化学学报 ›› 1982, Vol. 40 ›› Issue (8): 730-736. 上一篇    下一篇

论文

脂族酰基过氧化物分解动力学的研究——Ⅱ.过氧化月桂酰在苯中分解产物的鉴定和反应机理

刘有成, 雷学工, 金汝城   

  1. 兰州大学化学系
  • 投稿日期:1981-04-16 发布日期:2013-06-03
  • 通讯作者: 刘有成

STUDIES ON THE KINETICS OF DECOMPOSITION OF ACYL PEROXIDE Ⅱ. DETERMINATION OF THE PRODUCTS AND MECHANISM OF DECOMPOSITION OF LAUROYL PEROXIDE IN BENZENE

LIU YOU-CHENG, LIU YU-CHENG, LEI XUE-GONG, JIN RU-CHENG   

  1. Department of Chemistry, University of Lanzhou
  • Received:1981-04-16 Published:2013-06-03

过氧化月桂酰(1)在苯中50℃分解的主要产物经鉴定为廿二烷、十一烷(烯)、正十二酸十一酯、十二酸及十一烷基苯等.其中廿二烷及酯的生成量不受1的起始浓度的变化及加入的捕获剂galvinoxyl(2)的影响,表明为笼反应产物.十一烷、十二酸及十一烷基苯的生成量随1的起始浓度的变化而有不同程度的变化.加入2后十一烷的量显著减少;十一烷基苯基本消失.有2存在时,1在苯中分解而得到的捕获产物经水解后生成3,5-二叔厂基-4-羟基苯甲醛(3)和2,6-二叔丁基-4-十一烷基苯酚(4).这些结果表明,诱导分解由十一烷基对溶剂分子加成而形成的十一烷基环己二烯自由基所引起,该自由基的偶合和歧化为主要链终止方式.结合动力学实验结果,提出1在苯中分解反应的机理.

The main products from the deoomposition of lauroyl peroxide(1) in benzene at 50℃ have been identified as doeicosane, undecane(undeoene), undeeyl dodecanoate, dodecanoic acid, undeoylbenzene ete. The molar percentage yields of doeicosane and undecyl dodecanoate were not affected by the initial concentration of 1 and. the addition of galvinoxyl(2) as scavenger, indicating that these were cage products. The yields of undevaae, dodecanoio acid and undeoylbenzene all varied to different extent with the change of initial concentration of 1 and, upon the addition of 2, the yield of undecane dropped significantly while undeoylbenzene practically vanished.