ',ij ... .i-j]tr;It.'
o. u '.,! ;..;ix t,.:.',. o 7. '". ,";: ia ^.-. r._.^" ',;: iti ;,. ';;eeu'>. c'^;,.c'-jc'.,..,i5,,^ :' -- ,l'.)...... .,i"'l
- u "i-i-f "-.l -i^i? O t ^ ^ ^.'^i.t ,. Oti;.,', i. 3.cf. h i,'. o-
"; i-I0 -..c c1- r ^^


-0, 51 I. O'T J_.l 1, r.
________ '___'___"
,- ( .-.. '1

,;-,,. ..,-, .
t..,






...:of. T .. ... :. ,;.' a .. ... ii..,,...' Of "-" = ;'r-1; A, .,L .-1 -
e ,.-'. t, ..;. ._.^ l '.i,.' ^il-r^-;, o f ,- .'_.'. ,", :' ,',,' < ';r ... c ,'** ,.-' r L ,,,.L',:'_,t i.c .., I s t .';
O ,L' i ; .' .:j ];.< ;.:,;,i- o f <,T.' : '* l C.'i o ): [ C .,c i.'.' J 'i- h > :.-*..* .-lO eC g ( ;:."./') '" ,":';':;

All the ,2, c: ,: .-c ....- ..." c"-. not
... .J Of it is a e2' >,t (
Lh t 5 i. -t L J" i,:,''-: _n t !L ,.-i; f 'ir t h .e ;' a :, y o ta e r
. "I "o t ,, "< .j I a. -( )- .
....*.i:t l' Lm o 'L S: L :: t: .;Vu.. ,Isw L,,.)fl'.i ,


.-l, r'.. r.,, nod ... fe ::" r ,le o' a ', ,,- :.ic',. 3. -i:: ";.




- t


ter arn cLio limited so th-t theLy bcion, ccli.us-i'.:ly to one b,'it.a

'f,.1 1 1:-iiA.V o1 .'... cou rt coc;- iS i.'t.ii.'i i two atr ll
th i...*p'.a.-:. f '-..fn.uV :':2, .T .ilu thiL L'e.".ro.j- t'. .1ives ot
tho fii t 1i. ,; to the ce.r:- o0 "r'1.i ,L -?ni',. bcT 1 :. ;;f the
;ecoi .. '...TO'i *i, o'.'. th 3 '- .C ; -1. C: i f" : 1 genera '.- ?';.t'*^;:i,.a 1io s
L.ydiircar .. .. n i tei:', t.l.,:,' b.. J Sxlo'"; t.b th. t[ribe of -.yc..U'. ".:..rx._'
es d! 13 .rau '.flcr.i ftC.i: ,L :u:;.i ii. .tc. 0Cyirx b.cior, oto
*th.vL t.a ta *.ZVYboi0L.^ Sflra CY..Zctu otic":1 ..inevi'l a1 oL t'-a tvwo tri
b.;;;'., u;.n tho d-o i0?i''.iL)i -,tub o ti-ly(:/src;.-y <.i, s a :-ii; v~ ,*the JenrLU
*..lr.O .': ;i'i w,' V,,, t 'i '. : rau. .I' .., ora 2'j 'i.,.'. Lj i.: "i~ o ,c *
co -: i.,i.. ..ta...... (. li ler ), ,';. h.t., iii .:Ge'T. an o il o.clC I, cnrl\ui_,oo...ic
.C. It" l ; w in ..h of ,ii-i 'j1 ., 3ocy L' c.. i .'.-
on. ."'. 1 .6 i,_,,.j .ia,
CVOk3 a.j.1,Jit
..h .;..U-, to thO i,. '.aic.(zw u. f z'o.0 o JO. :-. c otA,. h l..''c, at ..our
$3i10Uo0L2.i zb "'o Y LIJJl.iA.,.^ a & -Uor! 2 less C..,.LA.....--t .. j.L.f.i.
31e,'i'jc3 SOZ:U'3 of ti.2.C.A;V'U.cc'C. ?2.,: .'^* *.i'U a r,, Ii-L.intry nii to (*..r(LL'o
W '43on .'tu on to t, s.....y. o3.L c u t-. 0.uLa.Iloy.1 c g3 group.
'2.o F ':,.ztI (b 3 ),1 :1 ).' 'h 0h -t Ic.:l.., .:'i_ cicaicn u prop4 .' "r-i ,' of a
certain' ,umb-, i' oils o!v.i':^.ved I'roi ti-b e ;.ucL.: f.U'eJ deter,1i -
ned- i-,-... a3ut.ioi ,ere all aI ae in a p1-"o'o1 L, ri nlrr". ;, .:'."x ex -:ii ',.u -
lio. o.f '1or,1li !3r jo \.. .;jfl ,.;., u-t; 'A.i at ,'!u tion icy ..c the
or .y-2 .;.. i i. .. -ACr ica 1i. Oio.:.,i,.. I jiro.;y .: L i'LC1pVo
tUr. r,-v ..,: l:i -cc &' ..Ll. -K ad ..r:.iu -Lot :J ,1-i3oa, *. a the oth'-."'
a:, not *iJ.2 to r:ce ,.-.' LCL..or,-l where one findaA
^*rUli .aJ.;U f .;a .-4W. i ... o- .' '-.L ".ju ; -.c aeetu cUJ:hi-.; ror. !'Cl.*.ted
Qti hk_ i' t Oi
.. -.'ci,;. hiaj h;. '"D. y '-':'t:.'c cr a pur

.x. ,, -.
.... ', k .
* :., : ii .. :'.i.;L L:*v t..he z'ti i j.; "; ,. it is. s': i4 C ,_ .L ... 01m.
C e::t, xr'! ... A :4ik ,~ :;. (..'Ti-wt0 U."'- lOVC, L...s- .I t" : t.s:..,, "-
^:i:s ..L.ciin ,ms.'u i.'i .c\*t nrA0:'t an 2iss T7 .*v 3 3 froan. ^^.lf o-as 0 '.2 .4.. ".-hin..
, ,;' ,, 3 ... t' i 801e .. 7 t., i ,..> ,.'..;.c .i.ti .^
..f .-L.;t .. n *-.,-.* 'c cc:,., 1n-; Lu i,.t-c -.n,- t: C ..-:.., ,. ,:'.to'.....i oil as
saidl u,o .c "',- ,, cea1t t, its .._-..,
c ,iL-.,-- '.ii IT, .:. .,.. "e ..... '.; ",;.'.'L ,:,- c i; ,-.( .,L~. o ;^ic c:ic n
.,..,-* ,: '. '-<, .l! ,,.'-, .^:c:ic '.t:;.', it tJi' r f h ,,; ... ^'"' ;- y ?.. ^ .t
... i'f; tix' ..... I.::::J. .
c :. -, ;*_ '. n^ echirn (Oliver),c'..]J..'2 _''li or iC
tfouptie L .l-U' .&'!:;.'t-a ,h' ch rOWS ,.'.iarcu;.. t.. six uete-.so i. I-,L i:.\.t. -.vn
1i,,,e l i.. t. h i. "hcS- E, 1vy out^x' c :-rjQ
bL ur .. on !:"Lt, 'te .... ..rt o(oc \..a cL c' v t
grc~inri1. T'O.v a l1e-'~tlcrli]'e to__ji-sert'.
They '.': ii '.toL.i O" t.' -.. ... nit: e .sia er t. n t.te nii :.'".. 0:o,, ,& a-
, 's /,',e &i."'x Lt eG a 7u) .p IT ",Cl -. tLic/ s'e..53 1;-'.3 ti.- ,.;...i' i8
c ".i u;Lt..l to ,& :-" :.. W oi..-let.'.; J in ;r'-,! ;..;.4,E':Ly J.; not conil e et
te Lc:-rir.l .CC.,'i-L., of a uP2itc ...bJuir.-iil- oil -L,.-i; locIeo in
Zt".,eL) fvi.: ;.ccchJ0 cotyl2in :.,
-t. first t .he >.;li oil ..iv':,f cL a e't wio. d c o o.lor .i.in.
