SIOC English
化学学报
高级检索

化学学报 ›› 1959, Vol. 25 ›› Issue (3): 129-136,144.    下一篇

论文

游离基的立体化学Ⅰ.2-甲基丁酸的电解

H. J. Dauben. Jr1,2, 梁晓天1,2   

  1. 1. 西雅图华盛顿大学化学系;
    2. 中国医学科学院药物化学系有机化学室
  • 投稿日期:1957-10-21 发布日期:2013-06-03

STEREOCHEMISTRY OF FREE RADICALS——Ⅰ.ELECTROLYSIS OF METHYLETHYLACETIC ACID

H.J. DAUBEN. JR1,2, LIANG XIAO-TIAN1,2   

  1. 1. Chemistry Department, University of Washington, Seattle, Wash., U.S.A.;
    2. Laboratory of Organic Chemistry, Department of Pharmaceutical Chemistry, Chinese Academy of Medical Sciences, Peking
  • Received:1957-10-21 Published:2013-06-03

PDF

568

(1)用有旋光的2-甲基丁酸(RCO2H)在甲醇中进行Kolbe电解,并将该酸与丁二酸单甲酯进行Kolbe混合电解。从各种产物得知游离基(R·)不能保持其立体构型。(2)前人曾提出不同的机理来解释Kolbe电解反应。本文指出“过氧化酰”机理难以成立。

Methanolic Kolbe electrolysis of optically active methylethylacetic acid was carried out,giving,besides gaseous products (not collected),methyl s-butyl ether,3,4-dimethylhexane,s-butyl methylothylacetate and an ester of unknown structure.The s-butyl radical,pr+lucod from methylethylacetate anion ae the result of discharge at the anode and subsequent loss of carbon dioxide,was found to be unable to retain its stereo-configuration; this was reflected in the optical inactivity of the ether,the alkano and the alcohol part of s-butyl methylethylacetate.This was also demonstrated in the mixed Kolbe electrolysis between optically active mothylethylacetic acid and methyl hydrogen euccinate to give optically inactive methyl 4-methylhexanoate.