CuCl催化苯腙和丙炔酸甲酯Michael加成反应的机理研究

摘要

本文采用密度泛函理论(DFT)中的M05方法针对性的研究了以CuCl为催化剂催化苯腙和丙炔酸甲酯发生Michael加成的微观反应机理.采用Gaussian09程序,使用6-31+G*(Cu采用赝势基组LanL2DZ)对化学反应过程中的反应物、中间体、过渡态分子的几何构型进行了优化,同时进行了频率计算,所有过渡态都有唯一虚频,中间体和过渡态分子结构的合理性得到了确认.通过自然键轨道(NBO)理论分析了分子轨道间的相互作用.通过理论计算发现CuCl催化苯腙和丙炔酸甲酯发生Michael加成反应的位点在苯腙的N原子上,反应的速控步骤活化能为34.86 kcal/mol,相关的理论研究结果与实验反应现象相吻合.%Using the density functional theory (DFT) M05 method, we studied the reaction mechanism of the Michael addition reaction of phenylhydrazone and methyl propiolate catalyzed by CuCl. Under the basis set level of 6-31+G* (Cu using the pseudo potential basis set of LanL2DZ), we optimized the configuration of all the reactants, transition states and intermediates of Michael addition reaction with phenylhydrazone and methyl propiolate catalyzed. Meanwhile, we calculated the frequency and found out that all the transient states have the only imaginary frequency; moreover, we confirmed the rationality of intermediates and transient states. We analyzed the interaction among molecular orbits via natural bond orbital (NBO). Theoretical calculations showed that the reaction site of the Michael addition reaction of phenylhydrazone and methyl propiolate catalyzed by CuCl is the N atom of phenylhydrazone. And the results showed that the reaction rate-determining energy is 34.86 kcal/mol. The final result of our theory study agrees with the experimental data.