高等学校化学学报

高等学校化学学报 ›› 2000, Vol. 21 ›› Issue (11): 1708.

• 论文 • 上一篇    下一篇

卡宾与醚C—H键插入反应的理论研究(Ⅲ)CX2(X=H,F,Cl)与甲乙醚C—H键插入反应

冯大诚1, 林启君1, 马万勇2, 王焕杰1   

  1. 1. 山东大学化学学院, 济南 250100;
    2. 山东轻工业学院化工系, 济南 250100
  • 收稿日期:1999-08-02 出版日期:2000-11-24 发布日期:2000-11-24
  • 通讯作者: 冯大诚(1947年出生),男,教授,从事量子化学和分子反应动力学研究.
  • 基金资助:

    教育部博士学科点基金;山东省自然科学基金(批准号:Y98B09028)资助

Theoretical Studies on the C—H Bond Insertion Reaction of Carbenes with Ethers (Ⅲ)——Insertion Reaction of CX2(X=H, F, Cl) with Ethyl Methyl Ether

FENG Da-Cheng1, LIN Qi-Jun1, MA Wan-Yong2, WANG Huan-Jie1   

  1. 1. College of Chemistry, Shandong University, Jinan 250100, China;
    2. Department of Chemical Engineering, Shandong Institute of Light Industry, Jinan 250100, CHina
  • Received:1999-08-02 Online:2000-11-24 Published:2000-11-24

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摘要： 用量子化学从头计算方法在MP2/6-31G(d)水平上研究了CX2(X=H,F,Cl)与甲乙醚的C—H键插入反应.在甲乙醚的3个不同的C—H键(即甲基中α'-C—H键,乙基中α-C—H键和β-C—H键)上,反应势垒分别为123.8,32.5,157.3kJ/mol(X=Cl)和254.3,130.0,304.2kJ/mol(X=F).亚甲基与毗邻氧原子的各C—H键插入反应没有势垒,与乙基中β-C—H键插入势垒仅3.4kJ/mol.甲乙醚中乙基α-C上的C—H键最有利于CX2的插入,甲基上的C—H键次之,乙基β-C上的又次之.

关键词: 甲乙醚, 卡宾, 插入反应, 从头计算

Abstract: The insertion reactions between CX2(X=H, F, Cl) and C—H bonds of ethyl methyl ether have been studied at MP2/6 31G(d) level by using ab initio calculation. The potential barriers for three different C—H bonds(namely α'-C—H bonds in methyl group, α-C—H bonds and β-C—H bonds in ethyl group) are 123.8, 32.5, 157.3 kJ/mol(X=Cl) and 254 3, 130 0, 304 2 kJ/mol(X=F) respectively. No potential barrier is present in the insertion reaction between methylene and C—H bonds adjacent to the oxygen atom and the potential barrier for the insertion between methylene and β-C—H bond in ethyl group is 3.4 kJ/mol. C—H bonds of α-C in ethyl group of ethyl methyl ether are the most favourable to CX2 insertion, C—H bonds in methyl group come next and β-C—H bongs in ethyl group are the most unfavourable.

Key words: Ethyl methyl ether, Carbenes, Insertion reaction, Ab initio

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