Synthesis and properties of azamonocyclic energetic materials with geminal explosophores

Diversity-oriented synthesis of energetic pyrimidine structures with geminal explosophoric groups of geminal dinitro and azido-nitro groups via a novel reductive cleavage and oxidative coupling strategy is reported. Fluorine has also been introduced for the first time based on the nucleophilic coupling process. The obtained energetic pyrimidines are investigated via X-ray diffraction and theoretical techniques of electrostatic potential and proton affinity calculations. Both experimental and calculation results showed impressive detonation performances and good application prospects of the energetic pyrimidine structures. Among them, DNNC exhibited great promise as a green oxidant in solid propellant formulations to replace ammonium perchlorate (AP). TNHA (ρ = 1.79 g cm-3, D = 8537 m s-1, P = 32.69 Gpa) and TNHF (ρ = 1.85 g cm-3, D = 8517 m s-1, P = 32.64 Gpa) proved to be ideal candidates for high explosives due to their high densities and detonation properties. Moreover, TNHA could also be applied as a potential underwater explosive owing to its great heat of formation.