-...itc :wr: .l1 an "..wi; i,, flavor ., th.e yie?!,. o.f oil 0o v..t i l.iLe. C-,rt bin
sanmplesj, ,r:-.n, oextr ;,,-tc. _.. z tt. "exr in a '.-o diet tpp-r;- tu.-; -- ,' 5
.er ,.rNt m:. oil ."ILu .3"t.'." per c ,: c .a"e t ;1c;o J ,n.; to Q'(." 0-i.. L.

'"ji .i ,,. yJer' "ati o ,f_,iues v;hich it contrI.us,
n oIui ciicT..:. ";-i~'ll cI.;e_', oil .is "o .i,..., Its :,r, ci:l. ?'o ;J.t'Ili-
ee a -:' I"- fo lI ,,'.',
'+e l "i ; p i ,, oi .. 4C. -'t~s
*.. avity at p 0o. .... *.,
fluex of rvonc.cetion (L'oa1), 1.4?-"
*.otatr'y i o.,?'" *,, a,,, ,, &qu.3 I'.1
.. J. I,..L ica.OT- n ber', *,,, .. 1 ,
7i.;*'., J,:' "^';l ..,. '! .K '"" ( "- :.' ") o o, ,, ...*




- 3


'e hr.ve b9e...m the ;tuuJy of' *tb,.' Cop.i:'-ition 01 V,hcl ve'ioua
cov.otituentvs witilhout 1k.,-" any operation which ,voulk, altle,'S
tlh ir n.atU re,
If,..iC io:-dtn.; to .. V ol 1..-irK. f:r-,-'n i-',,r- th, Lc ,cid' contain 27
;-A'e' cent o." chcuijt'suo?.'? ..'l, i houl., be ea:y; to extr.act
t4 ich:u, I .10;(oo. Tlne i."on Q'.4;''J flot. uL oil b1y :iiple .r-,L:tlll Ua-
tion. I.e..'oso t'"ut.r .. r- ot o-t.r d nre:u aw ; .o..to OLz' ex
.4e L.- tiion.
-..n uslriii alte;'n..tively acetone ,-n-il prtr.fieu.. ether- a lar.
... LI *'Clr of t.rieswe h.,\,, cy,..,Lr.:l 2.;' t, D d'.i. *lyceri
>.*- oCJ' ,o'li ir3" .. t,: r. I .!r)-;Y ect 3*,V9:...:tt.ln 1c, a first 2
i..r. -&"on, Ai't,,, I.,; .,.2; I li.j-1riou6 U:' ,jii1i ..t(L.-..," c ',o hove ob
ut..2,i3.. a subst..nce o.' s'eiut: cop iste-L.cy Ii ce h ytall'
./-,j 1 rL:. : flL,.-,.ilary &kS6es ; l',,. ch melt s..L- i-.,L, a& 'i
o' L_ e .'-J i i .S LWj C
1...er .i.' ;- crLliLoWa aboo.6 the fsuion [..i.. its
,U w-. 'L-ry '-xiO1 ..-fl.d Jibxn nwr er era,.n rA!.'-on t.L.,Y coro Itant.
jhAc 2LID t'uncc' YJau the-. coi;.'crt in i wr state.
*It .)us.3 s'P.G the follow.il.. 7hv AT?-. O:L., ,' ,I'?'l i '.2.l co .i.tc,'. S;
t.*.oiti.; is'o L t 1
t- :1.)0i:i. t'c~at4.o*X) f~uI--


.-*- cific rst-.ti'u. .-
Th teopetiLc"3l .L.. incp: 1t12.'xiz*or ct tnCliU.12.UC, ;&ar ^u is a-
~~~ ~ ",' 4' ."



tout ;.,.._,JL,"- the s. ;*ui'icatc-, _.uu.f.' -.bout lti.L
.... :.' -.tic ,'}E .' .i't., of the Io i.,GL JJ. ;UCrCY. ., tle .ro1'itct
-.1 iIii.,..i t.j to L-'.:.i a r'i-'.t(.i e oa i.l :,.'. .'..t,'
.;:'fL; Fh:...t.i a 7w
..'ij3,.: f y On reH.ov/i,1;., the. ,8G].t'.,'sit, b$. ,.. -L~'ill .*l.itngwe r!...'e./c ,b-
'.o.'-lned an vi]y 3. ] 1..if t .L:tbet ta'.lj.leyellow in -o.l, u'ih ,'r

p..I -. IT& 1
Q-. a e -..uic ... oc-.. ii. o. .':-.c al n .: o
l,-' l.- ', 3 I ..,,-1-



2.ca.. .. 1': Lcn.'
.... %iJ ... ; jL .-:L .
-l *.,;i;t 'L.r.j' .,. a l';i ." rot: ".-yr''
.,,... vwmich is of iT6.,::t i ..<,-.;c;',.-:w Co.,.c... ;Z .in.." uorli. &ee'C oil,
C S thc' t A ,- o .; ,,r.I.., \ I i .L' U'e ...-...y W .solL s
lo', 2.02l b iL. : -. .~k c, th-i .Lee'C4 Of Cii u-."d. ITO..-ILt &:d i1
'.lh : io Uncb i'cl :U h t t2o;i_," L":"tl.l.i. ; *: itb h it- 'LV."

;:r't .* cy UJ.1. A JOlf. nts 7r-
' ,'n .ri .i L. ,,- '*,u.;.;.:.*.L .-ic'ro i bOCUoc a l i-t.- e... e p;-i"'ts8
crystalline ;,J.;.ce,'AAi(c. J, *, ; per c-'i.t,;.',t *- c: ;*PJAL; 4 it;P
%o 4 tip
-q '..,.lyo-;'ride.8 a ,.' In ;,' a i;i--;"-h ro:L.;tory power,'; .. )c' cent, .n
cu;ixarai'in-.; s- ,.ories "l' crystc.:I.liz,.tions of "t;-:, ,-":.L'.y.; p:rt,
1t o .hir'..; of 1.Auvh irrport.-,nce was fount. e hEL':e oa wind by a
..;,.; lab1'U-. Ious t.itj*...i ., h..;ve '..ni eIVt.. Au-. ia Joiw,-a i
-. e cEi"l)-!. ]liave continued:', t.he. L..LLL' V Oi t ,! ..;t." T'ou.i hich".
is ,b'ta.:irne:. b, sappo:; ic" l.oo vWith achol C o. .c hve
u;ie ]
1 ..t,.l cr.tallizat.ion, (uruI;ly from .alcohol),
;:' .. r'.ctic'.uc ,l distill.Atin;- o- utL. eth'yl c,..ton:,n "UfZ"'

;.,, r ''i-,':tioral pai oi iic ,o ti(t ).
.'*,' t1,.' ,1.2 t.; ,,ait 1X i, 1L.A:. aQ',e t...t ^W .a':i1', C




- 4 o


tate (Method of Heinz).
:e have not gone into these operations in detailbut have
only given those examples f-romra the experimental part in the
me iio. QflLILOJ~jrl.
In comibining the methods which we have oho'n,-v;e h:w e deter
mined approxi-martely the composition of each group of glyceri -
des of iorli seed oil.rthe crystallizable glycerides contain 85
per cent chnuliooyic .-citi ard 15 oper cent pa itic acid. The
pasty glycevideu contain 8:', per cent of ch'auIsLoogTic acid. The
rest consists of Edliost equal (jquantities of palr.itic acid .a"nd
a nef6 liuLLid acid pOssesieA:f rot,.tory pouer~v;hich we call Jor-
lic acia, ihe liquid glycerides conttiuin 7 per cent chnrulmoo -
gric acid,10 per cent pal3itic acin- nu i. per cent -,orlic acid.
-Jhul;,1moog-ic ,cid, -.orli seed oil cont:..ins about 80 par
cent,which we have satisfLlcturily extrnactcx in very uood yield.
-ecui wni .'renshvll (r-.,ction- tion of Ch.-ulfniooL;ra 1. il. ,j,2er.
