Evidence of self-protonation on the electrodic reduction mechanism of an anti-Helicobacter pylori metronidazole isostere

The electrochemical reduction mechanism of 1-(2-ammoniumethyl)-2-methyl-5-nitroimidazole bromide (2) in DMSO+ 0.1 mol l1 TBAP has been investigated by cyclic voltammetry and macroscale electrolysis, on a glassy carbon electrode, in comparison with metronidazole (1). The cyclic voltammogram of 2 is represented by three reduction waves, one of them at less negative potential, when compared to the first wave of metronidazole which indicates that it undergoes easier reduction. There is evidence for a self-protonation mechanism in the electroreduction of 2, represented by the absence of the first wave in the successive cyclic voltammogram, by the disappearance of the first reduction wave upon addition of base and increase of the same wave in the presence of exogenous proton donors. The stoichiometry of the reaction, at the first reduction wave, involves 0.8 mol electron mol1 and yields 0.2 mol of 4e/4Hþ reduced derivative (probably an unstable hydroxylamine) and 0.8 mol of the amine derivative, the conjugated base of 2. The second and third waves are typical for nitroaromatic reduction and are related to the reduction of the nitro group in this aminoderivative.