溶剂分子对甲酰胺及其衍生物分子内氢转移催化作用的研究  

Ab initio Study of the Catalytic Effect of Solvent Molecule in Intramolecular Hydrogen Transfer in Formamide and Its Derivatives

作　　者：金艳玲[1] 牟晓兰[2] 张柏林[2] 王秀岩[2] 

机构地区：[1]辽宁师范大学化学系,大连116029 [2]中国科学院大连化学物理研究所分子反应动力学国家重点实验室,大连116023

出　　处：《Chinese Journal of Chemical Physics》2003年第6期445-454,共10页化学物理学报（英文）

基　　金：ProjectsupportedbyNKBRSFandNSCF(2 0 0 730 4 4 )

摘　　要：在B3LYP/ 6 311++G 水平下 ,通过计算所形成二元团簇的能量来研究水、氨、甲醇、氟化氢等溶剂分子对甲酰胺及其衍生物分子内氢原子转移的催化作用 .简单描绘了在有水、氨、甲醇和氟化氢等溶剂分子存在时 ,甲酰胺及其衍生物分子内氢原子转移的过程 .结果表明 ,当有水、氨、甲醇、氟化氢等溶剂分子存在时 ,从甲酰胺 甲酰胺酸转变的能垒会降低 .而且不同的溶剂分子对甲酰胺 (FA)、N 甲基甲酰胺 (MF)和N ,N 二甲基甲酰胺(DMF)的催化能力各不相同 .在这四种溶剂分子中 。The intramolecular hydrogen transfer of formamide and its derivatives in the presence of water, ammonia, methanol and hydrogen fluoride was studied by the hybrid functional method (B3LYP) in conjunction with 6-311++G** basis set, and the progress of proton transfer in the presence of water, ammonia, methanol and hydrogen fluoride was focused. The energy barriers for formamide<---->formamidic acid isomerization were reduced when it was catalyzed with a solvent molecules (water, ammonia, methanol or hydrogen fluoride). The catalytic effect of different solvent molecules to formamide, N-methyl formamide and N,N-methyl formamide was different. Among the four molecules, the catalytic effect of hydrogen fluoride was most effective.

关 键 词：甲酰胺 甲酰胺衍生物 催化作用 氢转移 溶剂分子 

分 类 号：O643.3[理学—物理化学]