Nitrolysis of nitrosamines

The conversion of a nitrosamine to a nitramine can be affected by either nitrolysis or oxidation. While the results of these two reactions are identical, they are mechanistically very different. For this reason, the oxidation of nitrosamines is discussed separately in Section 5.9. 

The choice of reagent determines whether a nitrosamine undergoes conversion to a nitramine by either nitrolysis or oxidation. An example is given for the conversion of 1,3,5-trinitroso-1,3,5-triazacyclohexane (109) to l,3,5-trinitro-l,3,5-triazacyclohexane (3) (RDX) - the use of 30 % hydrogen peroxide in 99 % nitric acid at subambient temperature goes via oxidation of the nitrosamine functionality, whereas dinitrogen pentoxide in pure nitric acid makes use of a nitrolysis pathway via C-N bond cleavage. 

The nitrolysis of nitrosamines has been relatively unexplored because of the high toxicity of such substrates. Atkins and Willer have prepared a number of cyclic 1,3-dinitrosamines 

Synthesis of cyclic nitramines using the method of Atkins and Wilier (ref. 117) 

Entry Substrate Nitrosamine (% yield) Nitramine (% yield) 

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