5-取代1，2，3-三唑互变异构反应机理的理论研究
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摘要
本文采用Gaussian98W程序包中的密度泛函B3LYP/6-311++G**方法对气相和水相中的1,2,3-三唑及5-卤(-F、-Cl和-Br)代1,2,3-三唑;5-(-CHO、-CFO、-CHS和-CFS)取代1,2,3-三唑;5-(-OH和-SH)取代1,2,3-三唑和5-COOH取代1,2,3-三唑,共计四个系列的互变异构体进行了几何构型全自由度优化,获得了它们在气相和水相中的几何构型和电荷分布,讨论了取代基团的不同和溶剂化效应对互变异构体的几何构型、能量和电荷分布以及互变异构反应活化能的影响等;并进一步研究了N1-H、N2-H和N3-H型三唑之间的互变异构机理:(a)分子内质子迁移;(b)水助质子迁移。计算结果显示:b途径所需的活化能较低,大约仅为a途径的一半。
Molecular structures of 1,2,3-triazoles and C5-(-F,-Cl,-Br;-CHO,-CFO,-CHS, -CFS; -OH,-SH; -COOH) substitued-triazole tautomers were calculated by the B3- LYP method at the 6-311++G** level both in the gaseous and aqueous phases with full geometry optimization. The geometrical and electronic structure of the tautomers of 1,2,3-triazoles and C5-substitued-triazole and their transition states were obtained. The influence of the different substituents and solvent effect on the geometrical structure,energy,charge and activated energy were discussed. The reaction mechanism of tautomers of 1,2,3-triazoles and C5-substitued-triazole were also studied. There are two reaction pathways: (a) intermolecular proton transfer; (b) water-assisted intermolecular transfer. The calculated results showed that process (b) has lower activation energies than (a).
Molecular structures of 1,2,3-triazoles and C5-(-F,-Cl,-Br;-CHO,-CFO,-CHS, -CFS; -OH,-SH; -COOH) substitued-triazole tautomers were calculated by the B3- LYP method at the 6-311++G** level both in the gaseous and aqueous phases with full geometry optimization. The geometrical and electronic structure of the tautomers of 1,2,3-triazoles and C5-substitued-triazole and their transition states were obtained. The influence of the different substituents and solvent effect on the geometrical structure,energy,charge and activated energy were discussed. The reaction mechanism of tautomers of 1,2,3-triazoles and C5-substitued-triazole were also studied. There are two reaction pathways: (a) intermolecular proton transfer; (b) water-assisted intermolecular transfer. The calculated results showed that process (b) has lower activation energies than (a).
引文
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