Nitroso group transfer from N-nitrososulfonamides to thiolate ions. Intrinsic reactivity

Abstract

The nitroso group transfer from N-nitrososulfonamides to thiolate ions was studied. Based on the results, the reaction rate is strongly dependent on the nature of the leaving group (alfa -13.0), but virtually independent of the basicity of the thiol (beta aprox. 0.1). This dependence is ascribed to the presence of a nucleophile sesolvation equilibrium that is followed by the arrack of the thiolate ion on the niroso group via a concerted mechanism. The equilibrium constants for the loss of a nitroso group form a nitrosothiol and correlations, the parameters alfa, beta and beta nuclef were obtanided.