Hydrolysis of aryl N-methyl-N-arenesulfonylcarbamates

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.

DOI: https://doi.org/10.1039/b009146o

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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