A new azoqlkyl isothiouronium salt and hydrolysis of its complexes

Abstract

The multidentate ligand, (1,11bis(isothiouroniumchloride)-1,11-diphenyl-1,11azoethane) 34 has been synthesized and its reaction with metal ions studied. The synthetic route (Scheme III) of the ligand involved the conversion of acetophenone into acetophenone ketazine. The 1, 4 addition of chlorine to ketazine 28 at - 78°C gave 1,11-dichloro-1,11-diphenyl-1,11-azoethane (dichloazoalkane) 29. Nucleophilic displacement of chloride by thiourea in acetonitrile at room temperature afforded the bis(isothiouronium) salt 34 which was characterized by IR., MS. and NMR spectroscopy and elemental analysis. Hydrolysis of isothiouronium salt with NiC12 under basic conditions afforded incompletely characterized derivatives 37 and 38. IR Spectroscopy analysis showed that the ligand had been completely hydrolyzed to form a dimercaptide 36. The method used in the preparation of the ligand is operationally simple. Furthermore, it makes use of mild conditions, which are compatible with many common, functional groups. The salient features warrant its broad utility in organic synthesis.