A Comparison of the Thermal Decomposition of Nitramines and Difluoramines

The decomposition rates and product distributions of a number of nitro- and difluoramino-substituted six-membered rings were compared:  nitrocyclohexane (I); 1,1-dinitro-cyclohexane (II); 1,1,4,4-tetranitrocyclohexane (III), 1,1,4,4-tetrakis(difluoramino)cyclohexane (IV); 1,4-dinitropiperazine (V); 1,4,4-trinitropiperidine (VI), and 4,4-bis(difluoramino)-1-nitropiperidine (VII). The study suggested the following order for susceptibility to decomposition:  N−NO2 > C−(NO2)2 > C−(NF2)2 The difference in bond energies among the compounds is small. Geminal bis(difluoramino) compounds appeared to be somewhat more stable than the corresponding gem-dinitro compounds though they released more heat during decomposition. Where a nitramine functionality was present, the nitroso analogue was observed as a major decomposition product. The decomposition of gem-bis(difluoramino) and gem-dinitro compounds exhibited similarities. Both experienced loss of one geminal NX2 group followed by the rearrangement of the remaining ...