Cham,( p. LG6.-4-1-3) have ztuuie. in 19., the
pre par.ri -Lion of Chaulviooyric .;id Yn hydnoc ",-pic aci, ten
I'rom the ecds of the Dor,.togenouL. i:ur'zii,4.iA .n-d have [propea-
rerd after very laborious o;ei,;,: iouv (fr..ctional; distill-...tioTs
of the ethyl ev. tors and repeated cryatUl.izationr of the' uif'-
rent ;ncid ractions3 froui 1 kg. ztzrtinj matoic:.l;10C g. of"
chnau1mooryic ucid,FA-I 50 go hydnocarpic aciu. ;or'li oGiA does
not contain f.Lyanoc.r:.ic acid,amd -Jive& rivi to six tilimes as
much ch..,iulnoo rio acid. Tha oxerixsern).l p-wt seovs the best m
thoua of itC'ep,. ,tio.L
In pose-2i.sion of anr Importa.t :uaitity of ur,- chuulmou-ric
4-cciuwe have e'fectec a propsr'ti-'on of trich-kuy.uloojrine by a
synthetic procecss'T;hie h wa have succeeded in e:-:tractin.; directly
f:raa 'orili oil.h aulhrioo.-ige acid hao bean known more than 2.2 ye-
r. ,oarshowevertr ichaul.oor11in1 has never yet been described.Its
preparation does not present ,_r'e&t difficulty* e bn.ve applied,
point by pointthe general methods indicated by the -iutch che -
mList .chelji in 13'AS. It consists of estecritfyir pure glycerlrine
with a l-..r4e excess of fatty acid at about lC', at a pressure
of' about Uu0-,5 n.r.of i.,e-cury.;'.2ter several crystallizationsr from
acetic, Lrich6liulmooorine is obt:ainaeu in the formci of colorless,o o
dorieass crystalspcoaezesinj the i'ol.owir.l phyL-ca-l ar;ia chemical
charac te r iL tics
Melting- point 3 459
Inuex of Nfi'1actio ri 474
DJensity D10 0, o-137
npecCl'ic $otition 64. 5%'
-.a&,juonilficAtio nuiaber li,.'. 6
louine num-ber 87*3
It is worthy of note that the LaoltirC point of trichoulaoj
rin-: iv reinnrkLtbly low (439) compared with that of chRulmoo-r1"ic
acid, 632. 'ralth ,lycerideBs of.the solid fatty acids of
thias series ienorally hove a higher uoltir point than the acids
from vWnhich they are derived.
aliic *.cici. The presence of this Etcid in J-orli oil has
been shown by 7ouidinj and ors. .e hb.ave,howevor,alo found it
in the three groups of rlycor'ideo vhich ;ue have separated at the
boerinlilk; of the vork. .e h-'.ve shovn its preoeancc in the exenini
tion of the pr-duct as pi'uveoc by the fc,.ctiornal distillation of
the ;ithyl enters. Yhunir rotatory ;,owr is no;blVy inferior to
that of those fractions,Ithe ioc.inre nuurber is wee.ker cind the sapo
nil'icrtion nui;ibor hi,;her# On reIisti.lli,; these fr'Ctioni seve -




a 5e-


ral times we h,.ve isolated a cer-Lain c:u-.,ntity of' on ether'oe:l salt
haviri: only a we.:k rotatory po':er .-e have e;-trate h the fTLty a -
cidCb by saponii'i.:iontiie l-:.tte r then recryttallizeWd 'ev:n'-a. ti-
Ie"J fr, u :.lchol,: finally urJiuh& ; r... p "uct v;hich rltd shatCr
ply at C,'.5-, heon mixted with p..-.iritic acid the -i.p.driet-, not chaz
*e 'iQ tVriy tV is was nut -.cco. -r .. '" y hm.iuo uo ,it va
.ais-ol,.i.'i ni-n -[cohol 'nd fr--ctionnliy 9rin 'clpitn:ted by uccc-'sive
additions of an alcoholic soluLion of malie'ium" F-eotit.e, 'he uuve
r-.1 fractions mliolt-J ;tt cI.' L A ,i P.T.h p 0,oves cOnCII.L;.:i\ 0ly thin.t o -.1-
mitic icid alone wa 1)r'e4,er t.
].40 1c .c.xi a. h ',e i:ol;-..tt ..0 ;rua. tiw ll i "lyc i.-... of
-aoull oil n. o IUJ LCiLv\Dich is li:,ulcl at crd3iza'y tlcie'3.urC a vs .id
whose p!z.ycic.- and chemical propertieLs ,.,e are brininL.; to a con
clu10ion,..il.ch dues nut b-alon:; to the liner "perie;Dbut t.0 te cy-
clic st'ie; of the o5aT family v.'ith chaulmoo_.ic *3',i hy-MLocr-rpic
acide. ",b- iodine nauabeit sbowS that it has .mi ethyl. ne lirdPir,i..o
re so thain these two acios. ihe molecular d 'i-ht wei: usterrmined
and the tbrwjla C4 ha.-, 0 attributed to it.-,e have cbta.ined this
Pi. the itrce seee cjud 1 have cl-ariacterize& it anr jiiven it the na-
me of ;,-rlic acid.
Th' j:,'ureet product ':hiel we lLnve obtained has ,.1j iucine iintriber
of 170Qthe theoretlca-l bein 10S1. It was imposlble to attain the
fi:.ure,cithi-r because the product contained a little -h..;llmoo,.iric
acid,or atlso because thlie ethylene bond '(id not fix the theoreti -
cal qu'intity of hl-dogen. These two e).planationc axclubue all but
one oth-r. .* ,ppea l ;or a second only for t i nao eeds of ou, ca-
soewe a-ve ciiscAcorered a maet.ou. for Qbtiinin; the &a:ir.ius value
for the iodine of *klic aeid, It is nfLceGaIIKJ to tue a '-- O
ce s of an acaltic aci6 coiution of bromine iodine (Tuetliod of Ha -
nus), If t-he theoretical qu:nitity of ]i.jo..ern only i: employed the
ethylew r youpe is not completely s.:iturate,--. It ta.keU o'roui 3 1/2
to 4 titAes thi u:,',ntity to arrive at tho value 170. It i3 proba -
ble th-it iLk,.,r thc.'.e conditions Liho reaction is incon.conplleP It
is not th ; jir;st tie thlt the ethylezie ;-'oup showed the saeii re-
action.
.VG, re ")7w..''re'..L SFz-' v.. saIlt of Jolic .....cid .orlt of. 21
U:; ,> .-'na. 2. '1'hc last th-oc ,'lts "rwere obitaine'c irs the form of
an amoiL1ous r;.aps,GOi'c- or 0.2d'. vt,-OCuO"L1.he s8-it c-' -u nutnbly hal
tL- for:, o0 a very brilla..zt t:u. tra1-nslucent 'un. Ihe salt of Li
is solid at the or'.Ar.r.2t Leug,. tiro, It ha.d the forr-; oi a Z.oap5
but was not ry.-.llin it L.ta .A 3" to a lupaccr to
1Thr'ey and 'ec0?pcJG. Iie<..ti.,': on an oil ba't tuLrn5 it yellow.
It -ch--:r_5s cnc t.oiters about l .
,'e hau-:: tried to ott:-in "e'. '-tl ox'Leic derivatives of '.orlic
:cid in the hopa, tir t certui, of tho n;i would be cry. talline 6,e ha
ve preor,'ro the hydrcoylianic-uthe diethy. uid;-j uici the -mide of
::orlic ocid. The last one c.lcne vui; obtained crystallinre antiU rel-
,, id hu as x- a .',
ted at 55- -;ie delerl-Ginration o.: nitrogjen by the m4eldahl metnod

foun, d 4,.3 aic., 5.Od
Sorii -icid,'which is a liquid fatty acidis difficult to obt-.in
,;)Ui'.a e b!lieve~neverthelosthat we h-ve cle..rly idsrtifie: that
r1,s mirnlaiaLeo principle,the lack of t;vrtin. m.te-ricl hrvinj pre-
vente&, further stay of the subject.
