Araújo, M. Eduarda M.; Campelo, Margarida; Iley, Jim and Norberto, Fatima
(2001).
Hydrolysis of aryl N-methyl-N-arenesulfonylcarbamates.
Journal of the Chemical Society: Perkin Transactions 2
pp. 494–497.
Abstract
Tertiary sulfonylcarbamates 1 were prepared by reaction of a sulfonamide anion with aryl chloroformates. These
previously unreported compounds hydrolyse in aqueous media to the parent sulfonamide and phenol. The pH–rate profile shows both spontaneous and base-catalysed processes. The reaction is also catalysed by buffers. Kinetic data for the hydrolysis of these compounds by HO are best interpreted in terms of a mechanism involving rate-limiting
formation of a tetrahedral intermediate from nucleophilic attack of hydroxide ion at the carbamate carbonyl carbon
atom. For the 4-nitrophenylsulfonyl compound 1h decomposition of the tetrahedral intermediate appears to be
rate-limiting with the sulfonamide anion, rather than the phenoxide, functioning as the leaving group. The buffer catalysed process is consistent with general base-catalysed attack of water at the carbamate carbonyl carbon atom.
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