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Theoretical studies on the alkaline hydrolysis of N ‐Methylcarbamates
Author(s) -
Katagi Toshiyuki
Publication year - 1990
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.540110411
Subject(s) - chemistry , alkaline hydrolysis , alkoxide , hydroxide , nucleophile , hydrolysis , carbamic acid , tetrahedral carbonyl addition compound , ion , medicinal chemistry , isocyanate , elimination reaction , reaction coordinate , computational chemistry , inorganic chemistry , organic chemistry , catalysis , polyurethane
Abstract The reaction mechanisms of the alkaline hydrolysis of N ‐methylcarbamates were studied using the AM1 method by assuming two possible pathways: (1) nucleophilic attack of hydroxide ion on the carbonyl carbon to give a tetrahedral complex followed by its breakdown to carbamic acid (B AC 2); and (2) proton abstraction by hydroxide ion at the nitrogen atom followed by elimination of the alkoxide ion to form N ‐methyl isocyanate (E1cB). Reaction coordinate analysis showed that the reaction mechanism is determined by both the stability of an intermediate and the energy barrier for elimination.