Electrosynthesis of diazene oxides under oxidation of nitramine anions at Pt in MeCN in the presence of nitrosobenzene

Abstract

The electrooxidation of anions of primary nitramine salts RNNO ⁻₂ M⁺ (R=Me, Et, methoxyfurazanyl; M⁺=Bu₄N⁺, Li⁺, Na⁺) at a Pt anode in the presence of nitrosobenzene in divided and undivided cells was studied by potentio-and amperostatic electrolysis. Solutions of alkali metals and tetrabutylammonium salt in anhydrous MeCN were used as supporting electrolytes. Electrolysis can result in the formation of the corresponding diazene oxide, whose yield depends on the nature of the cation of the supporting electrolyte. In an undivided cell, the yield of diazene oxide increases owing to the regeneration of nitramine anions due to cathodic deprotonation of the nonionized form. The latter is formed by the stabilization of some radical intermediates by the elimination of hydrogen atoms from the components of the medium.