A study of the alkaloids of Glaucium fimbrilligerum

A STUDY OF THE ALKALOIDS OF G l a u c i u m f i m b r i l l i g e r u m A. Kh. Y u n u s o v and I . A. I s r a i l o v UDC 547.943 Continuing a study of the alkaloid composition of G. fimbrilligerum [1] from different growth sites, we have investigated the plant collected on July 13, 1971, in the flowering period, in the environs of the village of Yurkun' (Pamir-Alai). Chloroform extraction gave 0.39% of combined alkaloids, and by separating these with respect to their solubility in organic solvents, by the preparation of salts, and by column chromatography on alumina, we isolated sanguinarine, ehelenythrine, protopine, allocryptopine, isoeorydine, corydine, isoboldine, and bases with mp 132-133°C and 200-201°C. The base with mp 132°-133°C (frommethanol) has the composition CI8H21NO3, [Oi]D--62.3° (c 0.78; chloroform) Rf 0.3 [benzene-chloroform-methanol (5 : 2 : 2) system]. The base is sparingly soluble in ether and benzene and readily soluble in alkalis. The IR spectrum shows absorption bands at 1510 and 1600 cm-I (aromatic ring) and a broad band at 32003600 cm-I (hydroxygroup). UV spectrum, k max 228, 288 nm (log e 4.14, 3.73). The mass spectrum of the base lacks the peak of the molecular ion, and the maximum ion is one with m/e 192, which is characteristic for the benzylisoquinoline alkaloids [2]. The NMR spectrum of the base taken in trifluoroacetie acid shows a three-proton doublet due to an N-CH3 group at 2.64 ppm (J=4 Hz), a three-proton singlet (OCH3) at 3.51 ppm, two one-proton singlets at 6.11 and 6.42 ppm from two para aromatic protons, and a four-proton quadruplet at 6.55 and 6.72 ppm (J= 8 Hz) from two equivalent pairs of ortho aromatic protons. Methylation of the base with diazomethane gave the O,O- dim ethyl ether with mp 59-60°C the methiodide of which, with mp 132-133 °C (from methanol), was identical with an authentic sample of the methiodide ofO-methylarmepavine [3]. The facts given above indicate that the base with mp 132-133°C is N-methylcoclaurine [4], first isolated from plants of the genus Glaucium. From the combined nonphenolic alkaloids of G_.:fimbrHligerum collected in the village of Daraut-Kurgan (Pamir-Alai) [I] we have additionally obtained a base with the composition C20HIgNOs, mp 213-2140C (chloroform-methanol), ion]D±0°. UV spectrum: ~'max 238, 290 nm (log e 4.13, 4.01). The IR spectrum has absorption bands at 935 and 1040 em-I (methylenedioxygroup, 1500 cm-I (aromatic ring), and 33503600 em-I (hydroxy group). The NMR spectrum shows signals in the form of a three-proton singlet at 2.20 ppm from an N-CH3 group, a four-proton signal at 5.95 and 5.99 ppm from two methylenedioxy groups, and signals from four aromatic protons at 6.66 and 6.70 ppm. The mass spectrum of the base shows the peak of the molecular ion with m / e 353 and those of ions with m/e 352, 335, 322, 304, and 294. The spectral features given are characteristic for alkaloids of the chelidonine type. Acetylationof the base with acetic acid gave the O-acetyl derivative. The NMR spectra of the base and its O-acetyl derivative were identical with those of chelidonine and its acetate [5]. Thus, the base that we have isolated is dl-chelidonine. LITERATURE 1. 2. 3. 4. 5. CITED A. Kh. Yur~sov, I. A. Israilov, and M. S. Yunusov, Khim. Prirodn. Soedin., 681 (1973). M. Ohashi, J. M. Wilson, H. Budzikiewicz, M. Shamma, W. A. Slusarchyk, and C. Djerassi, J. Amer. Chem. Soc., 18, 2807 (1963). S. Yu. Yunusov, R. A. Konovalova, and A. P. Orekhov, Zh. Obshch. Khim., 10, 641 (1940). R. R. Arndt, J. Chem. Soc., 2547 (1963). C-Y. Chen and D. B. MacLean, Can. J. Chem., ~ 3001 (1967). Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Trahslated from Khimiya Prirodnykh Soedinenii, No. 4, p. 538, July-August, 1974. Original a r t i c l e submitted F e b r u a r y 19, 1974. ©19 76 Plenum Publishing Corporation, 22 7 West 17th Street, New York, N. Y. 10011. No part o f this publication may be reproduced, stored in a retrieval system, or .tranxmitted, 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 front the pub#sher for $15.00. 555  (...truncated)