螺环[2,3]己烷氢解反应机理的理论研究

在ＨＦ／６－３１Ｇ＊＊水平上（并用ＭＰ２法进行了相关能校正），应用从头算子分子轨道法和能量梯度技术，研究了螺环〔２，３〕己烷氢解反应的机理。结果表明，该反应主要的２个途径为：（１）螺环〔２，３〕己烷氢解经四元环过渡态生成乙基环丁烷；（２）螺环〔２，３〕己烷氢解经四元环过渡生成生成１，１－二甲基环丁烷。计算结果２个途径活化能均过大，表明在催化剂条件下，反应难以进行。

A THEORETICAL STUDY ON THE MECHANISM OF HYDROGENOLYSIS OF SPIRO [2,3] HEXANE

The mechanism of the hydrogenolysis of spiro 2, 3] hexane is studied theoretically by ah initio MO method at the level of MP2/6-31G**. There are mainly two paths for the reaction: (1) The hydrogenolysis of spiro 2, 3] hexane yields ethylcyclobutane via a four-membered ring transition state. (2) The hydrogenolysis of spiro 2, 3] hexane yields 1,1-dimethylcyclobutane via a four-membered ring transition state. The theoretical results show that this reaction can hardly happen without catalyst because of too large activation energy.