MONO- AND SESQUI-TERPENE HYDROCARBONS OF THE ESSENTIAL OIL OF CANNABIS SATIb’./1

HENK HENDRIKS, THEO M. MALINGR~, SIEB BATTERMAN and REIN Bos Laboratory for Pharmacognosq and Galenical Pharmacy. University of Groningen. The Netherlands

Key Word Index-Cunnuhis sutiw; Cannabinaceae; essential oil; mono- and scsqui-terpcne hydrocarbons: iso- caryophyllene: /3-selinene; selina-3,7( I I)diene. selina-4(14). 7( 1l)diene.

The presence of cannabinoids in the essential oil The terpene hydrocarbon fraction obtained bq of Cannabis sativu L. has been reported pre- means of column chromatography on Si gel elut-

viously Cl]. In this communication the results of ing with light petrol (bp < 40’) was divided into a the investigation into the mono- and sesqui-terpenc mono- and sesqui-terpene hydrocarbon fraction hydrocarbon fraction are presented. together with by vacuum distillation. All the monoterpene previous work (Table I). hydrocarbons previously mentioned [2---S], except

Table I. Mono- and sesqui-terpene hydrocarbons of the essential oil of C’rrr~wh~.s scltiw I... mentioned in previous and present work

Component

cl-Pinene (+ z-thujene) Camphene /j-Pinene Sabinene A’-Carene A’-Carene a-Phellandrene Myrcene r-Terpinene Limoncne B-Phellandrene cis-Ocimene g-Terpinene trans-Ocimene p-Cymene Terpinolene Longifolene isocaryophyllene tmns-r-Bergamotene /j-Caryophyllene [&Humulene p-Farnesene /%Selinene x-Selinene /GBisabolene Curcumene Selina-3.7( 1 I)diene Selina-4( 14),7( 1 I)diene Unidentified Total mono- and sesqui-

terpene hydrocarbons

Nigam Hood c’t a/.[21 Lousberg Stahl and Kundc[4] i’i 0/.[5]

0, * and Salemink[3] /, + 0 * 0 I, 0

1.3 + 34 0. I + 0.7

0.X + 3.3

+ + + 0. I +

1.3 + I.0 0.1 + tract 2.8 + i-0 1.7 +

+ 0.2 1.3 + trace

+ 0.7 0.4 + (1. I

+ 0.6 33.0

5.0 X-O 45.7 23.0 37.5 I60 7.0 I39 5.1 9.8

8.6 7. >

3.2 I.4 I.4

-1. .$

92.6 80.5

~ Not reported; + no quantitative data reported; n.d. not detected. * Percentage of the essential oil. t Percentage of the sesquiterpene hydrocarbon fraction. $ Several sesqui-terpene hydrocarbons unidentified.

Present work ” *

,I

I .50 0.06 I 49 n.d. n.d.

trwz ‘ 0.87 0.97 w7 0.45 0. I 3 0. I 4 trace 0.34 ow 0.10 n.d. I .iO

(

36.S8

9-39 2-47 3.30 l-73 n.d. n.d. 5.20 3.1x

+ 14.0:

+ 53.5

Phytochemical Reports 815

sabinene and A4-carene, were found to be present as shown by GLC co-chromatography with refer- ence compounds. The sesqui-terpene hydrocarbon fraction was divided into several smaller fractions on a AgNOJ column (Si gel containing 20% AgNO,). From these fractions the sesquiterpene hydrocarbons were isolated by preparative GLC. Their identity was established by comparing the IR and NMR spectra with those of pure reference substances. As far as known the presence of iso- caryophyllene, a-selinene, selina-3,7( 1l)diene and of selina-4( 14) 7( 1l)diene has not been reported pre- viously. Further information on the identity of the 20 unknown sesqui-terpene hydrocarbons and the fraction containing the oxygen components in which pulegone and r-bisabolol have been identi- fied for the first time, will be given in a later com- munication.

Phpxhemr.w~, lY75. Vol. 14. pp Xl5 Xl6 Prrgamon Press. Prmtrd m England.

1.

2.

3.

4.

5.

6.

From a chemotaxonomical point of view it is in- teresting to note that many of the components shown in Table 1 were present in the essential oil of Humulus lupulus L [6].

REFERENCES

Malingre. Th.M., Hendriks, H., Batterman, S. and Bos, R. (I 973) Plzarm. Wrekblad 108, 549. Nigam, M. C., Handa, K. L., Nigam, I. C. and Levi, L. (19651 Can. J. Chem. 43. 3372. Lou&erg, R. J. J. Ch. and Salemink, C. A. (1973). Pharm. Weekblad. 108, 1. Stahl, E. and Kunde, R. (1973). Tetrahedron Letters 30, 2841. Hood, L. V. S., Dames, M. E. and Barry, G. T. (1973). Nature 242, 402. Naya, Y. and Kotake. M. (1972). Bull. Chem. Sot. Japan 45, 2887.

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TRITERPENE ACETATES AND D-( + )-PINITOL FROM DRYMARIA DRUMMONDII

XORGE ALEJANDRO DOMI’NGUEZ, JORGE MARR~QUIN and MARCOS GUTIERREZ M.

Departamento de Quimica. lnstituto Tecnolbgico y de Estudios Superiores de Monterrey, Sucursal de Correos J., Monterrey N.L., Mkxico

(Received 30 July 1974)

Key Word Index--Drpwria drumnm~dii; Caryophyllaceae; triterpenes; oleanolic acid acetate r-amyrin acetate; isoursenol acetate; pinitol

Drymaria drummondii (alfombrilla), Voucher specimen. No. 7306 deposited in the Herbarium of Dept de Biologia, ITESM Source: Chihuahua, Mex. Uses Unknown. Previous work-Drymaria drummondii and D. arenarioides., both known in northern Mexico as “alfombrilla”, and D. pachy- phylla from Arizona are annually responsible for serious loss of cattle, particularly in drought years when other forage is not available [l]. Their toxi- city has been well established [2], but no chemical studies have been reported.

Present work-The dried whole plant (5.0 kg) was Soxhlet extracted successively with light petrol

I’,!, 10 IJ 3 Y

and EtOH. Each extract upon concentration yielded an oily residue on which preliminary tests for alkaloids, saponins and flavanoids were run [3]. Only saponins were detected in the EtOH extract.

The residue (62 g) obtained from the light petro- leum extract, was chromatographed on Si gel. Elu- tion with increasing gradients of C6H,-CHC13 gave first 0.6 g of oleanolic acid acetate, mp 266 268”, C32H,004 (M’ at m/e 498). [x], UV, IR,

, NMR, mmp co-TLC; on hydrolysis oleanolic acid was obtained, mp, mmp co-TLC [a] IR. The second component proved to be rx-amyrin acetate