化学学报 ›› 1959, Vol. 25 ›› Issue (3): 136-145. 上一篇    下一篇

论文

Ⅱ.2-甲基丁酰过氧化物在液相中的热解

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——Ⅱ.THERMAL DECOMPOSITION OF METHYLETHYLACETYL PEROXIDE

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

用四氯化碳及一溴三氯甲烷作溶剂,进行过氧化2-甲基丁酰的热裂反应。在四氯化碳中产生2-氯丁烷、丁酮、2-甲基丁酸(可能以酰氯形式存在)、2-甲基丁酸2-丁酯与六氯乙烷。在一溴三氯甲烷中产生2-溴丁烷、氯仿、2-甲基丁酸、2-甲基丁酸2-丁酯与六氯乙烷。从所得产物2-卥代丁烷可以看出游离基(2-丁)不能保持其立体构型,发生完全的消旋作用。

The thermal docompoeition of optically activo mothylothylacotyl peroxide in carbon t)trachloride gave s-Imtyl chloriMe,2-butanone,methylethylacetic acid ( probably in the form of tlio acid chloride),s-butyl methylethylacetate and hoxachloroethane.Decomposition in bromotricliloromethane gave chloroform,s-butyl bromide,methylethylacetic acid,s-butyl methylethylacetate and hexachloroothane.Carton dioxide and other gaseous products were not collected.The optical inactivity of s-butyl chloride and s-butyl bromide,together with tho results of Pau Ⅰ (preceding paper),supports the general view that a free radical is incapablo of maintaining its stexoo-configuration.Control runs showed that tho s-butyl halides were optically etablo under the experimental coeditions.