Computational study of the alkaline hydrolysis of acetanilide

被引:12
作者
Cheshmedzhieva, D [1 ]
Ilieva, S [1 ]
Galabov, B [1 ]
机构
[1] Univ Sofia, Dept Chem, 1 James Bourchier Ave, Sofia 1164, Bulgaria
来源
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2004年 / 681卷 / 1-3期
关键词
ab initio calculations; hydrolysis; acetanilide; amides; reaction mechanism;
D O I
10.1016/j.theochem.2004.04.045
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
RHF/6-31 + G(d), B3LYP/6-31 + + G(d,p), and QCISD/6-31 + + G(d,p) quantum mechanical computations were carried out in studying the mechanism of alkaline hydrolysis of acetanilide. The computations showed that in both gas phase and water solution the rate determining stage of the reaction is the nucleophilic addition of the hydroxide ion and formation of a tetrahedral intermediate (TD). The first stage is followed by low energy conformational transformation yielding a structure that is favourable for the next process. The decomposition of the tetrahedral intermediate is shown to be a concerted process involving cleavage of the C-N bond and spontaneous proton transfer. No evidence is found for the formation of a dianion intermediate along the reaction pathway. The theoretical computations reveal that the energy profile of the reaction is quite different in gas phase and in solution. All stationary points in water have higher energy than the reactants. The reaction is exothermic in both gas phase and solution. (C) 2004 Elsevier B.V. All rights reserved.
引用
收藏
页码:105 / 112
页数:8
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