Acta Chimica Sinica ›› 1999, Vol. 57 ›› Issue (9): 974-980.

Original Articles

### 3-羟基-3-甲基-2-丁酮和苯甲酰甲酸甲酯热分解反应的 理论研究

1. 北京师范大学化学系.北京(100875)
• 发布日期:1999-09-15

### Studies on the mechanism of thermodecomposition of 3-hydroxy-3- methyl-2-butanone and methyl benzoylformate and calculations of thermal rate constants

Chen Jiehao;Wang Yan;Feng Wenlin

1. Beijing Normal Univ., Dept of Chem..Beijing(100875)
• Published:1999-09-15

The mechanism and kinetics for the decomposition of 3-hydroxy-3- methyl-2-butanone and methyl benzoylformate have been studied by using the ab initio RHF/6-31G method. The calculated activation barriers of the two reactions are 251.42kJ/mol and 247.94kJ/mol, respectively, which are in reasonable agreement with the experimental data. The calculated results show that the decomposition of two reactions is a concerted process with hydrogen transferring and bond breaking via a five-membered cyclic transition state and a six-membered cyclic transition state, respectively. The thermal rate constants of the two reactions are obtained by calculating microcanonical probability fluxes through transition state, which are fairly accurate, by comparison with the experimental results.

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