烯丙基乙烯基醚锂1,2-迁移机理研究  

STUDY FOR MECHANISM OF 1,2-SHIFT IN LITHIUM ALLYL VINYL ETHER

作　　者：吴志勇[1] 李吉海[1] 

机构地区：[1]山东大学化学与化工学院,济南250100

出　　处：《山东大学学报（理学版）》2002年第3期248-251,共4页Journal of Shandong University(Natural Science)

摘　　要：以从头算方法 (6 31G基组 )研究了烯丙基乙烯基醚锂化物发生乙烯基从氧到碳上的 1,2 迁移的机理 .乙烯基烯丙基醚同锂试剂 (RLi)反应 ,但尚未重排前 ,烯丙基端的C3—O醚键就已断裂 ,而不是锂离子和烯丙基负离子呈离子对形式存在 .过渡态构型类似一个二取代的反式三元环结构 .重排反应的活化能较高 (137.4kJ/mol) ,然而整个反应的放热效应也相当高 (176 .5kJ/mol) ,因而它是一个反应速度相当快的重排反应 .Ab initio HF/6 31G calculations have been performed for the rearrangement mechanism of 1,2 shift in lithium allyl vinyl ether.In this rearrangement the vinyl shifts from O to C.The ether link C 3 O has been broken,in fact,after allyl vinyl ether acted with lithium agent but the rearrangement did not happen.The configuration of transition state is like as a trans disubstituted three cycle.The activation energy of the rearrangement is higher (137.4 kJ/mol).Because of much large exothermic effect of whole reaction,however,it is a fast rearrangement.

关 键 词：烯丙基乙烯基醚 1 2-迁移 机理 过渡态 活化能 从头算 

分 类 号：O641.12[理学—物理化学]