N-Nitroamines

Similar features were found for N, C -coupling reactions of silyl derivatives of N-nitroamines (473a,b) and BENA (434a) (Scheme 3.252) (501). 

Nitration of the aminopyridines and their methyl derivatives reveals some interesting facets. The amino group strongly activates the positions ortho and para to itself towards nitration, but reaction proceeds via the N-nitroamines. 4-Aminopyridine undergoes nitration via the iV-nitroamine (65) to yield 4-amino-3-nitropyridine (equation 40). Nitration... 

Certain aromatic nitroso compounds can be obtained in good yields by irradiation of the corresponding nitro compounds in 0.1 M aqueous KCN with uv light.592 The reaction has also been performed electrochemically.593 When nitro compounds are treated with most reducing agents, nitroso compounds are either not formed or react further under the reaction conditions and cannot be isolated. N-Nitroamines have been reduced to N-nitrosoamines with Bu3SnH-azobisisobutyrylnitrile.594... 

Direct amination of aromatic rings 1-25 Aminoalkylation of aromatic rings 1-32 Rearrangement of N-nitroamines 1-33 Rearrangement of N-nitrosoamines... 

Challis BC, Li BF. 1982. Formation of n-nitroamines by photolysis. IARC Sci Publ 41 31-40. 

The reaction of piperidine with N2O4 yields both the N-nitroso- and N-nitroamines. The yield of nitrosamine increases with increasing [piperidine] but levels off at ca 50 %, whereas the nitroamine yield increases almost linearly. The two products are believed to arise from the two isomers of N2O4 (Scheme 17), the nitroamine resulting from homolytic fission of the N—N bond, whilst the nitroso product is formed by initial heterolytic fission of the N—O bond in the nitroso nitrate form (Challis and Kyrtopoulos, 1978). 

De Armas, P., Francisco, C. G., Hernandez, R., Salazar, J. A., Suarez, E. Steroidal N-nitroamines. Part 4. Intramolecular functionalization of N-nitroamine radicals synthesis of 1,4-nitroimine compounds. J. Chem. Soc., Perkin Trans. 11988, 3255-3265. 

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