HnC—NHm(n=1,2,3;m=1,2)脂肪胺系列脱氢反应的同系规律

The Homologous Law of the Dehydrogenations of HnC-NHm (n=1,2,3;m=1,2)Fatty Amine Series

本文基于量子化学从头计算结果,采用内禀反应坐标法确定了HnC-NIIm(n=1.2.3;m=1.2)脂肪胺系列脱氢反应的势能剖面和反应途径,讨论了各脱氢反应的反应性指数随反应温度的变化。结果表明,在这些分子的脱氢反应过程中,氢气分子的形成和它从反应物分子上的消除是以协同的非同步反应方式进行的。其中各1.2-脱氢反应途径上都存在一个1.2-H迁移反应过程,而在各1.1脱氢反应途径上都存在分子内旋转过程。反应指数的综合考察表明,这些分子的脱氢反应只能接1.1-脱氢反应方式完成。

The ab initio calculations have been performed with the dehydrogenations of the HnC—NHm(n=1. 2. 3; m=1. 2) fatty amine series. Their reaction pathways and potential energy surfaces have been determined by the Intrinsic Reaction Coordinate (lRC) method. We have discussed the changes of their reactivity exponents with reaction temperature. Our results indicates that the formation of H2 molecule and its elimination from reactant are con- certed but nonsynchronous in each dehydrogenation process. The common characteristic of geometry changes lies in that there is a 1. 2-H shift process occured in each 1. 2-dehydro- genation process and an intra-molecular rotation process occured in each 1, 1-dehydrogena- tion process. The synthetic investigation in the reactivity exponents reveals only the 1. 1- H2 elimination processes to be the possible pathways for dehydrogenations of HnC—NHm(n =1, 2, 3; m=1, 2) fatty amine series.