.e hplve cn.eLi attention to a fact which we hi-v,-e d^iccovered in
the coarse of our researches on the work of two .-m:ricanar.. .-.n
ani :6rensh.lhl (U..-.. publicc Iealth .),r3vice Tul1.o1, lA,p .12-z3,
iy~si4)) Chom. .b{3,ly;.i(: l^p^6




- _6- -


who obtained in 1.1, f. can the rotlti-r liquors from the crystalli-
zation of chulmooiTic and hydnoc rpic -icida from c.cuimercial cbaul
moorn oila liquid acid h.-ivin, a rotation of ,5'.,,and an ioline
number of lIG-l',hich they Aid not _;ive :u-y name It .ceeats to be iden
ticacl v;wlth our -,orlle ncid.Unfortunately th2 st.:srtin" wateri:ai. Was
obtained from a uncertain bot.anicl- origin. In faction sea.lin: cora
mrrcizlly under the nafn oa" chaulmoo.;ra oilthere is usu;.-'ll1y meGnt
the oil of h:.ulrooa Tr'akto,.no -tirzii,vhich is -:r oil obtui
ned frown the eeos,_ of vr.riouL, Iyunocarpi, .e have h:1-. very ,reat
ifficuluti.s in referring to th',, writinaj ofi .,-'n *n .renshall,
which wore not in the fornm of scientific periodicalsbiut in the
form of a bundle of reprints for the attetiLon of tb:.: officials (f
i.he Public Hy"iene .Jervice of thie United -t..teC.

itiuut enLeri,': into .jrent.. (let'illgwe d-'Qcribe o.i1 ithe operations
whichh w'-e h.;v? uoed to est.boii.sb tilei ,in lnlc :'es AitS f-or thLs stj
c~y.
r Pe".1-ration oof W h xii o.iprc ci fo,, .'li (l..
Gorli Oil 0 is 8i onJ. vvi-?d o-ri exc:co 1. icoholicsrxia.
For. ex:a.ploe.
100 j. oil
i 50 g, rQjuL,20 Ger cauiit
{e flux 1/2 hour
Of UL ..ee in.,. b ;.-.x
t'he uixa.Lure of Sc*i.o obt"-.ined l *isBOveG in ",-.2-'-: coeu by ;.;n
excos o:C u l in a v.ra C.-,tory funAILel. The fatty -ici.: Iiberi.t-d is
re.etet.Ly extr;:-ct by .>' .5'inv with ether, i treal solution
is ..'ahed ,ith 1a-, lozI ); the v-c.'a!;incc :e ..,oi -d then drled
Thith I0r.,,S4. The ether is di tit. ledo a the last tcVces of sovent
driven to. by he.- tii; on -.ate;r bA1th in a sti'crwt COf under rsdu-
....d pr"3s lre,
"-'his .aurifi-1 by prsfolv in 4 art. of cent hot alco-
hol :-id allowedd to crystallize. It is filtered by auction, The sa-
me operation is pezeated throe tlc oricl finally giwij a fai,.ly pu
re -"Looic aci.. Ito prLy 1i v.erieL by uCzJWn; oL its m. p.
io. i b" .'. rotI..toll, !'o..,e'.t1-,.:LroLfc industrially extr.xcteod oils
the cryotali thu; obtIC,-,.,.. ottiae t.-tll colored. ('n ctiAtill..tion un-
der rotuiceC "Ve.ssLE.Oti It-,t traces of ir.urity are removed. It
is v.ra inconvenientl.. At 23t12 the acid comus over urJer a pressure
of 14 ./2 n. .'e prefer to is.till in the forM ofi the ethyl er-ter
"dhich ccolc-ao ov0r' -t a mucii Iox..er te;:'.eraitture.
.he acid is li5etec 5 hour, t le, .t,to boilin';,, .r rl.Ux
,itlh equ';:.l psrtn of VG per cent ,.cohol nd 3 poi' cent of itt
veJ:.bht of -ure -U ,A4. ".- two layers are ep.rat:--- th- ethyl ester,
infj;.,'l.uble in the nlcohol,forms the lower layca. ALa3 iL .ec.,Atte,:!
clisolve';:: in etl-er -,nr.'t washedd several ti1eaIfirL t witii s:t Vi.ter,
then with TIi or in., ry i.. .ter to remove .'ill trae s of H....J ,n (istil-
ling the ether~the ves-.iri-. reuLt-nin,:" is Pthyl caLi.LiooJIaLe "_dC is
brou.n in color, 'ihis i,3 purified by distillation under reduced press
sure, The ,-cjor part paOse., oaer at Ll3-2., at a ;ressure of 13 m
of uarcL,.'y. Lhe pure ethy.l ch.,ulioo :rate is obt..inuu absolutely co
lole.,, Ln _.lLjo..irainrk by tha or'uin.'y method od extractiz.' the
solution with ethcr a."zer !.ciQii.liyi:,ethe aicd i. ob..-e.,Afte.r e-
v..co.oration ofLf the otlert'ie (ch.-,u eooisr'c acid is fimiLdly crystal-
lizeu I',OWi alcohol,
It separates out in very brilliant colorless laminae,without any
o(Qor. 'ihiu cICd iaa the following characteristics




S7-


.elting point GS
.aturation number 198.6
S o..ine nicbubr" 90.7
LotO.tij." 61@ ._. 7 L

The m. p. anI rotation :r,.i thw samei as Voundi by tower ;-/jd Barrow
cliff, Lhe theoretical saturation nhmrber is 198 ad iouine wa
ber is C&.6.
..jythtic -reiaarg"iin of rilchnulmoo:.ine, .'e h.Qva already
shu,.n that we have uaed the general i:eto- for p.-pcipmj the gly
corideUL. as described by 2cheij.*i hich conc.,it: in her:-tinj at IJoJ
under pnartial vacuum a large excess of fatty aciJ *-vith pure gly-
cerine. L:assins in dry 'On gas servea both the p-.rrose of stir-
rin, up the mass .aiC carryin:. off the 'i'l0 foCiJ2J &urir. the est!
rig'ication.
e have uued puAe glycerine of comw-rce which X.;e have recti-
Mied by distil.lation zmidor reduced pressure. ,,'e haLve reected
the first .nci last actionsn, t.rio glycerine which we uGeI- passed
over AXt .309 at a pr'..S.ire of 16 i9 chau .ic acid wa
pure IrQcGL&Ct which we preparcu.
0numo. .1 cid. waa

hix-ve heated the mixture of ch:.uljaoogric uci r n:i glzcerine
dui'in. ei.jit,,rl uyf at 'ie rate of C to 7 hours rpc-:' r-iy. .e have
ato;)o', when we saw no further char-e in the aspect of the Ue -ais
afrl& no more droplets- of H2(O lonnec on the ,1 do- of the i's3k. We
have Uius obtaineoa a sirupy product "-;ithou a ouor.-",ince ;e ha-
vs used a large excess oi chaui.Luioo.Ti .cid,the ci-La dc product was
-ewhcu with sovoral .)ortinu of warm ..Lcohol to reiove the la.t
traces of free ;;ici. .'ter everal. recrystalizA.tion: fro alco -
hol.,tie tricnulioorTrne formed colorlessoorleou ,:ryit,.l ,dry
to the touchmelti)y at 45.,ancA reim.inir i.c-i.d Zor a. lonr time
an. t4kin. on a sti fJ acr.y,.trr.w..hcentvitreous appuea'a;cce.*e hl
vO iven te principle ciiomicnj :'r!U 911yic':.l propec1i.
The J:xtrac.c io of^ pi' >,'!.itic -"i t^?' ""- "i ,]ljy-
C C "u 1'-' r, "iL ,,..C.. i-t
cee'ides
'-.he alcoholic moLher liquor.s co'iln;. fruit t4i2 exti. action of cha
ulmcooLT -ic an acic frou the solid ;lycericies as zonc-. :tLratto,.&llo
edt to c'yct.-lllze -anij 'Ives a different piociuct 'with a lo'.eir L7eel
in,- poini, .; have thus obtoained,:ior exmnple,one caSt of
cryut-lrsealting., at .%,havi.-, a rotation of 2`9Q .2 C ,n iodine
number of 2.4;two per cent of a product moltir';.: a;t -11iwith a ro
t.tio, o." 152 4.C' andi iodi-ne n'u,,be- of -'.. The f-.cL tha.t
theo rottory pow'ei' Is notably lo''/er sos t a hso.ici faLty acid
vUith a normril chin is present. -I'y fr?:.ctional di.ctillatlon c'f the
ethyl esters,?nud by cryStl_ li.atior, of te cids co,; fro there
Uti fractions show a weal rci.t.ory povicrthe whole cif' uhich v
succea"uiully extracted,
The -ac C obtixie by the cc-'n.co.Lr-.tion of th' v1.oth'r liquors
of the chuiooric acid -. nd ertii.fyinrL with ethyl :.Icohol in
the rc,-en.-e of sulfuric acid was ..ctiorwlly iij tilled murder rj
duce-i pressuree i a current of C02.
