The decomposition rates and product distributions of a number of nitro- and difluoramino-substituted six-membered rings were compared: nitrocyclohexane (I); 1,1-dinitro-cydohexane (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)-l-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 NX2. Where X was oxygen, loss of the initial nitro by homolysis was favored; rearrangement of the remaining nitro followed by homolysis of NO resulted in a C=O bond. Where X was fluorine, the initial difluoramino may have been lost as HNF2. The remaining difluoramino reacted by losing fluorine, leaving C=NF or by losing HNF, resulting in =C-F; the latter was mainly observed.