Clean nitrations: Novel syntheses of nitramines and nitrate esters by nitrodesilylation reactions using dinitrogen pentoxide (N2O5)

Article abstract of DOI:10.1016/S0040-4020(97)00093-8

In this novel nitration method dinitrogen pentoxide (N₂O₅) in an inert solvent is used as the nitrating agent, thereby removing the need for strong acids as the reaction medium. The N₂O₅ cleaves heteroatom-silicon bonds, in silylamines and silyl ethers respectively, to yield the desired energetic groupings (nitramines or nitrate esters respectively) without liberation of acids which would occur with conventional substrates (amines or alcohols). These nitrodesilylation reactions proceed cleanly and in good yield, and the scope of the reaction is illustrated by 29 examples, some of which produce high energy compounds, notably plasticisers and an energetic polymer precursor. These reactions are therefore potentially clean nitrations for the manufacture of energetic compounds which will minimise the impact of this activity on the environment in the future.