Alkaloids of Corydalis marschalliana

ALKALOIDS Kh. and OF Corydalis marschalliana G. K i r y a k o v , I. A. Israilov, S. Y u . Y u n u s o v UDC 547.943 We have studied the alkaloids of the plant Corydalis m a r s c h a l l i a n a P e r s . (family P a p a v e r a c e a e ) g r o w ing in Bulgaria, the alkaloid c o m p o s i t i o n of which has not been studied p r e v i o u s l y . The d r y plant {1 kg) was e x t r a c t e d with methanol. The alkaloids w e r e e x t r a c t e d f r o m the e v a p o r a t e d methanolic solution with 2% hyd r o c h l o r i c acid. The acid solution was washed with ether. The solvent was distilled off, giving two substances: (I) - white c r y s t a l s with m p 256-257°C; (II) - yellow c r y s t a l s with m p 238-239°C. The acid solution was m a d e alkaline with 25% a m m o n i a and shaken with ether, and then with a m i x t u r e of benzene and butanol (3:1). Distillation of the solvents g a v e 0 . 5 6 % o f c o m b i n e d e t h e r - s o l u b l e alkaloids and 0.1% of c o m bined b e n z e n e - b u t a n o l - s o l u b l e alkaloids. When the e t h e r - s o l u b l e alkaloids w e r e t r e a t e d with methanol, a b a s e s e p a r a t e d out with rap 220-221°C (ethanol), which w a s identified by a mixed m e l t i n g point, IR s p e c t r o s copy, and T L C as l - a d l u m i d i n e [1]. The methanolic m o t h e r solution f r o m the e t h e r - s o l u b l e alkaloids was c h r o m a t o g r a p h e d on alumina. The f i r s t f r a c t i o n s , eluted with b e n z e n e - e t h y l acetate (95: 5) yielded b a s e s with m p 192-193°C (ethanol) and 194-195°C (ethanol). The l a t t e r was identified as d-bicuculline [1]. Another two alkaloids w e r e isolated f r o m the following f r a c t i o n s . The f i r s t had rap 197-199°C (ethanol), [O~]D+224° (c 0.53; CHC13), mol. wt. 325 ( m a s s s p e c t r o m e t r i c a l l y ) . This b a s e f o r m e d a c r y s t a l l i n e methiodide with m p 242-243°C (decomp.) and a O - m e t h y l ether with mp 132-133°C. T h e i r UV, m a s s , and NMR s p e c t r a w e r e c h a r a c t e r i s t i c f o r aporphine alkaloids. The d i r e c t c o m p a r i s o n of our b a s e with a n a u t h e n tic s a m p l e of d - b u l b o c a r p i n e showed t h e i r identity. The second alkaloid was identified as d - c o r y d i n e [2]. The f r a c t i o n s eluted by a m i x t u r e of benzene and ethyl acetate (9 : 1) g a v e a b a s e with mp 154-155°C, which was identical with an authentic s a m p l e of l - d o m e s t i c i n e [3]. B e n z e n e - e t h y l a c e t a t e (1:1) eluates yielded alkaloids with mp 204-205°C and with m p 122-123°C (methanol), [~]D+48.7 ° (c 1.15; CHC13), which w e r e identified as protopine and d-tsoboldine [4, 5]. A b e n z e n e - m e t h a n o l (9 : 1) f r a c t i o n yielded a b a s e with m p 240-241°C ( c h l o r o f o r m - m e t h a n o l ) , and one with nap 258-260°C. Thus, f r o m Corydalis m a r s c h a U i a n a we have isolated l-adlumidine, d-bicuculline, d-bulbocarpine, d - c o r y d i n e , / - d o m e s t i c i n e , protopine, d-isoboldine, and t h r e e b a s e s unidentified b e c a u s e of their s m a l l amount with mp 192-193°C, 240-241°C, and 258-260°C. LITERATURE 1° 2. 3. 4. 5. CITED M. U. I b r a g i m o v a , M. S. Yunusov, and S. Yu. Yunusov, Khim. P r i r o d n . Soedin., 438 {1970). R. A. Konovalova, S. Yu. Yunusov, and A. P. Orekhov, Zh. Obshch. Khim., 9~ 1939 {1939). M. S h a m m a and W. A. Slusarchyk, Chem. Rev., 64, 659 {1964). I. A. I s r a i l o v , M. S. Yunusov, and S. Yu. Yunusov, Khim. P r i r o d n . Soedin., 194 {1968). Z. F. I s m a i l o v and S. Yu. Yunusov, Khim. P r i r o d n . Soedin., 43 (1966). 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 Academy 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, p. 411, 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 21, 1973. © 1975 Plenum Publishing Corporation, 227 West 17th Street, New York, iV..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 t his article is available from the publisher for $15.00. 418  (...truncated)