Preparation of Nitramine-Nitrates by Ring-Opening Nitration of Aziridines by Dinitrogen Pentoxide (N2O5)

Article abstract of DOI:10.1016/S0040-4020(01)87980-1

Thirteen aziridines, bearing various types of substituents on the ring nitrogen, were treated with N2O5 in chlorinated solvents at sub-ambient temperature and formed 1,2-nitramine-nitrate products by a novel ring-opening nitration reaction analogous to that established for the corresponding oxygen heterocycles (epoxides).A wide variety of classes of aziridine underwent the reaction (N-alkyl, N-(nitroaryl), N-acyl and N-imidyl), the yields in many cases being high (70-82percent), although in one category (the N-(alkylcarbonyl)aziridines) competing deacylation reactions resulted in reduced yields.Also, aziridines bearing groups capable of liberating nitric acid with N2O5 (i.e. those with O-H, N-H or unsubstituted aryl groups) gave rise to greatly reduced yields of the nitramine-nitrates owing to competing rections, principally polymerisation/oligomerisation.