化学学报 ›› 1958, Vol. 24 ›› Issue (2): 162-169. 上一篇    下一篇

论文

制备氯霉素的中间体的合成

高怡生, 潘百川, 陆顺兴, 陈志豪, 徐修容   

  1. 中国科学院药物研究所 上海
  • 投稿日期:1957-11-28 发布日期:2013-06-03

SYNTHESIS OF INTERMEDIATES FOR THE PREPARATION OF CHLORAMPHENICOL

KAO YEE-SHENG, PAN PEI-CHUAN, LOH SHEUN-HSING, CHENG CHI-HAO, SHU HSIU-YUNG   

  1. Institute of Materia Medica, Academia Sinica, Shanghai
  • Received:1957-11-28 Published:2013-06-03

1.本文叙述从苯-乙烯酮或对硝基苯乙烯酮开始用甲氧汞化反应合成α-溴-β-甲氧基-苯丙酮或α-溴-β-甲氧基-对硝基苯丙酮。此两种溴化物均与邻苯二甲酰亚胺钾作用生成单及双邻苯二甲酰亚胺衍生物。2.α-邻苯二甲酰亚胺-β-甲氧基-对硝基苯丙酮以异丙醇铝还原获得DL-threo-l-对硝基苯-2-邻苯二甲酰亚胺-3-甲氧基丙醇,其构型的确定系制成其醋酸酯后与已知物比较而证明。3.β-甲氧基-对硝基苯丙酮与溴在醋酸中作用不能取得单溴化合物而获得α,β-双溴对硝基苯丙酮。后者与邻苯二甲酰亚胺钾生成双-邻苯二甲酰衍生物。此化合物以异丙醇铝还原获得1-对硝基苯-2.3-双邻苯二甲酰亚胺丙醇。

The utilization of phenylvinylketone(Ⅷ) or ρ-nitrophenylvinylketone (Ⅵ)[1] as starting material for the preparation of chloramphenicol has been described.By employing the reaction of methoxymercuration[2],both Ⅷ and Ⅵ reacted smoothly with mercury acetate in methanol and followed by successive treatment with potassium bromide and bromine to give α-bromo-β-methoxy propiophenone(ⅩⅣ,b.p.110-120°/1 mm),which had been prepared by Rebstock[3] in impure form from α-bromo-β-methoxypropionyl chloride and benzene through Friedel-Crafts reaction; or α-bromo-β-methoxy-ρ-nitropropio-phenone(Ⅸ,m.p.41-42.5°).