A facile synthetic approach for diazepine and/or benzimidazole derivatives through the reaction of enamenic carbon or nitrogen was developed. On the account of steric factors, compound 2 reacts with isophthaloyl chloride to produce poly heterocyclic compound 5 by via nucleophilic enamenic carbon. On the other hand, upon using acylating agent like diethyl succinate, the cyclocondensation takes place at nucleophilic enamenic nitrogen to furnish the benzimidazole derivative 7. Depending on the reaction condition, CS2 undergoes cyclocondensation with compound 2 in DMSO to afford triheterocyclic compound 10, while the diazepine 12 was formed in basic medium. Cyclocondensation of o-phenylenediamine 1 and two equivalents of acetophenone in acid medium produced quinoxaline 15. The thiourea derivative 16 was obtained from the nucleophilic addition of 1 to NH4SCN. In addition, benzimidazole 18 was formed via cyclocondensation of compound 16 and chloroacetyl chloride. Furthermore, the reaction of diethyl malonate with two equivalents of 16 furnished benzimidazole derivative 19. Finally, thiadiazolobenzimidazole 21 and/or benzotriazole 24 were obtained as the result of reaction of 16 with CS2 and/or HNO2, respectively.