1, 2-Dithiolium salts

Abstract

A new method for the synthesis of 1, 2-dithiolium hydrogen sulfates by the oxidation of 1, 2-dithiole-3-thiones with hydrogen peroxide in acetic acid has been developed. From 4-(p-tolyl) 1, 2-dithiolium hydrogen sulfate a series of salts containing anions of inorganic, heteroorganic, and organic acids (Cl⁻, Br⁻, I⁻, ClO ⁻₄ , CNS⁻, VO ⁻₃ , HMoOO ⁻₄ , S₂O ²⁻₃ , S₂O ²⁻₈ , Cr₂O ²⁻₇ , Fe(CN) ³⁻₆ , Fe(CN) ⁴⁻₆ , B(C₆H₅) ⁻₄ , F₃CCOO⁻, C₆H₂(NO₂)₃O⁻) has been obtained. 4-(p-tolyl)-1, 2-dithiolium salts containing the anions NO ⁻₂ , NO ⁻₃ , ClO ⁻₃ , BrO ⁻₃ , SO ²⁻₃ , SO ²⁻₄ , S₂O ²⁻₅ and Cl₃CCOO⁻ dissolve in water and do not precipitate in double decomposition reactions. The reactions of 4-(p-tolyl)-1, 2-dithiolium hydrogen sulfate with sodium sulfite, disulfide, and hydrogen sulfide lead to the formation of bis[4-(p-tolyl)-1, 2-dithiol-3-yl] sulfide and disulfide and the sodium salt of 4-(p-tolyl-1, 2-dithiole-3-thiol, respectively. The reaction of 4-(p-tolyl)-1, 2-dithiolium hydrogen sulfate with solutions of salts of the alkali metals containing the anions of weak acids F⁻, CNO⁻, HCO ⁻₃ , CO ²⁻₃ , B₄O ²⁻₇ , HAsO ²⁻₄ , PO ³⁻₄ , CH₃COO⁻, ClCH₂COO⁻, etc.) forms bis[4-(p-tolyl)-1, 2-dithlol-3-yl] oxide. [8, Table 3].