8-二甲基-7-甲氧基-5-烯-壬腈氧化物环加成反应机理  

The reaction mechanism of intramolecular 8-dimethyl- 7-methoxy-5-ethenyl-nonanenitrile oxide cycloaddition

作　　者：孙成科[1] 林雪飞[1] 

机构地区：[1]曲靖师范学院化学系,云南曲靖655000

出　　处：《分子科学学报》2002年第1期14-18,共5页Journal of Molecular Science

基　　金：云南省教委科学研究基金资助项目 ( 0 0 12 2 4 ) ;曲靖师范学院科研基金资助项目 ( 2 0 0 0 0 9)

摘　　要：用过渡态理论和AM 1方法 ,对 8-二甲基 - 7-甲氧基 - 5 -烯 -壬腈氧化物分子内环加成反应机理进行了研究 .结果表明 ,存在两种产物的平行反应 ,对两个反应的速率常数比值的计算 ,得到反式和顺式的产率比为 90 .5∶9.5 ,与实验产率比值 (≥ 85∶15 )结果接近 .The reaction mechanism of 8-dimethyl-7-methoxy-5-ethenyl-nonanenitrile oxide cycloaddition has been studied with the molecular orbital AM1 method and transition state theory.The result show that the title compound generates the stereoisomers (P a and P s )via transition states TS a and TS s respectively.The stereoselectivity is determined by the ratio of the rate constants of two reactions.The value is 9.5(that is anti/syn=90.5∶9.5),that is in good consistence with experiment (exp.anti/syn≥85∶15).The determining factors of the rate ratio come from the joint contribution of the activation enthalpy and activation entropy.

关 键 词：8-二甲基-7-甲氧基-5-烯-壬腈氧化物 环加成反应 反应机理 过渡态理论 AM1方法 量子化学 

分 类 号：O623.761[理学—有机化学] O621.256.7[理学—化学]