化学学报 ›› 1961, Vol. 27 ›› Issue (2): 97-105. 上一篇    下一篇

贝母植物碱研究 ⅩⅢ.西贝素中仲醇羟基及羰基的位置和A,B环的立体化学

刘铸晋1, 陆仁荣1, 何凤珍1, 朱子清2, 黄文魁2   

  1. 1. 中国科学院有机化学研究所;
    2. 兰州大学化学系
  • 投稿日期:1959-07-31 发布日期:2013-06-03

A STUDY OF FRITILLARIA ALKALOIDS XIII.THE CHEMISTRY OF SIPEIMINE (IMPERIALIN)THE LOCATION OF THE SECONDARY HYDROXYL AND THE CARBONYL GROUPS AND THE STEREOCHEMISTRY OF RINGS A AND B

LIU CHU-TSIN1, LOH JEN-YUNG1, HO FUN-ZWUN1, CHU TZE-TSIN2, HWANG WEN-KEUI2   

  1. 1. Institute of Organic Chemistry, Academia Sinica;
    2. Department of Chemistry, Lanchow University
  • Received:1959-07-31 Published:2013-06-03

从旋光数据及脱氧西贝酮的紫外光谱考虑,将西贝素的仲醇羟基定在C-3β-位.为便于解释脱水西贝素异常的化学及光谱性质,认为它具环丙基酮类型的结构,从而西贝素中的羰基应位于C-6.众多的旋光数据对这推断亦无矛盾.对西贝素中叔醇基的位置及其A,B两环的立体化学也有所讨论.西贝素的结构式经推定如(ⅩⅠⅤ)式.

A survey of the molecular rotation data and an examination of the characteristics of the UV absorption spectrum of desoxosipeimone (desoxodihydroimperialon, Ⅱ), coupled with biogenetic considerations, appear to favour the location of the secondary hydroxyl group in sipeimine (imperialin) at C-3.The carbonyl group of sipeimine is tentatively assigned to C-6 in order to account for the unusual chemical and spectral properties of anhydrosipeimine (Ⅹ), which seems to be-have like a cyclopropyl ketone.In the meantime, an extensive study of existing rotation data indicates that position-6 is equally acceptable as position-7 as the site of the carbonyl.The latter position has been favoured by Morgan and Barltrop[11].The location of the tertiary hydroxyl group and the stereochemistry of the rings A and B are discussed.The structure of sipeimine (imperialin) is provisionally presented as (XIV).