SOLVOLYSIS OF ALKYL CHLOROSULFATES: PART I. REACTION OF n-PROPYL CHLOROSULFATE WITH NUCLEOPHILES

Abstract

The effect of various reagents on the rate of hydrolysis of n-propyl chlorosulfate in 10 M aqueous dioxane is reported. Halide ions increase the rate of reaction (I− > Br− > Cl−) but perchlorate is without effect. Hydroxide and pyrrolidine have a strong accelerating effect, but only at higher concentrations. These observations support a bimolecular mechanism: rate-determining displacement by nucleophile on carbon, with OSO2Cl− as the leaving group. The present results are not in accord with a previous proposal that alkyl chlorosulfates react by rate-determining sulfur–chlorine bond fission followed by fast displacement by nucleophile on carbon.