Rates of reaction of benzenesulphonyl chloride with some nucleophiles in aqueous solution

Abstract

The rates and activation parameters for the reaction of some common nucleophiles with benzenesulphonyl chloride in aqueous solution have been determined. With aniline, azide, imidazole, thiosulphate, and fluoride, stable products are obtained. With pyridine, nitrite, and acetate, catalysis of the hydrolysis of benzenesulphonyl chloride occurs. The pyridine and acetate reactions have solvent isotope effects of 1·10 and are probably cases of nucleophilic catalysis. No reaction could be detected with thiocyanate, iodide, and bromide. Comparison with analogous data for reactions at saturated carbon and carbonyl carbon indicate that sulphonyl sulphur occupies a position between the two carbon centres with respect to factors determining nucleophilic reactivity.