Efficient N-nitrolysis of highly deactivated 3,3,7,7-tetrakis(difluoramino)octahydro-1,5-bis(4-nitrobenzenesulfonyl)-1,5-diazocine (1) has been achieved by the use of protonitronium reagent formed in the system nitric acid-trifluoromethanesulfonic acid, producing 3,3,7,7-tetrakis(difluoramino)octahydro-1,5-dinitro-1,5-diazocine (HNFX, 2) in 65% yield in a nonoptimized reaction. The crystal structure of the first morphology of HNFX contains cavities in the form of channels through its unit cell; the observed density is 1.807 g.cm(-)(3).

A method for sulfonating aminophosphazenes with the use of 1,3-propanesultone is described. The alkanesulfonation reactions were first developed with small molecule phosphazene cyclic trimers as models for high polymeric phosphazenes. High molecular weight poly(aminoph0aphazenes) were then sulfonated using similar techniques. The structure and properties of the alkanesulfonated polymers were examined by DSC, intrinsic viscosity, and W, and 'H NMR spectroscopy. This synthetic approach to sulfonated polymers is valuable for the development of new biomedical materials, membranes, reversibly cross-linkable polymers, surfactants, and polyelectrolytes.

No abstract

Difluoramination of a tetrahydro-1,5-diazocine-3,7(2H,6H)-dione to the corresponding 3,3,7,7-tetrakis(difluoramino)diazocine was achieved by a judicious choice of protecting group. Arenesulfonyl protecting groups for the diazocine nitrogens proved superior to acetyl during the slow disruption of the transannular bridge in 9-oxa-3,7-diazabicyclo[3.3.1]nonane intermediates by difluorosulfamic acid. While a 1,5-ditosyl derivative failed to proceed beyond the product of addition of difluoramine to one ketone carbonyl (hemiaminal 6), the use of 4-nitrobenzenesulfonyl as the protecting groups lowered the nitrogens' basicities below that of the oxygen site in the dione and intermediates, allowing the reaction to proceed to a gem-bis(difluoramino)diazocine product (11). A safer procedure for handling difluoramine is described.

Recently, a new class of materials having high-energy, gembis(difluoroamino)-substituted heterocyclic nitroamines, has gained attention for use as high-energy oxidizers: HNFX [1,2] and TNFX [3] have been synthesized under strongly acidic conditions from their corresponding ketone derivatives by using an excess of difluoroamine.