Synthesis and Characterization of Aromatic Secondary and Tertiary Amines and a New Imidazolone from Dicyanoimidazole

Article abstract of DOI:10.1016/0040-4020(95)00284-F

Aromatic primary amines substituted with electron donating groups such as methoxy and methyl at the para position undergo nucleophilic aromatic substitution (S_NAr) reactions on 4,5-dicyano-2-fluoro-1-methylimidazole (2) in dimethyl sulfoxide at room temperature to give secondary amines substituted with dicyanoimidazolyl groups.Aromatic primary diamines and hydrazine similarly react with 2 to give new secondary diamines.Aromatic primary amines substituted with electron withdrawing group such as nitro group and also secondary amines such as carbazole react with 2 only after activation of the amine by deprotonation using sodium hydride.The electrophilicity of 2 is high enough to react with oxyanions such as nitrite and carbonate anions and also polar aprotic solvents via O-attack at 60 deg C to give a new imidazolone, 4,5-dicyano-1-methyl-3-(4,5-dicyano-1-methyl-2-imidazolyl)-2-imidazolone (10a).UV-Vis spectra of the newly synthesized compounds are described.