Synthesis of 3,3-bis(difluoramino)octahydro-1,5,7,7-tetranitro-1,5-diazocine (TNFX), a diversified energetic heterocycle

The syntheses of new 3,3-dinitro derivatives of the 1,5-diazocine ring system are described. Highly deactivated precursor ketones hexahydro-7,7-dinitro-1,5-bis(2- and 4-nitrobenzenesulfonyl)-1,5-diazocin-3(2H)-ones (18) have been difluoraminated to the corresponding gem-bis(difluoramino)diazocines (19). The 1,5-bis(4-nitrobenzenesulfonyl)diazocine derivative undergoes N-nitrolysis with the protonitronium reagent formed in the nitric acid–trifluoromethanesulfonic acid–antimony pentafluoride system to produce 3,3-bis(difluoramino)octahydro-1,5,7,7-tetranitro-1,5-diazocine 2 (TNFX), containing nitramine, gem-dinitro, and gem-bis(difluoramino) structural components.