化学学报 ›› 1956, Vol. 22 ›› Issue (2): 103-111. 上一篇    下一篇

论文

自由基反應的研究——Grignard試劑與2-溴代-2, 3-二甲基丁烷及與1-氯代-1-甲基環己烷在二鹵化鈷存在時的反應

劉有成   

  1. 蘭州大学化學系
  • 投稿日期:1955-12-30 发布日期:2013-06-04

STUDIES OF FREE RADICAL REACTION. THE REACTION OF GRIGNARD REAGENTS WITH 2-BROMO-2, 3-DIMETHYLBUTANE AND WITH 1-CHLORO-1-METHYLCYCLOHEXANE IN THE PRESENCE OF COBALTOUS HALIDE

LIU YU-CHENC   

  1. Department of Chemistry, Lanchow University
  • Received:1955-12-30 Published:2013-06-04

由2-溴代-2,3-二甲基丁烷与溴化苯基鎂在二溴化鈷存在時所起的反應得到如下產物:2,3-二甲基丁烷(35%),2,3-二甲基丁烯-1(31%)及2,3-二甲基丁烯-2(約2%)。由1-氯代-1-甲基環己烷同溴化甲基鎂或溴化異丙基鎂在二溴化鈷存在時的反應得到甲基環己烷,1-甲基環己烯及次甲基環己烷的混合物。此外,還得到少量的高沸點產物,大概为一雙聚合物。在不飽和的單體中,有相當一部分为次甲基環己烷。用鹼處理2-溴代-2,3-二甲基丁烷所得到的烯烴中合有79%的2,3-二甲基丁烯-2和21%的2,3-二甲基丁烯-1。1-氯代-1-甲基環己烷與鹼起消除作用時則只生成1-甲基環己烯。自由烷基在液相中的歧化作用可能为一雙分子反應,烷基分子中的α-碳原子土所具有的氫原子的數目對於烧烴形成的定向表現一定的影響。

2-Bromo-2, 3-dimethylbutane decomposes when treated with phenylmagnesium bromide and cobaltous bromide to give 2, 3-dimethylbutanc (35%), 2, 3-dimethylbutene-1 (31%) and 2, 3 dimethylbutene-2 (ca. 2%). l-Chloro-l-methylcyclohexane decomposes when treated with methylmagnesium bromide or isopropylmagnesium bromide and cobaltous bromide to give mainly a mixture of methylcyclo-hexane, l-methylcyclohexene and methylenecyclohexane. A small amount of a high-boiling product, probably a dimer, was also obtained. In the unsaturated monomeric fraction considerable amount of methylenecyclohexane was found.