Enaminonitrile 2 was a valuable intermediate in organic synthesis, thus it reacted with various N-, C- and O- nucleophiles to furnish aminopyrido[2',3':3,4]pyrazolo[1,5-a]pyrimidine, triazolo[4,3-a]pyrimidinone, aminoisoxazole, benzo [4, 5] imidazo [1, 2-a]pyrimidine, aminopyridinone, hydroxylarylchromene, arylchromenes, pyrano [2,3-d]pyrimidinone and thiopyrano [2, 3-d] pyrimidinone incorporating α-naphthylamine moiety in a good yield. The chemical skeletons of the newly acquired compounds were interpreted by elemental analysis, FT-IR, MS and proton NMR spectroscopic techniques. Toxicological parameters showed a remarkable insecticidal action when the previously products were examined against the cotton leafworm, Spodoptera littoralis, under laboratory conditions. Regarding to LC50 and LC90 values, α-naphthylamine derivatives 7, 8, 9, 20 and 4 indicated a proper toxic effect with LC50 values of 19.551, 23.422, 28.181, 33.700 and 38.163 ppm, respectively, and toxicity index being 32.43, 27.07, 22.50, 18.81 and 16.61%, respectively, comparing with the already recommended insecticide, acetamiprid 20% SP (LC50 value, 6.340 ppm, toxicity index, 100%).