甲醇羰基化氨解制甲酸反应机理的量子化学研究.docVIP

PAGE PAGE 18 甲醇羰基化氨解制甲酸反应机理的量子化学研究 摘要本文通过b3lyp/6-311+g(d,p)水平分别对甲醇羰基化氨解合成甲酸和甲醇羰基化水解合成甲酸的反应进行计算。甲醇羰基化氨解合成甲酸包括甲醇与一氧化碳羰基化氨解合成甲酸甲酯，甲酸甲酯氨解生成甲酰胺以及甲酰胺碱性条件下水解三个反应；甲醇羰基化水解合成甲酸包括甲醇与一氧化碳羰基化氨解合成甲酸甲酯和甲酸甲酯水解两个反应。本文通过对以上反应路径推断，反应物、过渡态、产物和中间体的优化及能量分析，渡态虚频的唯一性，找到了相应的唯一过渡态，并找到了制约合成路径的关键反应步骤。通过计算发现甲醇羰基化氨解整个反应过程中，CH3OH+CO生成TS1所需的活化能最高，因此甲醇与一氧化碳的羰基化反应是整个合成路线的关键反应步骤。经过两种制取甲酸路径的对比，甲醇羰基化水解制取甲酸相对来说所需酸碱环境和加热温度等条件相对容易一些，并且在原子利用率上更符合经济性绿色化学。 关键词羰基化氨解水解过渡态 IRC Quantum Chenical Stuy Methanol Carbonylation Amino Acid Solution Preparation Reaction Mechanism Abstract There we have talked about two ways for utilizing methanol carbonylation to synthesize formic acid, one was ammonia solution and another was hydrolysis. Both of them were based on b3lyp/6-311+g(d,p) carbonylation of methyl solution of ammonia includes three reactions: methanol with carbon monside under carbonylation synthesis of methyl formate, then by the solution of ammonia methyl formate to synthesize formamide and hydrolysis formamide under the alkaline condition, carbonylation of methanol synthesis of formic acid by hydrolyzing incould methanol with carbon monoxide carbonylation and ammonia synthesis of methyl formate and methyl formate hydrolysis. This article based on the above reaction pathway infer something which include reactants, transition state, intermediate products and intermediates’ optimization and energy analysis, then find the corresponding uniqueness transition states, and find a path to restrict the synthesis of key reaction step through the transition state of imaginary frequency. Throughout the reaction we found the carbonylation of methanol ammonia solution by calculating, the step of CH3OH + CO →TS1 requires the highest activation energy. Therefore, the carbonylation reaction of methanol with carbon monoxide reaction is a key step of the synthesis route. Contrast the two kinds of preparation formic acid, carbonylation of methanol hydrolysis to prepare formic acid requires pH environment and temperature con