The Photochemical Reactions of 9,10-Anthracenedicarbonitrile and 1,4-Naphthalenedicarbonitrile in Acetonitrile in the Presence of Bases

Article abstract of DOI:10.1016/S0040-4020(01)85074-2

Irradiation of 9,10-anthracenedicarbonitrile (DCA) in MeCN-MeOH or MeCN-H2O containing hydroxides or methoxides leads to 9-methylimino-10-anthracenecarbonitrile (isolated, but easily hydrolyzed to the corresponding amine).Minor products are polycyanated amines and 9-hydroxy-10-anthracenecarbonitrile.Irradiation in neat MeOH causes decyanation.In both cases the first step is reduction to DCA^-*, which persists for hour under these conditions.Evidence for the mechanism leading from the radical anion to the observed products is supplied.The key steps are protonation to yield the radical DCAH^* and addition of the latter to acetonitrile, or to better nucleophiles when these are present. 1,4-Naphthalenedicarbonitrile is similarly transformed to the 4-amino-1-carbonitrile.