Synthesis and properties of secondary N-nitroamines

Secondary arylamines and related compounds can readily be converted into th e corresponding N-nitroamines by treatment of their organomagnesium derivat ives with butyl nitrate. The yield of the products ranges from 45 to 77%. S econdary aromatic N-nitroamines are characterized by IR absorption bands in the regions 1517-1536, 1285-1299, and 755-759 cm(-1), regardless of the su bstituent in the aromatic ring. According to the H-1 and C-13 NMR data for substituted N-methyl-N-phenylnitroamines, the interaction between the subst ituents through the aromatic ring is weak. alpha-Splitting of N-methyl-N-ph enylnitroamines under electron impact suggests that the Ar-N bond is anomal ously weak. The dipole moments of N-methyl-N-phenylnitroamines can be inter preted in terms of stronger conjugation of n-electrons of the imide nitroge n atom with n-electrons of the nitro group rather than with the aromatic pi -system.