Acid-catalyzed decomposition of stable 1-(2,1-benzisothiazol-3-yl)-3-phenyltriazenes

Abstract

Abstract The acid-catalyzed decomposition of unusually stable 1-(2,1-benzisothiazol-3-yl)-3-phenyltriazenes in either aqueous perchloric acid or an aqueous mixture of perchloric and acetic acid was studied under pseudo-first order reaction conditions at 25 °C. Different products were obtained according to substitution on nitrogen N-3. For a triazene carrying hydrogen, the corresponding 3-amino-2,1-benzisothiazole and benzenediazonium salts were formed whereas in the case of substitution by an alkyl group (methyl and n-butyl) the 2,1-benzisothiazole-3-diazonium salt and N-alkylaniline were obtained. The observed rate constant (kobs) of the acid-catalyzed decomposition increased, initially, nonlinearly with increasing concentration of acid. Subsequently, kobs decreased slightly and at high acid concentration, increased steeply once again. An A-SE2 mechanism in which protonation of the triazene nitrogen proceeds simultaneously with cleavage of the N–N bond is proposed. Tautomerism of 1-(2,1-benzisothiazol-3-yl)-3-phenyltriazene was investigated using 1H NMR spectroscopy.