Aminolysis of 4-Nitrobenzenesulfenyl Chloride

The reactions of 4-nitrobenzenesulfenyl chloride with substituted benzylamines proceed through three pathways, the uncatalyzed (k₂) and catalyzed (k₃) paths including solvolysis (k_o) by the solvent. The large value of primary normal kinetic isotope effects imply that the proton transfer occurs concurrently from benzylamine to Cl atom of the substrate. The β_x and ρ_x values for the catalyzed path, k₃, are greater than those for the uncatalyzed path, indicating that greater degree of bond formation in the catalyzed TS compared to the uncatalyzed TS. Nucleophilic substitution reactions at a dicoordinated sulfur compound take place through a bimolecular mechanism as well as a tricoordinated sulfur compound. These reactions are well known to proceed through a stepwise mechanism with a hypervalent sulfur species(sulfuranide) as an intermediate or through a single step with synchronous bond formation and breaking