F'it :.;itj.lLigon.
-ressure 12 13 rm. of ix"rcurv.
Ter,. .':t. ofi fractionec i Ta,.tor.r Pover
(1) 2u9-J.5Q 14 solii. at *.Q) 0-lO'
(L) 1-l7Q ,29 (solid .-t O) Pt-,.
(3) .i'3-19 1I;-. (liquid) 39-0




- 8 W *


(4) 219-219 27 (liquid) 429-20,
(5) 221,-39 3 ( ) 450-3C*
(6) 223-272 4 ( ) 440-C,
Thon isolating the inactive fItty ,ciduand distill-n1r; the first
products aua in.
.,eco .i Asis i jlln..tion
Pressure 13 m1. of imorcury.


(1) LOL-9Q 3
(2) -09-122 -b
(a) Ll--14Q 20
(4) L-14-17fi i1
(5) .-17,-LOS 19
(6) 220-239 2
..cSiG uc pyroenous,
On e.,trnctin; the fatty acids from fraction. .,. nud 4,.and cryj
tallizing" these frou alcohol rnd deterLling their rotatory power,
-:ciC 2 24s 5u'
3 383 54t
4 549 O0
Thc acids obtained from the second fractionwmelt at 59!shave a
satur-.tion nusiaber of 2C'9 n.od an iodine nLubor o. ;'1.3. ( n recryd-
tallizinc: fLromna alcohol ::ad de eterr.inir,g the rot:toury poIer after
V r'ds *
:.otrtory Power
2d cryustllization 22Q
3id 139 ..,'
4th 3& "2".
5th 30 O0
Cth 0 0
The inactive acid obtained melted at uZ.59 and huci a sat'ir'.tion
numriber of' 2169, It is identical with palmrltic >cld'idwhich has a m.
p. of 6 g and a saturation aiuiiber of 2109
The list value is a little hi.jher thai tlht which we obtained.
:e have subjected our pl.mitic acid to a series of fractional pro
cipitations to make sure of its purity.
One aid sixty-five hundredtia g. of the A ci was dissolved in
36 c.c. of -.'5 per cent alcohol azni a 3 pa.r cent solution of mcVjri
sium acetate in E.lcohol added corresponding' to one-fifthUi of the
molecular quantity, 'iThis operation was repLeated five times and
each fraction crystallized froia a little alcohol. 'he qunti-ty ob
tined waa sufficient for determraining the melting point. 2he five
fractions all melted at 62,S59.'Ihe palmitic acid used wastherelob-
ro,co.vipletely free from ihomologous fi'atty acids.
Lxtraction of 'orlic ,.cid. The major part of the lioquia jlyceri
des of ,iorli oil consists of .J;orlic acid. 'Ihis was extracted as
follows;:
Th-e g-lycerideu were saponified with equal weights of 45 per cent
alcohol and half of their weight of 36 per cent NaOh. 'The solution
was acidified with YI6 and the fatty acids extracted with ether,.The
ether solution is separated from the water aid dried with mnhydr'ous
Ra9 S04 The ether is distilled. off and the acid obtained had a
slugish consistency and was yellow in color* On crystallizing so-






veral times for 90 per cent alcoholthe major p.trt of the solid
acids came out. The mother liquors were concentrated as much
as possible ithe residue is filtered by suction to separate the
crude liquid acids. These present one-third of thle total acids.
This is esterified with ethyl Llcohol in the presence of 104.
The ethyl esters are poured into ordinary ether,witshed wittfl salt
water and then ordinary H1O, 7.. evaporating thie etherit remains
in the form of a dark brown liquid. This is rectified by distil-
Intion give palmitic acid. The other fraicLions which were still
slightly yellow in color were mixed and distilled a second time.
The iodine number of each fraction was tiken to de .erriuirne its ri
chnriess in .3orlic acid.
fTessure 15 mm. of H.,
oriperature I.eit% lodine number
(1) L2l1-1.b 4 103
() 215-189 13 117
(3) Ua-2 4) ..C128
(4) 220-222 27 1401
(5) L2L-U5b 16 149
:,esidue i, ne ous 4 149
The theoretical iodine number of ethyl gorlate is 166,vihicb
shove wbi4 h distillation products are richest.
F-l~ACTI0ONS 3,4,^ ~.m-; CO~...II.Lb XIii.u/.IJTILLL..),
Temperature Pressure ri. ,,e iaht I Iodine number
(1) 212-189 14 2 6
(2) 213-189 13 14 10G
(3) 215- 9B 13 Li 126
(4) 219-21 13 30 138
(5) 2199 fixed 12 23 15.
(6) :19-20C 12 5 154
-esidue .ndt los s
T'ihe ethers absolutely Clear and colorlesshave a slijgtly
-irouintic odor which is not dizajreeablo,but the io'iine number
of tho end products not bein% very. high,it seemed superfluous
to undertake rnw "istillntionsbecause each operation invol -
yes the loss of an appreciable quantity of the product lby hea
tinj. ,'.e :ewre satisfied with saponifyin oe.:ch fraction ex a
tracting the fatty acids vigorously cooling them and elimina-
ting the solid products by filtration ,,e have thus obtained:
(1) 'Thitesolid ,-cids still conta-m.inated with oil, whosc iodi
ne number varies from 10- to 13',-. -issolved in alcohol, they
have allowed a mixture of paliAitic acid and chaulinoo.jrie acid
to crystallizo,the dorliq acid remaining in the mother liquors;
(2) liquid aci3ds slightly yellow colored made up chiefly of the
gorlie acidwhose iodine number varies from 150 to 170 according;
to th-:' fractions from which they come. The theoretical number of
a CJs81t+L acid,possesoing two ethylene bondsawould be 131.
e hc1eve subjected to distillation under reduced pressu'edif-p
ferent fractions of this acid v-.bose iodine nuwiber reached 160,
A jain of 7 to 8 points over this vwfluo sometime- caused the loss
of 12C per csnt of' product in the form of tarry residue we have aj
so been forced to determine immediately the physic:-l an chemical






properties of the purest garlic acid we have obtauinded.
Gorlic acid is a colorless liquid which turns siihly yellow
in conta-Ct vith air, It has a peculiar odor .,iid an .cridburning
taste.
Theoretical valuo
Density at 182 C, 0.9364
Index of refracti
on &5J& I- *
,totatory power CUQ 18'
Index of saturatJ
on 1i9.5 Lul
Iodina number(0(a-
nus) l16 181.4

1
For ClQ1F30O2 (with two ethylene bonds)*
Lithii U -., Uorlate. t;.e proprred the lithium gorlate b.- boiling on
the reiflux conuonsor for two hours a solution of ,-orlic :-cid in
70 por cent alcohol in the presence of a quatitity of. lithium
carbonate correO.orc-ing to twice the theoretical qcur.tity, '.e
then separated byr filtration the excess oF lithium, c-rbonnte.
The o2coholic solution wa. concentrated by distill -'tion. The vq
ry colubie lithlui..s-aclt was not dcpoiAtec..'J.ie solution vwas left
for se;:eral Clays in a vacuum veil jnr in the pre.cMce of sulfu-
ric acid, .', hnite,-wrinAiled pellicle was for',,eCI with a soapy,
noncryst.lline 'e.'rnce aniLd the e(ttice mao -r'CLdWLlly solidi
Ifioa,
By cbcckinj the evaporation before solifif'ication is comply
tela solid part and alcoholic mother liquors may be aep.,rated.
