Reductive dimerization of benzothiazolium salts

Abstract

Three different types of reaction products were obtained from the reduction of 2-substituted 3-methylbenzothiazolium salts using Na : Hg (1 wt%). Depending on the 2-substituents, two types of dimeric compounds were obtained: the 2-cyclohexyl-, 2-phenyl-, and 2-(p-tolyl)-substituted species are reduced to the corresponding 2,2′-bibenzo[d]thiazoles, while their 2-((p-OMe)C₆H₄)- and 2-((p-NMe₂)C₆H₄)-substituted derivatives afford cis-[1,4]benzothiazino[3,2-b][1,4]benzothiazines. Furthermore, in the presence of molecular O₂, new disulfide derivatives were obtained from the bibenzo[d]thiazoles. The products were obtained in a moderate to good yield, and the structures were confirmed using single-crystal X-ray diffraction. The electrochemistry and further reactivity towards different oxidants of the dimeric compounds were studied; the 2,2′-bibenzo[d]thiazoles show oxidation potentials similar to that of ferrocene and are converted back to the corresponding benzothiazolium cations by mild oxidants such as TCNQ. In contrast, the benzothiazino-benzothiazines show no oxidations in the solvent window of THF.