Mechanism and thermodynamics of chlorine transfer among organochlorinating agents. Part III. Autocatalytic pathway between N-chloro-succinimide and chloramine-T

Abstract

Chlorine exchange between the chloroimide and the chlorosulphonamide has been found to be subject to autocatalysis with intermediate formation of dichloramine-T even in the presence of large excess of toluene-p-sulphonamide. The direct exchange appears to be relatively slow below pH 7, essentially all exchange being mediated through formation of the dichloro-compound. pH Profiles for the overall equilibrium and for the various postulated intermediate steps have been determined in both directions. In acidic solutions substantially below pH 4·55, the chloroimide was found to be thermodynamically essentially equivalent to chloramine-T as a chlorinating agent.