Interaction of copper complexes derived from 1,2-quinone monooximes (2-nitroso-phenols) with amines

The reactions of 1,2-diaminoethane with the copper(II) complexes of 4-methyl- and 5-methoxy-1,2-benzoquinone 2-oxime involve deoxygenation of the ligand and reduction of the metal, and lead to 2-amino-4-methylphenol and 2-amino-7-methoxy-3H-phenoxazin-3-one, respectively. Reactions of the copper(II) complex of 1,2-naphthoquinone 2-oxime with 1,2-diaminoethane and with aniline occur in an analogous fashion, and lead to dibenzo[b,i]phenazine-5,12-diol and 2-amino-1,4-naphthoquinone 4-N-phenylimine, respectively. The copper(II) complex of 1,2-naphthoquinone 1-oxime reacts with aniline to give bis(1,4-dihydro-1-imino-4-phenylimino2-naphtholato)bis(aniline)copper(II) and with 1,2-diaminoethane to give a complex mixture of products. The reactions are rationalized in terms of nitrene intermediacy.