Vinerinine — A new oxindole alkaloid from Vinca erecta

VINERININEFROM Vinca A NEW OXINDOLE ALKALOID erecta M . M. K h a l m i r z a e v , a n d S. Y u . Y u n u s o v V. M . Malikov, UDC , 7.944/1 F r o m the phenolic f r a c t i o n of the combined alkaloids of V. e r e c t a collected in the T a s h k e n t oblast in the flowering period [1], by c h r o m a t o g r a p h y on a column filled with alumina and elution with ether, we have isolated a new b a s e which we h a v e valled vinerinine. Vinerinine C22H26N206, tool. wt. 414 (mass s p e c t r o m e t r i c a l l y ) , [o~]~-74 ° (methanol), is r e a d i l y soluble in alkalis, c h l o r o f o r m , and methanol and l e s s r e a d i l y in ether. Its UV s p e c t r u m [~. m a x (ethanol) 224 nm, log £ 4.44)] is c h a r a c t e r i s t i c for oxindole alkaloids. The IR s p e c t r u m shows a b s o r p t i o n bands of a 1,2,3,4t e t r a s u b s t i t u t e d benzene ring (760, 810 cm -1) a C H 3 - C O O - C = C - O grouping, and an a m i d e c a r b o n y l (1720, 1635 cm-1). A b r o a d band at 3100-3500 c m -1 is a p p a r e n t l y due to OH and NH g r o u p s connected by hydrogen bond. In the m a s s s p e c t r u m (takenon an MKh-1303 instrument fitted with a s y s t e m f o r the d i r e c t introduction of the s u b s t a n c e into the ion source) of vinerinine t h e r e is the strong p e a k of the m o l e c u l a r ion with m / e 414 (100%) and p e a k s with m / e 222 (11%), 223 (50%), 224 (22%), 208 (21%), 205 (11%), 180 (14%), 69 (46%). The r e s u l t s of a c o m p a r i s o n of the m a s s s p e c t r a of majdine [2] and vinerinine showed that in t h e m the p e a k s of the alicyclic p a r t of the m o l e c u l e a r e s i m i l a r , and the peaks of the f r a g m e n t s of the oxindole p a r t differ by 14 ainu. In the NMR s p e c t r u m (taken on a J'NM-4H-100/100 MHz i n s t r u m e n t in CDC13, HMDS as internal standard, 5 scale) of the b a s e t h e r e a r e signals f r o m the protons of C H - CH3 (1.34 ppm, doublet, J = 6 Hz; 4.50 ppm, J = 1 0 Hz), Ar--OCH 3 (3.56 ppm, singlet), and COOCH 3 (3.77 ppm, singlet). In the w e a k - f i e l d region t h e r e a r e a o n e - p r o t o n singlet f r o m an olefinic proton (7.47 ppm) and a t w o - p r o t o n quadruplet at 6.50 ppm, J = 8 Hz and 6.70 ppm, J = 8 Hz, c o r r e s p o n d i n g to the ortho protons of an a r o m a t i c ring. T h e f a c t s given and the phenolic p r o p e r t i e s of the b a s e p e r m i t t e d the a s s u m p t i o n that v i n e r i n i n e is a m o n o d e m e t h y l d e r i v a t i v e of majdine and t h e r e a r e two p r o b a b l e "formulas f o r it - (I) or (Ia) ! R=OCH 3 R~= OH lrl 8.=OH R~,OCH3 LITERATURE CITED 1. 2. Sh. Z. Kasymov, P. Kh. Yuldashev, and S. Yu. Yunusov, Khim. Prirodn. Soedin., 260 (1966). M. R. Yagudaev, N. Abdurakhimova, and S. Yu. Yunusov, Khim. Prirodn. Soedin., 197 (1968). O r d e r of the Red B a n n e r of L a b o r Institute of the C h e m i s t r y of Plant Substances of the A c a d e m y of Sciences of the Uzbek SSR. 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. 3, pp. 411-412, M a y - J u n e , 1974. Original a r t i c l e submitted N o v e m b e r 23, 1973. © 19 75 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 by any means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written permission o f the publisher. A copy o f this article is available from the publisher for $15.00. 419  (...truncated)