钯催化脱磺合成芳基酮的机理研究

发布时间：2018-05-05 06:44

本文选题：密度泛函理论 + 钯催化反应　；参考：《淮北师范大学》2016年硕士论文

【摘要】：C-C键是构成有机化合物的主要骨架,因此开发研究构建C-C键的方法非常重要。过渡金属钯催化或参与的偶联反应被广泛地应用到构建C-C键和C-O键中当中,因此研究钯催化的偶联反应具有重要的意义。本论文中,我们分别采用密度泛函理论(density functional theory,DFT)中的Becke3LYP方法和密度泛函理论(density functional theory,DFT)中的M06方法进行计算。并在同等水平上做了频率计算,用来说明全部的驻点都是中间体(没有虚频)或是过渡态(一个虚频)和它在298.15开尔文时的能量。用IRC方法来阐明所有的驻点都是相互联系的。钯、硫原子采用的是lanl2dz基组,而其它原子都是用的6-31g*基组进行计算的。对以下工作进行了理论计算研究。目的是提供合理的反应机理,解释实验现象和实验结果,同时为相关的实验研究提供理论指导。(1)借助密度泛函理论对苯亚磺酸与苯甲腈在醋酸钯催化下生成二苯甲酮的反应进行了理论研究。研究表明催化剂中的醋酸根直接参与反应,同时说明了添加剂H2SO4在催化反应过程中起了一个促进的作用。(2)借助密度泛函理论对苯亚磺酸和苯甲腈在三氟乙酸钯催化下生成二苯甲酮的反应进行了理论研究,旨在寻找更优的催化剂。结果表明催化剂中的三氟乙酸根直接参与反应,且各步反应的活化能低于采用醋酸钯作催化剂。说明该反应采用三氟乙酸钯效果更好。
[Abstract]:C-C bond is the main skeleton of organic compounds, so it is very important to develop and study the method to construct C-C bond. Transition metal palladium catalyzed or participated in the coupling reactions are widely used in the construction of C-C bond and C-O bond, so it is of great significance to study the palladium catalyzed coupling reaction. In this paper, we use the Becke3LYP method of density functional theory (DFT) and the M06 method of density functional theory (DFT). Frequency calculations are made at the same level to show that all the stationary points are intermediates (no imaginary frequencies) or transition states (a virtual frequency) and its energy at 298.15 Kelvin. The IRC method is used to illustrate that all stationary points are interrelated. The palladium and sulfur atoms are calculated using the lanl2dz basis group, while the other atoms are calculated using the 6-31 g * basis group. The following work is studied theoretically. The aim is to provide a reasonable reaction mechanism and explain the experimental phenomena and results. At the same time, it provides theoretical guidance for related experimental research. (1) the reaction of benzene-sulfonic acid and benzonitrile to benzophenone catalyzed by palladium acetate has been studied theoretically by density functional theory (DFT). The results show that the acetate in the catalyst is directly involved in the reaction. At the same time, the additive H2SO4 played a promoting role in the catalytic reaction. (2) the reaction of benzene-sulfonic acid and benzonitrile to benzophenone catalyzed by palladium trifluoroacetate was studied theoretically by using density functional theory (DFT). The aim is to find a better catalyst. The results show that the trifluoroacetate in the catalyst is directly involved in the reaction, and the activation energy of each reaction is lower than that of palladium acetate as catalyst. The results show that palladium trifluoroacetate is more effective than palladium trifluoroacetate.
【学位授予单位】：淮北师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O625.42

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