Alkaloids ofLeontice darvasica

2. G. P. Sidyakin and S. Yu. Yunusov, DAN UzSSR, no. 4, 39, 1962. 3. I. M. Fakhrutdinova, G. P. Sidyakin, and S. Yu. Yunusov, Uzb. khim. z h . , no. 4, 41, 1963. 4. Z. Sh. Faizutdinova, I. A. Bessonova, and S. Ytr: Yunusov, KhPS [Chemistry of Natural Compounds], 8, 257, 1967. 5. L. Avazmukhamedov and T. T. Shakirov, Uzb. khim. z h . , no. 5, 75, 1967. Institute of the Chemistry of Plant Substances, AS UzSSR 23 September 1968 U D C 547.944/945 ALKALOIDS OF L E O N T I C E DARVASICA S. Iska:ladarov and S. Yu. Yunusov Khimiya Prirodnykh Soedinenii, Vol. 5, No. 2, pp. 132-183, 1969 l~rom the e p i g e a l part of L. darvasica, f a m i l y Berberidaceae, collected in the flowering stage in the western Gissars range we have obtained 1.1°]o of total alkaloids by chloroform extraction. From them we have isolated thaspine [1], and from the mother liquor of the latter in the form of perchlorates N - m e t h y l c y t i s i n e and a new alkaloid darvasine with mp 146" C (ether) i n ] D --188° (c 1; ethanol), having the composition C15HzzNzO. Darvasine forms crystalline mono ~mlts: perchlorate with mp 250 ° C (ethanol), picrate with mp 281 ° C ( d e c o m p . , ethanol), and methiodide with mp 26')° C (acetone). The IR spectrum of the alkaloid has absorption bands characteristic for the carbonyl of a s i x m e m b e r e d l a e t a m and a double bond (1670 w, 1645 c m -t) and the UV absorption spectrum shows that these groups are i I i l conjugated in the form of the - - C = C - - N - - C = O chromophore (kma x 244 rap, log ~ 4.3). A study of the mass spectrum of darvasine (taken on a MKh-1303 mass spectrometer at an energy of the ionizing electrons of 40 V and a temperature of 85" C) has shown that it belongs to the matrine group of alkaloids with one double bond in ring C. The fragments formed by the e l i m i n a t i o n of the methyl and ethyl radicals from rings A and B are analogous to those of matrine and sophocarpine; however, the ions arising as a result of the degradation of ring C differ markedly from those of matrine and sophocarpine [2]. The peaks of the ions in the region of lower mass numbers are displaced by one or two a t o m i c units, as in leontalbine. The spectra of darvasine and leontalbine differ in the intensity of several peaks, which is explained by steric factors. The dehydrogenation of darvasine using p a l l a d i z e d asbestos (26C-270" C, 30 rain) gave hexadehydrodarvasine, i d e n t i c a l with octadehydromatrine [3]. The NMR spectrum of the alkaloid shows, in addition to complex signals of protons of various methylene and m e t h i a e groups, the signal of an isolated olefinic proton present in the a - p o s i t i o n to a heteroatom (r 3.19), which corresponds to a position of the double bond at C5-C17. The IR spectrum of darvasine lacks a trans band [4]. Consequently, the base is the first representative of the matrine alkaloids of the cis series and has the structure of 5, 17-dehydroisomatrine. @--., 1t REFERENCES 1. 2. 3. 4. S. S. E. F. Iskandarov, R. N. Nuriddinov, and S. Yu. Yunsov, KhPS [Chemistry of Natural Compounds], 8, 26, 1967. Iskanderov and S. Yu. Yunusov, KhPS [Chemistry of Natural Compounds], 4, 106, 1968. Ochiai, S. Okuda, and H. Minato, J. Pharm. Japani, 72, 781, 1952. Bholmann, B e t . , 91, 2157, 1958. 30 September 1968 Institute of the Chemistry of Plant Substances, AS UzSSR 115  (...truncated)