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Investigation of the potential energy surface for the first step in the alkaline hydrolysis of methyl acetate
Author(s) -
Sherer Edward C.,
Turner Gordon M.,
Shields George C.
Publication year - 1995
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560560709
Subject(s) - chemistry , methyl acetate , ab initio , solvation , transition state , hydrolysis , potential energy surface , computational chemistry , alkaline hydrolysis , conformational isomerism , tetrahedron , crystallography , molecule , organic chemistry , catalysis
The potential energy surface for the first step of the alkaline hydrolysis of methyl acetate was explored by a variety of methods. The conformational search routine within SPARTAN was used to determine the lowest energy AM 1 and PM 3 structures for the anionic tetrahedral intermediate. Ab initio single point and geometry optimization calculations were performed to determine the lowest energy conformer, and the linear synchronous transition ( LST ) method was used to provide an initial structure for transition state optimization. Transition states were obtained at the AM 1, PM 3, 3‐21G, and 3‐21 + G levels of theory. These transition states were compared with the anionic tetrahedral intermediates to examine the assumption that the intermediate is a good model for the transition state. In addition, the Cramer/Truhlar SM 3 solvation model was used at the semiempirical level to compare gas phase and aqueous alkaline hydrolysis of methyl acetate. © 1995 John Wiley & Sons, Inc.