N-GERMYL DERIVATIVES OF 4-NITROPHENYLAMINE: GERMYLAMINES, STABLE GERMA-IMINE

Abstract

N-germyl secondary amines of 4-nitrophenylamine were obtained by transamination from N-trialkylgermyldimethylamine, by transmetallation from the N-lithium derivative of 4-nitrophenylamine, or by intermolecular dehydrohalogenation between the corresponding halogermane and p-nitrophenylamine. Halogermylamines formed by the same methods are always obtained as a mixture with the corresponding diamine bis(4-nitrophenylamino)dimesitylgermane, and cannot be used as germa-imine precursors. However, elimination reactions from N-dimethylaminodimesitylgermyl-4-nitrophenylamine and N-dimesitylchlorogermyl-4-nitrophenylamine, formed from N-triethylgermyl N-dimesitylchlorogeryl-4-nitrophenylamine, yielded the thermally stable N-(4-nitrophenyl)dimesitylgerma-imine as a deep red amorphous powder. This germa-imine is moisture-sensitive, yielding (4-nitrophenylamino) dimesitylgermanol which adds to the germa-imine forming bis(4-nitrophenylamino)dimesitylgermyl) oxide which was isolated as an orange powder. N-4-nitrophenyl)dimesitylgerma-imine adds readily to chloroform yielding N-dimesitylchlorogermyl-4-nitrophenylamine. The 3+2 addition of the germa-imine to N-t-butyl-phenylnitrone gave an adduct whose thermal decomposition began at 100°C yielding benzylidene-4-nitrophenylamine and dimesitylgermoxane. The germa-imine addition to 4,5-di-t-butyl ortho-quinone led to the corresponding dimesitylgermadioxolane through decomposition at room temperature of a transient adduct. The formation of isobutene in this reaction is constitent with a Single Electron Transfer mechanism in the first step.