Thus, f r o m F. dshizakensis we have isolated two d i a s t e r e o m e r i c e s t e r s : chimgin [4, 5] and a new c o m pound which we hav'-e'called isochimgin which has the s t r u c t u r e of 2 f l - h y d r o x y - l , 7 , 7 - t r i m e t h y l b i c y c l o [ 2 . 2 . 1 ] heptane 4-hydroxybenzoate. LITERATURE 1.

2. 3. 4. 5.

CITED

M. Karplus, J. Chem. Phys., 30._, 11 (1959). T. J. Flautt and W. F. E r m a n n , J. Am. Chem. S.c., 85, (20), 3212 (1963). K. Biemann and J. Seibl., J. Am. Chem. S.c., 8_1.1,3149 (1959). Kh. M. Kamilov and G. K. Nikonov, Khim. Prirodn. Soedin., 718 (1972). V. N. B o r i s . v , A. L Ban'kovskii, V. L Sheichenko, and M. G. Pimenov, Khim. Prirodn. Soedin., 674 (1973).

SESQUITERPENE

LACTONES

FROM

S. V. S e r k e r o v , R . M. A b b a s o v , a n d A N. A l e s k e r o v a

Artemisia

hanseniana UDC 547.314

In the c h r o m a t o g r a p h i c s e p a r a t i o n on a column of alumina of the r e s i n obtained by aqueous e x t r a c t i o n [1] of the h e r b A r t e m i s i a hanseniana v a r . phylostachus collected in D e c e m b e r , 1974, in the Shemakha region of the Azerbaizhan SSR, we have isolated five c r y s t a l l i n e substances belonging to the group of s e s q u i t e r p e n e lactones. The column was eluted with hexane m i x t u r e s of hexane and diethyl e t h e r in r a t i o s of 4 : 1, 4 : 2, 4 : 3, 1 : 1, 1 : 2 , 1 : 3 , and 1 : 4 , diethyl ether, and c h l o r o f o r m . The volume of each f r a c t i o n was 100 ml. F r a c t i o n 4, obtained on elution with hexane, yielded a substance(i); fraction 3, obtained on elution with diethyl e t h e r gave substance (ID; f r a c t i o n 5, eluted with ether, gave substance (]]1); f r a c t i o n 7, also eluted with ether, gave s u b stance (IV); and a second c h r o m a t o g r a p h i c s e p a r a t i o n of the m o t h e r liquor f r o m f r a c t i o n 5 gave compound (V). Substance (I), C15H2003, mp 116-118°C ( f r o m hexane) was isolated in s m a l l amount. Its IR s p e c t r u m has the band of a ~/-lactone ring (1785 c m -1) and of a ketene group in a 6 - m e m b e r e d ring (1717 cm-1). By c o m paring melting points and IR s p e c t r a , (I) was identified as taurin [2-4]. Substance (ID, C15H2204, had mp 231-232.5°C (from ethanol). Its IR s p e c t r u m contained the bands of OH groups (3540 and 3460 cm-1), of a 7-1actone ring (1770 cm-1), and of a double bond (1650 cm-1). It f o r m e d a monoacetate C1yH2405 with mp 219-221°C. Oxidation led to a kete d e r i v a t i v e C15H2004, mp 263-264°C. A c o m p a r i s o n of the compositions melting points, and IR and NMR s p e c t r a of (ID and its d e r i v a t i v e s with the c o r r e s p o n d i n g c h r a c t e r i s t i c s of a r t e m i n and its d e r i v a t i v e s [2-4] showed t h e i r r e s p e c t i v e identities. Substance (liD, C15H2204, had mp 225-226°C, and it has been p r o p o s e d to call it phylostachin [5]. Its IR s p e c t r u m has the bands of OH groups (3460-3300 c m - l ) , of the CO group of a 7-1actone (1775 c m -1) and of a double bond (1650 cm-1). The IR s p e c t r u m of (IID differed f r o m that of a r t e m i n but was n e v e r t h e l e s s s i m i l a r to it. The NMR s p e c t r u m of (IID showed the singlet of an angular methyl group at 0.88 ppm, the doublet of a s e c o n d a r y methyl group with its c e n t e r at 1.23 p p m (J = 6 Hz), and o n e - p r o t o n singlets of an exomethylene group at 4.96 and 5.02 ppm. The signals of a lactone proton and of the protons of a hemihydroxy group w e r e s u p e r p o s e d in the 4.0-4.4 p p m region. The NMR s p e c t r a of (II) and (lID w e r e identical. Such a s p e c t r a l b e h a v i o r is c h a r a c t e r i s t i c f o r a - and fl-santonins [6]. Consequently, (IID differed f r o m (ID only by the o r i e n t a tion of the CH 3 group at Cli. A s e s q u i t e r p e n e lactone differing f r o m a r t e m i n only by the configuration of the Ctl a s y m m e t r i c c e n t e r has been d e s c r i b e d in the l i t e r a t u r e under the n a m e of arsubin [7-9]. Consequently, phylostachin and arsubin a r e one and the s a m e compound. Substance (IV), C15H2004, had mp 176-177°C (from ethanol). Its IR s p e c t r u m had the m a x i m a of an OH group (3500 cm-1), of the CO group of a 7-1actone ring (1700 cm-1), of the CO of a conjugated ketone group V. L. K o m a r o v Institute of Botany, Academy of Sciences of the Azerbaidzhan SSR, Baku. M a r d a r k y a n A r b o r e t u m , Academy of Sciences of the Uzbek SSR, Baku. T r a n s l a t e d f r o m Khimiya P r i r o d n y k h Soedinenii, No. 5, pp. 665-666, S e p t e m b e r - O c t o b e r , 1976. Original a r t i c l e submitted March 1, 1976. This mater~l is protected by copyright registered in the name of Plenum Publishing Corporation, 227 West 17th Street, New York, N.Y. 10011. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or b y any means, electronic, mechanical, photocopying, I microfilming, recording or otherwise, without written permission of the publisher. A copy of this article is available from the publisher for $ 7.50.

