Isolation of apohyoscine and of 6-hydroxyatropine from Physochlaina alaica

ISOLATION OF APOHYOSCINE AND OF 6-HYDROXYATROPINE FROM P h y s o c h l a i n a a l a i c a R. T. M i r z a m a t o v , K. L. L u t f u l l i n , V. M. M a l i k o v , and S. Yu. Yunusov UDC 547.944 F r o m the r o o t s of Physochlaina alaica E. Korot. collected in the period of the withering of the epigeal part, in addition to compounds found previously [1], we have isolated two alkaloids. The alkaloid (I), C17H19NO3, has mp 79-80°C (ether), M + 285. Its IR s p e c t r u m shows absorption bands at 705 and 780 cm -1 (monosubstituted benzene ring), 1700 cm -1 (conjugated e s t e r carbonyl group), and 1610 cm-1 ( / c := c ( ) . The UV s p e c t r u m of the alkaloid has a broad band at k 240-262 nm like the s p e c t r a of hyoscyamine [2]. In the NMR s p e c t r u m of (I) (in CDC13, 6 scale, JNM 100/100 MHz, HMDS as internal standard) t h e r e is a singlet at 2.40 ppm (3 H, N - C H 3 ) , two one-proton doublets at 5.65 and 6.15 ppm (C= CH2), a singlet at 7.22 ppm (5 H, monosubstituted benzene ring), a triplet at 4.95 ppm (Call) and a singlet at 3.17 ppm (C6H and CTH). The m o l e c u l a r weight of ~I) determined m a s s - s p e c t r o m e t r i c a l l y differs f r o m that of hyoscine by 18 m / e . The facts given above, and also the absence of a d e p r e s s i o n of the melting point of a m i x t u r e with an authentic sample shows that the base isolated is apohyoscine [3]. The alkaloid (II), Cl~H23NO4, has mp 68-69°C (carbon tetrachloride), [o~]~ 0° (c 1.9; methanol), M+ 305. The IR s p e c t r u m of (II) has absorption bands at 710 and 745 cm -1 (monosubstituted benzene ring), 1730 cm -1 (ester carbonyl group) and 3320-3480 c m -1 (broad) (hydroxy group). The UV s p e c t r u m has a broad band at ~. 250-270 nm s i m i l a r to the s p e c t r a of the tropane alkaloids [2]. The NMR s p e c t r u m (in CF3COOH , 6 scale) has signals at 2.73 ppm (3 H, singlet, N-CH3) , 4.82 ppm (C3H, triplet), 1.45-2.35 ppm (6 H, protons at C2, C4, and C7), 2.65-2.95 ppm (2 H, protons at C 1 and Cf), 4.50 ppm (C6H), 3.50-4.20 ppm ( 5 H , / ~ C H CH2OH,-OH at C6) , and 6.99 ppm (5 H, singlet, monosubstitutpd benzene ring). The m a s s s p e c t r u m of (II) has peaks of ions with m / e 305 (M+), 261, 156, 140, 96, 95, 94, 83, 82, 81, which are c h a r a c t e r i s t i c for alkaloids of the tropane group [4]. T h e r e s u l t s of a c o m p a r i s o n of the spectral c h a r a c t e r i s t i c s of the alkaloid and of 6-hydroxyhyoscyamine, the production of a diacetyl derivative (III) (NMR spectrum: 1.93 ppm, 6 H, singlet, CC14), and also the f o r m a t i o n of t r o p a n e - 3 a , 6 ~ - d i o l and of d , / - t r o p i c acid [5] on its hydrolysis showed that the new base has the s t r u c t u r e of 6-hydroxyatropine. I GHe OH LITERATURE CITED 1. R. T. Mirzamatov, K. L. Lutfullin, V. M. Malikov, and S. Yu. Yurmsov, Khim. P r i r o d n . Soedin., 415 2. A. W. Sangster and K. L. Stuart, Chem. Rev., ~ 1, 69 (1965). W. C. Evans and J. G. Woolley, J. Chem. Soe., 4936 (1965). E. C. Blossey, H. Budzikiewicz, M. Ohachi, G. Fodor, and C. Djerassi, T e t r a h e d r o n , ~ (1964). G. Fodor, J. Toth, and J. Vincze, Helv. Chim. Acta, 37, 907 (1954). (1974) [in this issue]. 3. 4. 5. No. 3, 585 O r d e r of the Red Banner of Labor Institute of the Chemistry of Plant Substances of the Academy of Sciences of the Uzbek SSR, and M. I. Kalinin Andizhan State Medical Institute. 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. 416-417, May-June, 1974. Original a r t i c l e submitted D e c e m b e r 29, 1973. © 1975 PlenumPublishing 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 of the publisher. A copy o f this article is availablefrom the publisher for $15.00. 427  (...truncated)