Electrochemical Reduction of Vicinal Dinitro Compounds

Article abstract of DOI:10.1021/jo00257a008

Six vicinal dinitro compounds and 1,1-dinitrocyclohexane have been studied by cyclic voltammetry, chronoamperometry, and controlled potential coulometry.For dinitro compounds 1-3, the electrochemical reduction at mercury electrodes in DMF was shown to proceed by an ECE scheme comprising initial reduction to a radical anion, which exples nitrite, forming a β-nitroalkyl radical that is more easily reduced than the original dinitro compound.The rate constants for expulsion of nitrite from the anion radical were determined at 0 deg C.Compounds 4 and 5 behaved similarly to 1-3 though additional reactions occur.The radical anion of trans-1, 2-dinitrocyclopropane, 6, reacts quickly and could not be detected. 1,1-Dinitrocyclohexane is reduced in an initial two-electron step forming nitrite and the anion of nitrocyclohexane.The later reacts rapidly with starting material to form 1,1'-dinitrobicyclohexyl, 2, which was detected by voltammetry.