N-germyl derivatives of 4-nitrophenylamine: Germylamines, stable germa-imine

N-germyl secondary amines of 4-nitrophenylamine were obtained by transamina tion from N-trialkylgermyldimethylamine, by transmetallation from the N-lit hium derivative of 4-nitrophenylamine, or by intermolecular dehydrohalogena tion between the corresponding halogermane and p-nitrophenylamine. Halogerm ylamines formed by the same methods are always obtained as a mixture with t he corresponding diamine bis(4-nitrophenylamino)dimesitylgermane, and canno t be used as germa-imine precursors. However, elimination reactions from N- dimethylaminodimesitylgermyl-4-nitrophenylamine and N-dimesitylchlorogermyl -4-nitrophenylamine, formed from N-triethylgermyl N-dimesitylchlorogermyl-4 -nitrophenylamine, yielded the thermally stable N-(4-nitrophenyl)dimesitylg erma-imine as a deep red amorphous powder. This germa-imine is moisture-sen sitive, yielding (4-nitrophenylamino)dimesitylgermanol which adds to the ge rma-imine forming bis(4-nitrophenylaminodimesitylgermyl)oxide which was iso lated 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-imi ne to N-t-butyl-phenylnitrone gave an adduct whose thermal decomposition be gan at 100 degreesC yielding benzylidene-4-nitrophenylamine and dimesitylge rmoxane. The germa-imine addition to 4,5-di-t-butyl ortho-quinone led to th e corresponding dimesitylgermadioxolane through decomposition at room tempe rature of a transient adduct. The formation of isobutene in this reaction i s constitent with a Single Electron Transfer mechanism in the first step.