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

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.

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

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/6-31 G* 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 easily when the phenylhydrazono acetic acid was substituted by electron-donating groups.