'.e extracted the fatty acids of the solid part and those of
the soap still in solution and found that the io-_.ine nVLbers of
each of then were appreciobly tho same (16b8 and lbU)
Lithium -orlAtc is slightly solublo in boiling ether (2 to
3 o- per hundred) and V-,'c tried to utilize this pr'oierty in or -
der to purity it* The ethereal solution,concentrated' and cooled,
allows a white,h.rd product to depositbut without mny z: ppeara j
ce of crystallization. The iotine number of the acid of the salt
thus purified amounted to 170,a figure already reached.
The attempts to pjepare barium gorlAateatrfeiiuii .-orlate: and.
copper gorlate ,ave us results even more unsalsi'.ctory.
*,mido of ;,orlic acid. -mfide of -orlic acid via prepar by
allowin'- ti.o chloride of the ;orlic eicid to patEs vory alowly in-
to a concintrateu ilid cooled SiluLion oC' f aELLom-ia.
In order to piej;,'e the -ciid chl.oriewe uaed thie wLiethod incd4
cated by H. : .eyer (14) it consiAts oUf o. aL". Lio2Al chloride to
react directly on the acid. .e ho staL ot tli, water bAth 2or tv/o
hours with the reflux cozienser a moisture of 2c ., of gorlic
acid ond bn .0 of thionyl chloride;the quantity ot rer_.^ent put
to work corre-pondod Lo 7 tile; the th'Soretic-l Quinrtity,-'o ,ai.
trained the boiling for two hours. 'fho liquid became very stron -
jly colored. The excess of thioiyJl chloridev w-s c.,Uefully distil
led. The chloride of the g&illc acid remainin;: wa's in the form
of a brown'oil, ,e conveyed it drop by drop into a saturateda
queous solutionl of a-,nonii. :..s at a temper'turi of -15Q. Ihe _
de was ixmnedi-itely precipitatedl. It v-i: crystallized anid sligh -
tly /yellow colored. .4t'-Ler having been decanLted,azhod with writer
and dried,we purified it.aby rei.eated st..lliaioij in acctone.




- 11 -


It melts at 95- iwe then determined ,the nitrogen there by the
jeldahl method (see pago ),
I.-egmio and Conc lsiong

The solid glyoerides of the gorli oil crystallized 16 or
17 times did not give us the pure trichalmoogrine. But the
presence of this compound in the gorli oil is certain,becaM
so chaulmoogric acid represents nearly 80 per cent of the
total,fatty acids, The high melting point of the crystalli-
zed glycerides obtained by us (53) as compared with that of
the synthetic trichaumoogrine (459),indicates that a palmni-
tic-dichaulmoogrine must exist in thie oil studied and that
there is probably formed a crystalline combination between
this compound and the trichaulmoogrine.
Cwing to the impossibility of extracting this last mentA
oned glycerides from the gorli oil,we prepared it synthetical
ly and we found that its boiling point was considerably lowe
red with respect to the acid itselfcontrary to that which-
is produced by the triglycerides of the fattysaturatea a
cids with normal chain.
7'e clearly distinguished the presence of palmitic acid
in the gorll oil and found that it contained about 10 per
cent of it.
Je finally extrated from the gorli oil a new,highly dex-
trorotatory liquid acld,whose constitution is certainly ve-
ry close to that of the chaumoogrTic and hydnocarpic acids.
.'e 'obtained it in almost a pure state and we give to it the
formula C--Qo"0*
Indepenenuela of the pentagonal nucleus which characte-
rises the acids of the chaulmoogric group,its constitution
should admit of two ethylene bonds which have not the same
capacity of addition. It is likely that one of them is
bouix. up in the cyclic part of the molecule and that the sa
cond is located in the long chain attached to the nucleus,
.le r.:e making a study of this acidof which gorll oil con
tains from 10 to 20 per cent of its weight.





Gorli oil Oncoba !l`chinata.
i '_Substitute for Chaulmoogra Oil.

ny indre and Jonatto,
Bull, Science Pharmoc.
No. 2, Feb., 1928$ p. 81-87,
Among all the medicaments used for combating leprosy,chalmoogra
oil isperhaps, the only one which has given encouraging results
thus fart In addition to this oil,which is extracted from the seeds
of the Taraktogenous ktlrziipa tree belonging to the family of Fla-
courtiacees and wkich haa been used for centuries in Indiathere &
re others supplied by the plants of the 3aine family which have ve-
ry much the same aspect,composition, physical, chemical aind therapea
tic properties. This resemblance is o0 ereat that these oils have
of ten been confused.
Although1 in India and Indo-China be probably means to say,-the spj
cies which yield the chaulmoogra oils are veiy numerous,only a sin
;le one of them has been known in Africa to the present timename-
ly,3orli oil,from 1-chinLta (Oncoba) (Oliver). For thio reason,it
swas an object of great interest. Cases of leprosy are still very
numerous in populations of our African possessions.
Origin of Gorli Cil.

Cncoba echirnata called Gorli or Katoupo by the nutives of ,es -
torn. A.'frica is a tree 46 probably should read 4 to 6 meters high
belongings to flacourtiacees, branch of the Oncoba. Different authors
have found it, in Oierra Leone,French Guinea, Ivory Coast. It 'bears
round,prickly fruits,looking like a chestnut.At the time of maturity
the envelop bursts ox]k the grains appear,rwhich are covered b'ith a
thick pulp inside of the fruit. 'he seeds are a little larger than
a srThin of wheat. 5hese are fnun-colored and measure on an average
of 8 x 4 mm. and weitg about. 06 grams, These are the arn&llest of
all chaulmnoogric seeds kmovm. They have a brown, coriaceous seminal
te:ument of ai jaded aspect and this tegument surrounds a white and
oily albuLmin. The cotyledons are slender and are plunged in the al
bumain. ',hen out with a knife no oil oozes out. They have rn oileo-
genous,sweet tastebut they leave an acrid taste which is quite p,
culiar to it.After grinding up the natives use them to make all
aorts of cintrnents u&ed for certain cutaneous eruptions. As much
as 6C per cent of' the oil may be extracted with ether.
dorli oil wqa studied for the ftrst time in 1913 by Jouldinrg
and Akers (Joulding and .'kers,Proc. Chem. "oc. of London, 913,29,p
197-8),who pointed out that it contained 87.6 per cent of chaulmog
gric acid and t.'%* per cent of liquid fatty acids. The oil obLai -
nod in the laboratory by extractions with ether has following" cha-
racteristics (jjidre,Contribution to the .tudy of oils oi' Chaulmoo-
gri Group, Comptes endure of .Acad. of Parisl9'5,18.,no.25,p.1089-
91) ;-
Density at 32B 0,9286
Index of refraction
312 1;D 31I 1i4740
.otatory power 56B a 100
Li. p. 409 a 422
.aponificetion 1o. 184,5
Iodine No. 98
In order to study this oil we first tried (without usinj an o a
operation capable of destroying its chemical components) to extract






the different glycerides from It by fractional crystallization,
By so doing we hoped to obtain directly trichaulmoogrine,which
we thought should be its principle constituent.After many crys
tallizations in acetone and petroleum ether,we obtained AirSt
solid,very white,well crystallized glycerides second,liquid lyce
rides with hijh rotatory power. The analysis showed us that
neither of these was a definite cheoic:Jl species,but were corao
sed o" a mixture of glycerides of chaulmoogric acid,palImitic A
cid and a new liquid acidsimilar in properties to chaurioogric
acid,which we have called gorlic acid.

,cids of Gorli Oil
;'e attacked the different elycerides thus prepared v ith the
aid of alcoholic NaOh and obtained the Va soaps corresponding
to the fatty acids. These soaps were Oecomposed by means of a
mineral acid. By so doing we liberated the fatty acids which
we rec.:.vered in ether. Three methiod-: were used to determine
their coimpo ition.
I. Fractional crystallization,usually in alcohol
2# Fractional distillation of the ethyl esters.
3. F'rac-Lional precipitation of the alcoholic so-
lutions of the acids v.'ith maLnesium or ba ace
tate according to the method ol 'einz.
