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Theoretical studies on the acid hydrolysis of methyl carbamate
Author(s) -
Lee Ikchoon,
Kim Chang Kon,
Lee Byung Choon
Publication year - 1987
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540080607
Subject(s) - chemistry , acetamide , hydrolysis , tautomer , nucleophile , mndo , carbamate , protonation , reaction mechanism , tetrahedral carbonyl addition compound , medicinal chemistry , alkoxy group , computational chemistry , leaving group , acid hydrolysis , organic chemistry , molecule , catalysis , ion , alkyl
The mechanism of the A2 acid hydrolysis of methyl carbamate was investigated using MNDO method. The reaction was found to proceed in two steps: (1) the rate‐determining nucleophilic attack of water on the carbonyl carbon of the N‐protonated tautomer involving the tetrahedral TS; and (2) the fast subsequent proton abstraction by the leaving group, NH 3 , to form products. The mechanism is similar to that involved in the A2 hydrolysis of acetamide. Effects of substituents, R 1 , R 2 , and R 3 in R 1 OCONR 2 R 3 , on rates can be predicted by the changes in electron densities on alkoxy oxygen and N, in complete agreement with the experimental results. We concluded that there is no need for invoking two different mechanisms for amides and carbamates since a common mechanism can easily accommodate all the experimental results.