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钩吻生物碱 Ⅰ.国产钩吻生物碱再研究和钩吻素子的构造

GELSEMIUM ALKALOIDS Ⅰ. REINVESTIGATION OF THE ALKALOIDS OF KOU-WEN, GELSEM IUM ELEGANS BENTH. AND THE CONSTITUTION OF KOUMINE

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【作者】 刘铸晋陆仁荣朱子清王其灏

【Author】 LIU CHU-TSIN-TSIN (C. T. LIU) AND LOH JEN-YUNG(Institute of Organic Chemistry, Academia Sinica)CHU TSE-TSIN (T. T. CHU) AND WANG CHI-HAO(Chemistry Department, Lanchow University)

【机构】 中国科学院有机化学研究所中国科学院有机化学研究所兰州大学化学系

【摘要】 1.重研究了国产钩吻生物碱,比较和改良这些生物碱的提取方法.除获得前人曾经报告的钩吻素子、钩吻素卯和钩吻素甲以外,还得到了两种新的次要生物碱,钩吻素丁和钩吻素戊,但未得钩吻素丙和钩吻素辰.钩吻素丁熔点232-234°,实验式暂定为C26H30N2O4;钩吻素戊熔点202-204°,实验式暂定为C19H22N2O;从紫外光谱推断,二者都是吲哚类型的生物碱.并修正钩吻素卯的实验式为C20H26N2O4,从紫外及红外光谱初步推测,它可能是一种内盐式的假吲哚类型生物碱. 2.对国产钩吻中的主要生物碱钩吻素子的化学结构作了初步解析.从光谱及化学证据推断,钩吻素子与钩吻素甲具不同的发色系统,前者属于假吲哚型,而后者已知是属于2-氧吲哚型的.虽然这两种生物碱都含环外乙烯基,Nb-甲基及可能具环醚结构,但是其脂环部分的构造按推断亦不相同.

【Abstract】 1. The alkaloid contents of Chinese gelsemium (G. elegans Benth.) have been reinvestigated. Various procedures of isolation of the alkaloids were compared and a more efficient one developed. The present authors isolated besides previously reported koumine,kouminidine and gelsemine two new minor alkaloids:koumicine, m. p. 232-4°and koumidine, m. p.202-4°.However, sempervirine and kounidine were not obtained.Empirical formulae C26H30N2O4 and C19H22N2O are provisionally assigned to koumicine and koumidine, respectively, and spectral evidences indicate that both these alkaloids are of indole type. The unconventional formula of kouminidine, C19H25O4N2, is revised to C20H26N2O4.Preliminary considerations based on UV and IR spectra suggest that kouminidine is possibly an indolenine type alkaloid with a zwitterionic structure.2. The constitution of koumine, the main alkaloid of Kou-Wen, has been preliminarily studied on spectral as well as on chemical ground. It is proposed that, in contrast to gelsemine, koumine probably possesses a pseudoindole ring system. Although gelsemine and koumine both contain an exo-vinyl, an Nb-methyl and most likely a cyclic ether linkage, the structures of the alicyclic parts of these two alkaloids appear also different from each other.

  • 【文献出处】 化学学报 ,Acta Chimica Sinica , 编辑部邮箱 ,1961年01期
  • 【被引频次】16
  • 【下载频次】202
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