This work presents the synthesis and spectroscopic caracterization of novel amidino substituited benzimidazoles 17-28, 5-cyano-N-substituited 38-41 and N-substituited 55-58 2-aminobenzimidazoles and benzimidazole derived Schiff's bases of 42-47. Target compounds were prepared by conventional reactions of organic syntheses as well as by microwave assisted reactions. Amidino substituited 1,2-phenylenediamines 10-13 as the main precursors for the synthesis of targeted amidino substituited benzimidazoles 17-28 were prepared starting from 4-amino-3-nitrobenzonitrile 4 by Pinner reaction. Target compounds 17-28 were synthesized by condensation of the prepared precursors 10-13 with the corresponding aromatic aldehydes 14-15 using p-beznoquinone as an oxidant. 5-cyano-N-substituited derivatives 38-41 and N-substituited derivates 55-58 of benzimidazole were prepared in several synthetic steps from 4-chloro-3-nitrobenzonitrile 29 or 2-chloronitrobenzene 48. 4-chloro-3-nitrobenzonitrile 29 and 2-chloronitrobenzene 48 were exposed to non-catalytic amination microwave assisted reaction with an excessive amount of amine. After reduction of nitro derivates, corresponding 2-aminobenzimidazoles were prepared in reaction with BrCN. Prepared 5-cyano-N-substituited benzimidazole derivates 38-41 in reaction with corresponding aldehydes 14-15 gives the Schiff base of benzimidazole 47˗47. The structures of all prepared products were confirmed by 1H and 13C NMR spectroscopy and mass spectrometry. The Pinner reaction in the preparation of amidino substituited precursors was monitored by IR spectroscopy.