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

The electrooxidation of anions of primary nitramine salts RNNO2-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- a nd amperostatic electrolysis. Solutions of alkali metals and terrabutylammo nium salt in anhydrous MeCN were used as supporting electrolytes. Electroly sis can result in the formation of the corresponding diazene oxide, whose y ield depends on the nature of the cation of the supporting electrolyte. In an undivided cell, the yield of diazene oxide increases owing to the regene ration of nitramine anions due to cathodic deprotonation of the nonionized form. The latter is formed by the stabilization of some radical intermediat es by the elimination of hydrogen atoms from the components of the medium.