According to circumstances one or the other of theca method
was used either with the initial mixture or with the fractiu..n.
separated by one of the two other processes. kWe were thus able
to dtLeriinae that the fatty acids of 'iorli oil consist chiefly
of 80 per cent chaulmoogric acidl.' per cent pr:ilmitic acid,and
IC per cent gorlic acid,tthe last being relatively more abuudang
in the liquid .lycerides.
Chaulamoo"x-ic ,,cid.

This was described for the first time in 1904 by ?o'.er tL_
Gorrmall (Gour. of Chem. Joc.,190i4,8, p. 838-51) vho extracted
it from haulmoogra oil (iaraktosnous iLurzii). It belong to
the series of acia, CH2N '41'2. Its foraiula is 818k-Cou It
is therefore an isomer of linoleic acid. It crystallize in
brillioit lamninaerm. p. 689. It distills without decoy1p ositlon
under .0 m.pressure at f47-89 in a 1/20 CHCl3 solution. It
has a rotatory power of 62 It is little soluble in organic
solvents except ether and CHC13. It is easily soluble in boi -
ling alcohol and crystallizes on cooling. It has the same che-
mlcal properties as the ordinary fatty acids,although it be -
longs to the series of acid3 ClUN 403,its iodine number on-
ly reaches 90,G,which corresponds to a single ethylene bond.q
reover,reagents like fused alkali,amylio IJaUHdo not seem to
attack it.'hlis peculiarity is explained by the fact that chau
moogric acid has a closed nucleous,and the ethylene bond is cfqn
stained in this nucleous.
Chaulmoogric acid iss
CH
ci CH C(Ch2)12 CooH.
C 2 CH
Amon._ the chaulmooZ>'ic oils studied thus far,gorli oil is
ne of those which contain the hig1st proportion of this acid.






1,oreover it is very easy to obtain pure,because it Is not mixed
with its homolojuehydnocarpic acid. In order to prepare itit
suffices to crystallize the mixture of total fatty acidstonee
or twice from alcohol. To purify it,it is distilled under redu-
ced pressure either directly on in the form of ethyl chaumoora
to. -.I'e obtained a rather larde quantity of very pure chaulmoo -
gric acid which we used to prepare synthetically the trichaulrmo
ogrine which had never yet been described.
Gorlic Acid.
Most of the authors who have studied the oils of the chhulmo
ogric Lroup have pointed out the existence in these oils of li-
quid acids having a high iodine number, These acicds,which are
not very abundant,are still not very well known, kower and Gor-
nail thought they belong to the series of unsaturated a.cids wi-
th norm--l chain in CH1N-40-. This opinion has been generally gdp
adopted by thu chemiot~who afterwards studied the oils of this
;.roup. ''c. succeeded in extracting from gorli oila liquid acid
whose chet.ical and physical properties do not place it in the
linear series,but in the cylic compounds of the family of chaul
moogric Fmd hydnocarpic acids. Its hi-gh iodine number indicates
that it has, a higher ethylenfe bond,than itse solid congeners.Li-
ks: them it has a hii.:h dextro rotatory power ( 5C9),a property
which clearly differentiates it fro, the group of the ordinary
polyethylene acids,with Which it had been confused..-ince we de-
alt with a now substance,we called it Gorlic Acid. Its formula
ought to be C17 H2 C0(OM The major portion of the gorlic acid
is to be found in the liquid glycerides of gorli oil. These -or
ly oils,being saponified hot by alcoholic NaOHRwe extratcd the
fatty acids of the soaps with mineral acid followed by aevevl&
shakings out with ether, Ve then euterified them by means of e-
tiyl alcohol in the presence of a small quantity of H2..04 aO
aubJectd the esters to a series of fractional distillations,
The less volatile portions having the highest iodine nuibiir r.re
richest in gorlic acid.lt is not possible to entirely separate
by fractional distillation, etbyl ] orlate froni ethyl chaulmoogTa
te,or gorlic acid from chaulfmoogric acid,since they distill at
almost the same temperature. afterr several fruitless attetupts,
wv- realize,. thtAi the beat nmetho&e of separation v'ould be to fil
ter several times at as low a temperature as possible the mixtq
re og liquid gorlic acid and solid chaulmoo1ric acid. The deri-
vatives of gorlic acid, are very difficult to obtain crystalline.
We prepared metallic salts such as L;;,1Ja,Cu and Li gorlafeas
-nly the last is solid* It has a soapy appearance and could not
be obtained crystalline,m.p.1633 into a luap,accoracing to i&aquen
nee
Amon;. the organic derivative s preo pared inalmeygorlaidelagor-
lic diethyl-^nide,gorlio hydroxamiad acid,vie obtained only a sin-
gle crystalline derivative the Lamide map. SS, *'*e then determ'i-
ned the nitrogen according to ijeldahl and obtained 4.35 per
cent nitrogen. (Theory for C'H310ik is 5.05 per cent.) Not ha -
ving been able to obtain a sufficient quantity of these crystal
line derivatives to enable us to purify the rorlie acici,owing
to a lack of crude material,we had to confine ourselves to a stu
dy of the product, which in its appearance and characteristics,
seemed to us to be purest* 'Jorlic acid is a colorless liquid tur
ning slightly yellow in contact with air# It has a peculiar odor
and burning,acrid taste,




4 ,W


"'ensity 189 0.QXG4
Index of refraction
at 19. I,478S
Rotation c0C 18'
-aturation number 1&G.5
Iodine number (1antus) 160S.6
Theoretical saturation number for C18H30O2 i 21C1 -nd tht
ory for iodine number is 181.4-
Conclusaions,

Gorll oil ie the only chatulmoogric which hr.;: thus far been
produced by tha plcjits of the Uf'ica.nx flora. It constitutes nt
the preoont time the bast source of chaulmoogiric ncid, It con
tdinn 75-8 it cor.tairs panlmitic acid (10 per cent) aind gorliic cid (10-12
per corin-),possessiGBi a high rotatory power and iodine number,
This new principle offers special properties end its therapeu
tic action merits study z.long with chnulmoo:;ric ',d li hydnocar-
pie acids,







Gorli Oil Oncoba Eohjinata.

Substitute for Chaulmoogra Oil.

By Andre and Jonatto,
Bull. Science Pharmnoc., "
No. 2, Feb., 1928, p. 81-87,


Among all the medicaments used for combating leprosy, chaulmoogra

oil is, perhaps, the only one which has given encouraging results thus far.

In addition to this oil, which is extracted from the seeds of the

Taraktogenous kurzii, a tree belonging to the family of the Flacourtiacees :

and which has been. used for centuries in India, there are others supplied

by the plants of the same family which have very much the same aspect,

composition, physical, chemical and therapeutic properties. This

resemblance is sO great that these oils have often been confused.

Although in India and Indo-China the ch-ulioo.-rv, oils are ve-ry numerous,

only a single one of them has been known in Africa to the preser.t time;

namely, Gorli oil, from Echina.ta (Oncoba) (Oliver), For this reason,

it was an object of great interest. Cases of leprosy are still very

numerous in populations of our African possessions,

rin of Gorli Oil.

Oncoba echinata called Gorli or Yatoupo by the natives of V-estern

Africa is a tree 46,meters high beloneirng to Flacourtiaceea, branch of
it
the Oncoha, Different authors have found/in Sierra Leone, reach GuLnea,

Ivory Ooast. It bears round, prickly fruits, looking like a cliestnut. '

At the time of maturity the envelop bursts and the grains appear, which

are covered with a thick pulp inside of the fruit. The seeds are a little







larger than a grain of wheat. These are faun-colored mad measure on

an average of 8 X 4 ma, and weigh about ,05 grams. These are the

smallest of all ohaulmoogric seeds known. They have a brown, coriaceous

seminal tegumnt of a jaded aspect and thin tegument surrounds a white

and oily albumin. The cotyledons are eleuder and are plunged in the

albumin. When cut with a knife no oil oozes out. They have an oileogenoua,'

sweet taste, but they leave an acrid taste which is quite peculiar to it.

