Synthesis Of 1,5-Bis(p-toluenesulfonyl)-1,5-diazcyclooctane-3,7-dione And Its Amination Investigation

Gem-bis(difluoramino)-substituted heterocyclic nitramines and the production thereof have been seriously pursued for their high-density and high-energy potential deriving from the intrinsically high energy of the difluoramino group (NF2). It is manifested that they may be much superior applied to explosives and solid propellant oxidizers. Meanwhile,3,3,7,7-tetrakis(difluoramino)octahydro-1,5-dinitro-1,5-diazocine, abbreviated to HNFX, is the most attractive candidate member of this class.In this paper, 1,5-bis(p-toluenesulfonyl)-1,5-diazocine-3,7-diol has been successfully synthesized by cyclodimerization using p-toluenesulfonamide and epichlorohydrin as the starting materials. With optimization of the parameters, such as the feeding ratio, solvent, reaction time, the type and the dosage of catalysts, the yield and purity of production have been remarkably improved.After different oxidation reactions, 1,5-bis(p-toluenesulfonyl)-1,5-diazocine -3,7-diol has been oxidated to the corresponding ketone 1,5-bis(p-toluene-sulfonyl)-1,5-diazocine-3,7-dione, an active intermediate which can be applied widely in gem-bis(difluoramino)-substituted heterocyclic nitramines. It was found that Swern reagents exhibited the best reaction effect of all. In addition, optimum reaction conditions, such as the feeding ratio of oxides, reaction time at low temperature and quenching time at room temperature have been obtained after several experiments.1,5-Bis(p-toluenesulfonyl)-1,5-diazocine-3,7-dioxiome has been synthesized using the dione compound as the starting material. With further optimization of the synthetic conditions, the optimized parameters are achieved.Meanwhile, we have synthesized some substitution compounds, such as acetic ester and p-toluenesulfonyl ester. Our ultimate aim is to achieve a potential energetic intermediate, containing difluoramino structural components, initiated by amination of dioxime compound and fluorination of its corresponding amine, and the further study is still in progress.