NITRATION BY OXIDES OF NITROGEN .8. PREPARATION OF NITRAMINE-NITRATESBY RING-OPENING NITRATION OF AZIRIDINES BY DINITROGEN PENTOXIDE (N2O5)

Thirteen aziridines, bearing various types of substituents on the ring nitrogen, were treated with N2O5 in chlorinated solvents at sub-ambie nt temperature and formed 1,2-nitramine-nitrate products by a novel ri ng-opening nitration reaction analogous to that established for the co rresponding 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 (70-82%), although in one category (the N-(alkylcarbonyl)aziridines) competing deacylation r eactions resulted in reduced yields. Also, aziridines bearing groups c apable of liberating nitric acid with N2O5 (i.e. those with O-H, N-H o r unsubstituted aryl groups) gave rise to greatly reduced yields of th e nitramine-nitrates owing to competing reactions, principally polymer isation/oligomerisation.