W. Dixon, F. Hibbert, J. Mills
1997
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0
Influential Citations
8
Citations
Journal
Journal of The Chemical Society-perkin Transactions 1
Abstract
The observed rate coefficients for the reaction of 2-methyl-, 2-phenyl- and 2-(4-nitrophenyl)-4H-3,1-benzoxazines to give the corresponding 2-aminobenzyl esters increase as the pH is lowered and reach a constant plateau value at pH 2–4 depending on the substituent. The plateau region corresponds to complete conversion of the benzoxazine to the protonated benzoxazine (SH+) which is the reactive species. Values of pKSH+ calculated by fitting the appropriate rate expression to the rate–pH profile and the pKSH+ values measured spectrophotometrically before significant reaction to the ester has taken place are in good agreement. For each benzoxazine the observed rate coefficients show a rectilinear dependence on buffer concentration. A mechanism is proposed involving addition of water to the protonated benzoxazine to give a cyclic tetrahedral carbonyl addition intermediate. At low buffer concentrations, buffer catalysed collapse of the intermediate to product is rate-limiting and the reaction is first order in buffer. At high buffer concentrations, collapse of the intermediate to product is rapid and addition of water to the protonated benzoxazine to give the intermediate is rate-limiting.