Phytoecdysones of Ajuga turkestanica

PHYTOECDYSONES OF Ajuga turkestanica V. Z. Usmanov, M. B . G o r o v i t s , a n d N. K . A b u b a k i r o v UDC 547.926:591.147 The c o m m i n u t e d l e a v e s (2.0 kg) of A. t u r k e s t a n i c a (Rgl.) Briq., family L a b i a t a e collected in July 1970 in the flowering stage (environs of the village of Baisun, S u r k h a n - D a r ' y a oblast) w e r e e x t r a c t e d with 12 l i t e r s of methanol. The methanolic e x t r a c t was concentrated, diluted with water, and t r e a t e d with p e t r o l e u m ether. The r e s i d u a l aqueous methanolic fraction, a f t e r additional r e m o v a l of methanol in vacuum, was c a r e f u l l y e x t r a c t e d with ethyl acetate. The ethyl a c e t a t e extract, b y c h r o m a t o g r a p h y on silica gel with elution by c h l o r o f o r m - m e t h a n o l (9 : 1) yielded substance (I) (0.025% o f the weight of the a i r - d r y r a w m a terial) with R f 0.71 [in a thin fixed l a y e r of s i l i c a gel, c h l o r o f o r m - m e t h a n o l (4 : 1)]. Subsequent elution with c h l o r o f o r m - m e t h a n o l (4 : 1) gave compound (II) (0.020%), with R f 0.50 ( s a m e conditions for c h r o m a tography). Substance (I), C2~H4408 had mp 158-160°C (methanol), [~]~ + 60.0 + 3.0 ° (c 1.00; pyridine) max~C'HsOH245 nm 0g ¢ 4,05); ~max KBr 3450 em -1 (OH), 1752 cm -1 (T-iactone),, 1660 em-~l (eyclohexenone). NMR s p e c t r u m in CsDsN at 100 MHz (~ scale, internal standard HMDS) 0.94 p p m (3H at C-19, singlet), 1.11 ppm (3H at C-18, singlet), 1.24 (6H at C-27 and C-29, doublet, J = 6 Hz), 1.44 (3H at C-21, singlet), 6.15 p p m (1H at C-7). In the m a s s s p e c t r u m of (I) (MKh-1303, 160 ° C, energy of the ionizing e l e c t r o n s 40 eV), in addition to the weak m o l e c u l a r peak with m / e 520, peaks of ions with m / e 502,484, 469, 466, 451, 448,433, 430, 415, 363, 345, 327, 300, 183, 157 w e r e found. T h e s e c h a r a c t e r i s t i c s show that compound (I) is c y a s t e r o n e [1]. Substance (II), C27H4407, was obtained with a double melting point 152-154°C and 235-236°C (from aqueous methanol) and also 242-244°C (from d r y acetone)], [ a ] ~ + 5 4 . 5 - 2.5 ° (c 0.52; methanol); ~max c,.~o~ 243 nm (Âg e 4,09); ~m~x Ksr 337O--345O (OH), 1660 cm - I (cyclohexenone). NMR s p e c t r u m (conditions analogous to those for cyasterone) (ppm): 0.93 (3H at C-19, sfnglet), 1.06 (3H at C-18, singlet), 1.24 (6H at C-26 and C-27, singlet), 1.44 (3H at C-21, singlet), 6.00 (1H at C-7). These facts, and also the m a s s s p e c t r u m of compound (II), containing the p e a k of the m o l e c u l a r ion with m / e 480 and ions with m / e 462, 444, 426, 408, 345, 344, 328, 327, 99 and 81 m a k e it p o s s i b l e to c o n s i d e r that (II) is e c d y s t e r o n e [2, 3]. The identity of (II) as e c d y s t e r o n e was also c o n f i r m e d by a d i r e c t c o m p a r i s o n with an authentic s a m p l e kindly given to us by Ya. K. Yatsyuk [4]. C y a s t e r o n e and ecdysterone have been found p r e v i o u s l y in the l e a v e s of Ajuga decumbens Thunb. ("kiranso") [5 ]. LITERATURE 1, 2. 3. 4. 5. CITED H. Hikino, Y. Hikino, K. Nomoto, and T. Takemoto, T e t r a h e d r o n , 24, 4895 (1968). P. Hocks and R. Wiechert, T e t r a h e d r o n Lett., 2989 (1966). H. H o f f m e i s t e r and H. F. Grtitzmacher, T e t r a h e d r o n Left., 4017 (1966). Ya. K. Yatsyuk and G. M. Segal', Khim. P r i r o d n . Soedin., 6_ 281 (1970). S. Imai, T. Toyosato, M. Sakai, Y. Sato, S. Fiijloka, E. Murata, and M. Goto, C h e m - P h a r m . Bull., 17__, 34O (1969). Institute of the C h e m i s t r y of P l a n t Substances, Academy of Sciences of the Uzbek SSR. T r a n s l a t e d f r o m K h i m i y a P r i r o d n y k h Soedinenii, No. 4, pp. 535-536, July-August, 1971. Original a r t i c l e submitted April 8, 1971. © 1973 Consultants Bureau, a division of Plenum Publishing Corporation, 227 West 17th Street, New York, N. Y. 10011. All rights reserved. This article cannot be reproduced for any purpose whatsoever without permission of the publisher. A copy o[ this article is available [rom the publisher for $15.00. 520  (...truncated)