Indirect electrolysis of various nitrobenzenes ortho-substituted by ester (OCOR), carbonate (OCO2R), amide (NHCOR) or carbamate (NHCO2R) group in dichloromethane is performed with a titanium complex (C5H5)(2)Ti+ in 1N aqueous sulphuric acid. Nitro compounds are selectively reduced to amino derivatives. Rearrangement of anilines ortho-substituted by ester or carbonate group into N-acylated o-aminophenol takes place in situ. 2-Substituted benzimidazoles are prepared from N-acylated o-phenylenediamines by heating in boiling acetic acid.