Kinetics and mechanism of the reaction of S,S-diphenylsulfilimine with a series of aryl halides

Abstract

The stoichiometry, rate constants and order of reaction have been determined for the reaction of S,S-diphenylsulfilimine with the substrates 1-fluoro-2,4-dinitrobenzene, 1-chloro-2,4-dinitrobenzene, 2-chloro-3-nitropyridine, 2-chloro-5-nitropyridine and 2-chloro-3,5-dinitropyridine. Arrhenius parameters and solvent effects have also been determined for some of these reactions. The results demonstrate that the reaction is a typical nucleophilic aromatic substitution process with no measurable base catalysis. A high reactivity of the sulfilimine reagent is observed and accounted for in terms of the contribution of the ylid form to the overall structure.