2-(4-甲氧基苯基)亚肼基乙酸与乙醛酸反应密度泛函理论研究(英文)  

A density functional theoretical study of the reaction between 2-(4-methoxyphenyl) hydrazono acetic acid and oxoacetic acid

作　　者：刘旭圆[1] 徐为人[2] 王润玲[1] 陈正隆[3] 胡骁[1] 程先超[1] 汤立达[2] 

机构地区：[1]天津医科大学药学院,天津300070 [2]天津药物研究院分子设计和药物发现重点实验室 [3]台湾国立中山大学化学院,台湾高雄80424

出　　处：《计算机与应用化学》2011年第3期257-260,共4页Computers and Applied Chemistry

基　　金：Supported by the National Natural Science Foundation of China (Grant No. 20972112);the Key Project Foundation of the Science and Technoloev Ministry of People's Republic of China (Grant No. 2007BAI41B01)~~

摘　　要：本文应用量子化学密度泛函理论（DFT）研究了2-（4-甲氧基苯基）亚肼基乙酸与乙醛酸的反应机理及动力学行为，并研究了不同取代基对反应的影响。在RB3LYP／6—31G＊水平上，优化了各反应通道的反应物、中间体、过渡态及产物的几何构型，计算了各驻点的振动频率、零点能和电荷分布。计算结果表明，该反应有2条反应通道，分别生成（2z）和（2E）－3-（4．甲氧基苯基二氮烯基）丙烯酸。产物发生了键长的平均化和电荷的重新分布。两反应通道具有相同的反应入口，Z式产物为主要产物，2－（4－甲氧基苯基）亚肼基乙酸中苯环对位被给电子基团取代，有利于反应进行。The reaction mechanism and kinetic behavior of 2-（4-methoxyphenyl） hydrazono acetic acid with oxoacetic acid, and the electronic effect of different substituents on phenylhydrazono acetic acid to the reaction rate were investigated in this paper using the density functional theory （DFT）. At RB3LYP/6-31G＊ level, the geometry structures of reactants, intermediates, transition states and products of every pathway were optimized, and the vibration frequencies, zero point energy and charge of each stagnation were calculated. The results suggested that this reaction had two pathways which formed （2Z） and （2E）-3-（4-mehoxyphenylazo） acrylic acid respectively. Both the two pathways had the same entrance and the Z-form product was the main one. The reaction would process more easilv when the nhenvlhvdrazono acetic acid was substituted bv electron-donating groups.

关 键 词：2-(4-甲氧基苯基)亚肼基乙酸 乙醛酸 密度泛函 反应机理 

分 类 号：Q71[生物学—分子生物学] TQ015.9[化学工程]