Nitronium salts nitramine formation

The reaction of primary aliphatic amines and nitramines with nitronium salts also leads to deamination and the formation of alkyl nitrates. 

The nitrolysis of substituted methylenediamines with nitronium salts can lead to a number of products depending on the nature of the substituents within the substrate. Electron-withdrawing or resonance-stabilizing groups favour the expulsion of an immonium ion and the formation of a secondary nitramine in yields between 58 % and 78... 

The nitration of nitramine (153) with nitronium tetrafluoroborate, followed by neutralization of the resulting dinitraminic acid with ammonia, also generates ammonium dinitramide (152). Neutralization of this reaction with alkylamines, instead of ammonia, yields the corresponding alkylammonium salts of dinitramide. The nitration of ammonia with dinitrogen pentoxide (15 %) or nitronium salts like the tetrafluoroborate (25 %) yield ammonium dinitramide (152) through the initial formation of nitramine. 

This scheme, however, has the disadvantage of ignoring the influence of the nitronium ion (NO ) on the reaction, whereas, as expounded in the chapter on nitration theories (Vol. I), the nitronium ion is of enormous importance for such a reaction. In this connection Lamberton [43] suggests alternative schemes which appear more probable. Scheme (8) leads to the formation of a nitramine and scheme (9) to a salt of nitric acid ... 

---