After grindirng up the natives use them to make all sorts of ointments used

for certain cutaneous eruptions. As much as 50 per cent of the oil toy

be extracted with ether,

Gorli oil was studied for the first tirne in 191 l by Goulding ond

Alksrs (Couldinp and Aimrs, Proc. Chem. Soc. of London, 191, 29, p. 197-8),

who pointed out that it contained 87,5 per cent of chaulmooCric acid and

12.5 per cent of liquid fatty acids. The oil obtained in the laboratory

by extraction with ether has following characteristics (Andre, Contribution

to the Study of Oils of Chaulmoogri Group. Comptee Rendus of Acad. of

Paris, 1925, 181, No. 25, p. 1089-91)s

Density at 32" 0.9286
Index of refraction
31a (1 31 1.4740
Rotator power 560 10'
M. ip. 40* 42
saponification tfc. 184.5
Iodine No. 98

In order to study this oil we first tried (without using an

operation capable of destroying; its chemical components) to extract the

different elyoerides from it by fractional crystallization. By so doing

we hope, to obtain directly trichaulmoogrine, which we thought should be

its principle constituent. After many crystallizations in acetone and

petroleum ether, we obtained first solid, very white, well crystallized







glycerides; second, liquid glycerides with high rotatory power. The

analysis showed us that neither of these was a definite chemical species,

but were composed of a mixture of glycerides of chauilmoogric acid,

palmitic acid and a new liquid acid, similar in properties to clhaulmoogric

acid, which we have called gorlin acid.

Acids of Gorli Oil.

We attacked the different glycerides thus prepared v.'ith the eid of

alcoholic NaOF snd obtained tlhe W soaps corresponding to the fatty acids.

These soaps were decomposed by means of a mineral acid. Biy 8so doing wei

liberated the fatty ncids Nhich we recovered in ether. Three methods

were used to determine thoir conpoaJ tlon.

1. Frne.ctional crystalli.ation, usually in alcohol.

2. Fractional uistillaLion of the ethyl esters.

3. iraotional precipitation of the alcoholic solutions of

the acids with mafnesium or Ba acetate according to the method of

IHeinz.

According to circumatanoesone or the othor of these irkethoda

was used either with the initial mixture or with the fractions separated

by one of the two other processes. We were thus able to determine that
p
the fatty acids of Gorli oil consist chiefly of 80 per cent chaulmoogrio

acid, 10 per cent palmitic anid, and 10 par cent gorlie acid, thie last /

being relatively more abundant in the liquid glycerides.

helauliroogric Acid.

This was described for the first time in 1904 by Power and

Gornall (Jour, of Chem. Soc,, 1904, 85, p, 838-51), who extracted it from

ohaulmoogra eoil (Traktogenous Itirzii), It belongs to the series of acid,

-4 OHM 40, Its formula is C18Hs2O2. It is therefore an isomer of




-4-


linoleic acid. It orystallizes in brilliant laninae,m, p. 68, It

distills without decomposition under 2.0 nunm. pressure at 247-80 in a

1/20 CHCla solution. It has a rotator power of +62. It i8 little

soluble ia organic solvents except ether and CHCIa. It is easily

soluble In boiling alcohol and oryutallizes on cooling. It baa the

same chemical properties as the ordinary fatty acids, although it

belongs to the series of acidaCHoNH-4Oa, its iodine number only

reaches 90,6, whichh corresponds to a single ethylene bond. Moreover,

reagents like fused alkali, amylic NaOH, do not seem to attack it,

This peculiarity is explained by the fact that chaulmoogrie acid has a

closed nucleus, and the ethylene bond is contained in this nucleus,

Chaulmoogric acid iss

4CH\
9) CH C(CH)12 COOH.


Among the chaulmoogric oils studied thus far, gorli oil is one

of those vhiich contain the highest proportion of this acid. Moreover,

it is very easy to obtain pure, because it is not mixed with its

homologue, hydnocarpic acid, In order to prepare it, it suffices to

crystalline the mixture of total fatty acids, once or twice from

alcohol. To purify it, it is distilled under reduced pressure either

directly or in the form of ethyl chaulroograte. we obtained a rather

large quantity of very pure chaulmoogric acid which we used to prepare

synthetically the trichaulmnoogrine which had never yet been described.

Gorlic Acid.

Most of the authors v4iho have studied the oils of the chaulmoogric

group have pointed out the existence In these oils of liquid acids having

a high iodine number. These acids, vtich are not very abundant, are still







not very well known. Power and CGorall thought thev belong to the

series of unsaturated acids with normal chan iJa CHjN-4O0. Tilii

opinion has been generally adopted bj the chemist, who afterwards

studied the oils of this group. We succeeded in extracting from

gorli oil, a liquid acid whose chemical and physical properties do

not place It in the linear series, but in the cvlic compounds of the

family of chaulmoogric and hydnooarpic aids, Its high iodine

number indicates that it has a higher ethylene bond, than its solid

congeners. Like them it has a high dextro rotator power (+504), a

property which clearly differeatiates it from the 1roup of the

ordinary polyethylene acids, with which it had been confused. Jiuce

we dealt with a new substa-Lce, we called it Gorlic Acid. Its formula

ought to be 017H29COOH. The major portion of the gorlia acid is to

be found in the liquid glycerides of gorli oil. These gorli oils,

being saponified hot by alcoholic NaOH, we extracted the fatty acids

of the soaps with mineral aoid followed by several shakiner, out with

ether, We then esterified them by mc s of ethyl alcohol in the

presence of a =all quantity of HG."a and subjected the esters to a

series of fractional distillations. 1Be less volatile portions having

the highest iodine niuwber are riehoet in gorlic acid. It is not

possible to entirely separate by fractional distillation, ethyl aOrlate
*
from ethyl chaulimocgrate, or morlic acid froi. chuImoogric acid, since

th..'y distill at alrrmost the samin temperature. After several fruitless

attempts, we realized that the best method of separation would be to

filter several times at as low a temperature as possible the mixture of

liquid gorlic acid and solid chaulmoofric acid. The derivatives of




S \ 6-


gorlic acid re very difficult to obtain cryJstallie. We prepared

metallic salts such as T, 3ao Ou aad LI acrlates. Only the last is

solid. It has a soapy appearance and could not be obtained Crystalline,

mI. p, 163" into a lump, according to lraquenie.

Among the organic derivatives prepared; a'-iely, gorlamde,

Zorllc diethylamide, 6orlio hydroxan.ic acid, we obtained only a single

crystalline derivatiB,the amide mrr. 950, W'.e then determined the

nitrogen according to Kjeldahl and obtained 4.85 per. cjnt nitrogen.

(Theory for I0g{13IB is 5.05 per Cent.) ';ot iaviag bear. able to

obtain a sufficient quantity of those cr;stalli-a derivatives to

oi'a'ble us to uurif the gorlic acid, oa.iai- to a lack of crude aatrlal,

ae had to confine our-alvae to a stud,' of the product, which in its

appearance and characteri-itics, seemed to us to be purest. Garlic

acid is a colorless liquid turning slightly yellow in contact with

air. It has a peculiar odor aili burninE, acrid, taste.

Denaitj 180 0.9364
Index of refraction
at 1ie 1,4793
Rotation +50* 184
Saturation number 199 5
Iodine number (Hanuj) 169*6
Theoretical saturation number for C18H.90 i0 201 and theory for

iodine number is 181.4.

Conclusions.

Gorli oil i# the only chaulmoogric qwgwh.ich has thus far been

produced by the plants of the African flora. It constitutes at the

present time the best source of ohaulinoogric acid. It contains 75-80

per cent of its weight of this acid. In addition it contains palmitic

acid (10 per cent) and garlic acid (10-12 per cent ),possessing a high

rotatory power and iodine number. This new principle offers special






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ohamlmg^grio and hydinooarpil *oA4u.

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