N-Trinitroethylamino energetic derivatives were obtained from carbon and nitrogen functionalization of nitropyrazoles and nitrotriazoles. N-Trinitroethylamino nitroazoles and N-amino nitroazoles were fully characterized by IR, multinuclear NMR spectra, and elemental analyses. Compounds 10, 11 and 15 were further confirmed by single crystal X-ray structuring. N-Functionalized nitroazoles have moderate to excellent thermal stabilities with good densities. Data based on impact and friction tests show these compounds range from very sensitive to insensitive. Theoretical calculations carried out using Gaussian 03 demonstrate good to excellent detonation pressures and velocities, as well as high specific impulse.

A highly efficient strategy of two different types of nitrogen-rich heterocyclic energetic compounds, featuring a single NH-bridge (–NH–) and a fused ring, was demonstrated by virtue of Dimroth rearrangement reactions using 4-amino-5-nitro-1,2,3-triazole as the precursor. Various nitrogen-rich compounds and their salts were prepared via this transformation and fully characterized using multinuclear NMR spectroscopy, IR, elemental analysis, and single crystal X-ray structuring. Their key properties, such as decomposition temperatures, densities, detonation velocities and pressures, and impact sensitivities, were obtained from theoretical calculations or experimental measurements. With different task-specific explosophores, the representative energetic compounds 6b and 18 exhibit great potential as high performance insensitive energetic materials and organic primary explosives, respectively. This work gives the classic Dimroth rearrangement new vitality to access diversified task-specific energetic materials.