论文部分内容阅读
用量子化学从头计算方法在 MP2 / 6-31 G( 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 1 2 3.8,32 .5,1 57.3k J/ mol( X=Cl)和 2 54.3,1 30 .0 ,30 4 .2 k J/ 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 3.4 k J/ 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 .
The C-H bond insertion of CX2 (X = H, F, Cl) with methyl ethyl ether was studied at the MP2 / 6-31 G (d) level by ab initio calculations using quantum chemistry. - H bond (ie, α-C-H bond in methyl group, α-C- H bond and β-C- H bond in ethyl group), the reaction barriers are respectively 1 2 3.8, 32.5, 57.3k There is no potential barrier to the C-H bond insertion between the methylene group and the adjacent oxygen atom, And the ethyl β-C-H bond insertion barrier is only 3.4 kJ / mol. The C-H bond on ethyl α-C in methyl ethyl ether is most favorable for the insertion of CX2, the C- H bond on methyl The ethyl β-C on the second.