Carboxyl Group Participation in Sulfate and Sulfamate Group Transfer Reactions

Article abstract of DOI:10.1021/jo00348a030

The pH dependence for the hydrolysis of N-(2-carboxyphenyl)sulfamic acid exhibits a plateau region corresponding to participation of the carboxyl function.A normal deuterium oxide solvent isotope effect indicates that proton transfer from the carboxylic acid is concerted with sulfamate group transfer to water.Hydrolysis of salicyl sulfate and N-(2-carboxyphenyl)sulfamate in ¹⁸O-enriched water yields salicylic acid and anthranilic acid acids with no enrichment, excluding catalysis by neighboring nucleophilic attack on sulfur by the carboxylate group.Intermolecular catalysis by carboxylic acids is demonstrated in the hydrolysis of N-(1-naphthyl)sulfamic acid; the mechanism is shown to involve preequilibrium protonation of the nitrogen followed by nucleophilic attack on sulfur by the carboxylate anion.Fast decomposition of the acyl sulfate completes the hydrolysis; this mechanism is considered to be the most efficient but is excluded in the intramolecular case which is constrained by the electronic requirements of displacement at the sulfur atom (6-ENDO-tet).