The Neutral Hydrolysis of Methyl Acetate. Part 2. Is There a Tetrahedral Intermediate?

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DOIResolve DOI: http://doi.org/10.1139/V09-011
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TypeArticle
Journal titleCanadian Journal of Chemistry
Volume87
Pages544555; # of pages: 12
Subjectcooperative mechanism; one-step mechanism; tetrahedral intermediate
AbstractA computational strategy that reproduces the experimental rates of hydration of formaldehyde, acetaldehyde, acetone, and cyclohexanone and the rates of acetic acid and 2-hydroxypyridine-catalyzed hydration of acetone has been extended to the results of the neutral hydrolysis of methyl acetate reported in Part 1. Calculations have been performed for one-step and two-step mechanisms, with cooperative assistance from one to three additional water molecules in the presence and absence of the acetic acid product. The calculations predict that, for the neutral reaction, a one-step mechanism will be favoured if tetrahedral intermediates have a short lifetime and do not interconvert prior to breakdown (case A), and a two-step mechanism will be operative if tetrahedral intermediates are allowed to interconvert prior to breakdown (case B). The experimental results are consistent with the predictions of case A. In the presence of acetic acid, case A predicts that the acid will contribute only 1.6% to the overall rate, a negligible acceleration over the noncatalytic process, and case B predicts general acid catalysis to be an order of magnitude greater than the experimental result. It is concluded that the neutral hydrolysis of methyl acetate is mainly a cooperative one-step process, and that general acid catalysis by the acetic acid product does not occur.
Publication date
LanguageEnglish
AffiliationNRC Institute for Fuel Cell Innovation; National Research Council Canada
Peer reviewedYes
NPARC number17101703
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Record identifier9bd5bf05-4917-4845-a54e-1db4112b11a2
Record created2011-03-09
Record modified2016-05-09
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