A novel series of naphthodiazepines 4a-e, 6 were synthesized through the reaction of 1,8-diaminonaphthalene 1 with either hydrazonoyl chlorides 2a-e, or bis-hydrazonoyl chloride 5, respectively. Moreover, new derivatives of thiazinoperimidine 9, triazoloperimidine 13 , and thiazoloperimidines 14,17 were produced upon the interaction of 1H-perimidine-2-thiol 7 with the reagents; epichlorohydrin, hydrazonoyl chloride 10, bis-hydrazonoyl chloride 5, and α-chloroacetoacetanilide 15, respectively. Additionally, the irradiation of 1,8-diaminonaphthalene 1 was accomplished at λ > 313 nm using a high-pressure mercury lamp in the presence of oxygen. All the products were characterized using spectroscopic and analytical techniques