Theoretical Study on the Mechanism of a New Synthesis Reaction of 1,3,5-Substituted-1,2,4-triazoles by Carboxylic Acids,Amidines,and Hydrazines  

作　　者：王志玲 汪智娜 卢秀慧 

机构地区：[1]School of Chemistry and Chemical Engineering,University of Jinan

出　　处：《Chinese Journal of Structural Chemistry》2018年第3期367-374,共8页结构化学（英文）

基　　金：supported by the National Natural Science Foundation of China(No.51102114)

摘　　要：The synthesis of 1,3,5-substituted-1,2,4-triazoles from α-imino-3-pyridine formic acid,acetamidine and anisole hydrazine as a model reaction in this paper and the synthesis mechanism of 1,3,5-substituted-1,2,4-triazole compounds from carboxylic acids,amidines and hydrazines have been first investigated with the B3 LYP/6-311＋＋G＊＊ method.According to the potential energy profile,it can be predicted that the course of the reaction consists of five reactions containing six elementary reactions.The α-imino-3-pyridine formic acid and acetamidine form first an intermediate product through a dehydration reaction; the intermediate product further combines with hydrogen ion to form a positive ion; the positive ion reacts with anisole hydrazine by a dehydration reaction to form another positive ion; then,followed by two isomerization reactions,the final reaction with the acetate ion（Ac-） produces the final product.The research results reveal the laws of synthesis reaction of 1,3,5-substituted-1,2,4-triazoles by the carboxylic acids,amidines,hydrazines and their derivatives on theoretical level.It provides the systemic theoretical basis for the synthesis,development and application of 1,3,5-substituted-1,2,4-triazole compounds.The synthesis of 1,3,5-substituted-1,2,4-triazoles from α-imino-3-pyridine formic acid,acetamidine and anisole hydrazine as a model reaction in this paper and the synthesis mechanism of 1,3,5-substituted-1,2,4-triazole compounds from carboxylic acids,amidines and hydrazines have been first investigated with the B3 LYP/6-311＋＋G＊＊ method.According to the potential energy profile,it can be predicted that the course of the reaction consists of five reactions containing six elementary reactions.The α-imino-3-pyridine formic acid and acetamidine form first an intermediate product through a dehydration reaction; the intermediate product further combines with hydrogen ion to form a positive ion; the positive ion reacts with anisole hydrazine by a dehydration reaction to form another positive ion; then,followed by two isomerization reactions,the final reaction with the acetate ion（Ac-） produces the final product.The research results reveal the laws of synthesis reaction of 1,3,5-substituted-1,2,4-triazoles by the carboxylic acids,amidines,hydrazines and their derivatives on theoretical level.It provides the systemic theoretical basis for the synthesis,development and application of 1,3,5-substituted-1,2,4-triazole compounds.

关 键 词：1 3 5-substituted-1 2 4-triazole synthetic reaction potential energy profile molar gibbs free energy of reaction（△rGm）- 

分 类 号：O626.26[理学—有机化学]