CAJ | 학술논문

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.
본문응용양자화학밀도범함이론(DFT)연구료2-(4-갑양기분기)아정기을산여을철산적반응궤리급동역학행위,병연구료불동취대기대반응적영향.재RB3LYP/6-31G*수평상,우화료각반응통도적반응물、중간체、과도태급산물적궤하구형,계산료각주점적진동빈솔、영점능화전하분포.계산결과표명,해반응유2조반응통도,분별생성(2Z)화(2E)-3(4-갑양기분기이담희기)병희산.산물발생료건장적평균화화전하적중신분포.량반응통도구유상동적반응입구,Z식산물위주요산물,2-(4-갑양기분기)아정기을산중분배대위피급전자기단취대,유리우반응진행.
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.