化学学报 ›› 1965, Vol. 31 ›› Issue (6): 470-475. 上一篇    下一篇

那可汀一类物的立体化学

黄文魁, 張振杰, 林根寿   

  1. 兰州大学化学系
  • 投稿日期:1964-09-15 发布日期:2013-06-03

STEREOCHEMISTRY OF NARCOTINE AND RELATED ALKALOIDS

HWANG WEN-KUEI, CHANG CHENG-CHIEH, LIN GENG-SHOU   

  1. Department of Chemistry, Lanchow University, Lanchow
  • Received:1964-09-15 Published:2013-06-03

利用那可汀还原产物制备铜络合物的方法测定l-α-那可汀(Ⅰ)(天然)与l-β-那可汀(Ⅱ)(人工制得)的相对构型分别为赤与苏。结合l-α-那可汀(Ⅰ)经一系列化学变化制得1-甲氧基-13-表蛇果碱(Ⅷ)为负旋光性的事实,推论l-α-那可汀(Ⅰ)与l-β-那可汀(Ⅱ)的绝对构型分别为1R:9S与1R:9R。从已知结构关系推知Narcotoline(Ⅺ)的绝对构型为1R:9S,α-(天然)与β-gnoscopine(人工合成)的相对构型分别为赤与苏。

Both natural l-a-narcotise (Ⅰ) and artificial l-β-narcotise(Ⅱ) were reduced by LiAlH4 to the α-diol (Ⅲ),m.p. 132°, [α]D15+51.2° (CHCl3),Al2O3 thin layer chromato-graphy Rf 0.63 (ether),and the β-diol (IV), m.p. 60-61°,[α]D15-59.5° (CHCl3),Al2O3 thin layer chromatography Rf 0.45 (ether),respectively. The latter was contaminated with a small amount of a-diol (Ⅲ),the yield of which was increased to 32% as the reaction time is prolonged to four hours. A copper complex (Ⅴ') could be prepared from the,β-diol (Ⅳ),but not from the a-diol (Ⅲ).From these facts, the relafive configurations of both l-α-narcotise (Ⅰ) and l-β-narcotise (Ⅱ) should be referred to as belonging to the erythro-and threo-series, respectively.