The decomposition rates and product distributions ofa number of nitro- and difluoramino-substituted six- membered rings were compared: nitrocyclohexane (I); 1,1-dinitro-cyclohexane (II); 1,1,4,4-tetranitrocyclo- hexane (III), 1,1,4,4-tetrak1s(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-NO_2 > C-(NOV_2 > C-(NFV_2 The difference in bond energies among the compounds is small. Gemini1.1 bis(difluoramino) compounds appeared to be somewhat more stable than the corresponding gem-dinitro compounds though they released more heat during decomposition. Where 3; nitramine functionality was present, the nitroso analogue was observed as a major decomposition product. The decomposition of getn-bis(dit'1uoramino) and gem-dinitro compounds exhibited similarities. Both experienced loss of one geminal NX_2 group followed by the reariarigement of the remaining NX_2. Where X was oxygen, lo~s of the initial nitro by homolysis was favored; rearrangement of the remaining nitrofo11.owed by homolysis of NO resulted in a C=O bond. Where X was fluorine, the initial difluoramino may have been lost as HNF_2. The remaining difluoramino reacted by losing fluorine, leaving C=NF or by losing HNF, resulting in=C-F; the latter was mainly observed.
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