599

(1670 cm-1), and of a double bond (1640 era-l). The OH group was t e r t i a r y , since it was not oxidized by c h r o mium trioxide and did not undergo acetylation. A c o m p a r i s o n of the composition, melting point, and IR and NMR s p e c t r a with those f o r t a u r e m i s i n [3, 10] showed t h e i r identity. A mLxture of an authentic sample of t a u r e m i sin and (IV) gave no d e p r e s s i o n of the melting point. Substance (V), C15H2204, had mp 193-194°C. Its IR s p e c t r u m showed the bands of OH groups (3470 and 3450 cm-1), of the CO group of a laetone ring (1753 c m - l ) , and of a 4ouble bond (1647 cm-1). It contained a methylene double bond (singlets at 4.96 and 5.14 ppm of 1 H each), an angular methyl group (singlet 0.76 ppm), and a secondary methyl group (doublet at 1.20 ppm, J = 6 Hz). On acetylation, a diacetate C19H2602 with mp 179-181°C was f o r m e d (giving singlets at 2.0 and 2.08 ppm). The IR s p e c t r u m of (V) differed f r o m that of erevanin [11]. However, t h e i r NM_R s p e c t r a differed, mainly by the nature of the splitting of one of the g e m inal protons of the hydroxy groups. Compound (V) is probably a new s t e r e o i s o m e r of erevanin. The IR s p e c t r a were taken on a UR-20 s p e c t r o p h o t o m e t e r in paraffin oil and the NMR s p e c t r a on a Varian HA-100D s p e c t r o m e t e r in CDC1s. The c h e m i c a l shifts are given in the 5 scale. TMS was used as int e r n a l standard.

LITERATURE i. 2. 3. 4. 5. 6. 7. 8. 9. i0. ii.

CITED

K.S. Rybalko, N. N. Ban'kovskaya, and R. I. Evstratova, Med. Prom. SSSR, No. 3, 13 (1962). N.A. Keehatova, K. S. Rybalko, V. I. Sheichenko, and L. P. Tolstykh, Khim. Prirodn. Soedin., 205 (1968). K.S. Rybalko, A. I. BanVkovskii, and V. I. Sheichenko, in: Medicinal Plants [in Russian], Vol. 15 (1969), p. 168. L.P. Tolstyl~h, V. I. Sheichenko, A. I. Bantkovskii, and K. S. Rybalko, Khim. Prirodn. Soedin., 384 (1968). R.M. Abbasov, AuthorVs Abstract of Candidate's Dissertation, Baku (1975). High-Resolution NMR spectra, Japan Electron Optics Laboratory COLTO. V.A. Tarasov, Sh. Z. Kasimov, and G. P. Sidyakin, Khim. Prirodn. Soedin., 480 (1970). V.A. Tarasov, Sh. Z. Kasimov, and G. P. Sidyakin, Khim. Prirodn. Soedin., 745 (1971). V.A. Tarasov, Sh. Z. Kasimov, and G. P. Sidyakin, Khim. Prirodn. Soedin., 676 (1973). K.S. Rybalko and L. Dolejs, Collect. Czech. Chem. Commun., 26_, 2909 (1961). R.I. Evstratova, V. I. Sheiehenko, A. I. Ban~kovskii, and K. S. Rybalko, Khim. Prirodn. Soedin., 239 (1969

GUAIOL Ferula

AND

HYDROXYAROMATIC

ACIDS

OF

ferulaeoides V. N. B o r i s o v , A. I. B a n ' k o v s k i i , V. I. S h e i c h e n k o , V. S. K a b a n o v , a n d M. G. P i m e n o v

UDC 547.913.5+547.587:633.88

F r o m the lipophilie f r a c t i o n of the r o o t s of F e r u l a ferulaeoides (Steud.) Korov collected in the phase of unripe fruit (Kazakhstan, village of Ueh-Aral, T a l d y - k u r g a n oblast on August 18, 1972) we have isolated a c o m pound with the composition C15H260 (M+ 222), mp 91°C, [ce]2~ - 26.3 ° (c 1.9; MeOH). The substance was identified (on the basis of its constants, composition, and IR spectrum) as a t e r t i a r y sesquiterpene alcohol p r e v i o u s l y isolated f r o m this botanical species and called shairol. According to K i t ~yalov [1], shairol is a bicyclic compound (of the guaiane type) with a t e r t i a r y hydroxy group and a difficultly hydrogenatable double bond [1]. We have continued the study of this substance. Its PMR s p e c t r u m (Varian HA-100 D, CC14, 0 - HMDS) showed the signals of two t e r t i a r y and two q u a t e r n a r y methyl groups at 0.92 (d, 3H, J = 7 Hz), 0.95 (d, 3H, J = 7 Hz), L06 (c, 3H), and 1.1 ppm (s, 3H). All-Union S c i e n t i f i c - R e s e a r c h Institute of Medicinal Plants, Moscow. T r a n s l a t e d f r o m Khimiya P r i r o d nykh Soedinenii, No. 5, pp. 666-667, September-October, 1976. Original article submitted March 1, 1976. This material h protected by copyright registered in the name o f Plenum Publishing Corporation, 227 West 17th Street, New York, N.Y. 10011. No part o f this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocop)Jing, microfilming, recording or otherwise, without written perm~sion o f the publisher. A copy o f this article is available from the publisher for $ Z 50.

600