Nitrative cleavage of other nitrogen bonds

Krimmel and co-workers ° have reported the synthesis of 2,4,6-tris(trifluoromethyl)-l,3,5-trinitro-l,3,5-triazacyclohexane (123) from the nitrolysis of the nitrosamine (122). 

The nitrolysis of fert-butyl substituted amines with dinitrogen pentoxide in nitric acid solves many of these problems. However, these substrates are not always accessible via the usual condensation routes. The acidic reagents frequently used for these nitrolysis reactions are not always suitable for substrates with acid-sensitive or easily oxidized functionality. 

Millar and Philbin have explored the nitrodesilylation of silylamines with dinitrogen pen-toxide for the synthesis of nitramines and their derivatives. These reactions, which involve nitra-tive Si-N heteroatom cleavage, are conducted in methylene chloride at subambient temperature. Trimethylsilylamines give high yields of nitramine product and reactions are clean (Table 5.8). 

Synthesis of nitramines, nitramides and nitroureas via the nitrodesilylation of A/-trimethyisilyl compounds with dinitrogen pentoxide (ref. 122) 

The reaction of the silylaziridine (136) with one equivalent of dinifrogen pentoxide in methylene chloride yields the At-nitroaziridine (137), whereas with excess reagent a mixture of the Al,Al-diniframine-nitrate (138) and the dinifrate ester (139) is obtained the former is a high-energy compound and of some difficulty to prepare via other routes. 

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The scope of nitrolysis is huge, with examples of nitramine formation from the cleavage of tertiary amines, methylenediamines, carbamates, ureas, formamides, acetamides and other amides. The deflnition of nitrolysis must be extended to the nitrative cleavage of other nitrogen bonds because sulfonamides and nitrosamines are also important substrates for these reactions. The nitrative cleavage of silylamines and silylamides is also a form of nitrolysis (Section 5.7). 

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