New Energetic Materials featuring Tetrazoles and Nitramines – Synthesis, Characterization and Properties

The alkylation of 2‐nitro‐2‐azapropyl chloride (2) and deprotonated 5‐amino‐1H‐tetrazole (3), 1H‐tetrazole (4), 5‐nitrimino‐1,4H‐tetrazole (5), 1‐methyl‐5‐nitrimino‐4H‐tetrazole (6) and 2‐methyl‐5‐nitraminotetrazole (7) afforded the products 1‐(2‐nitro‐2‐azapropyl)‐5‐aminotetrazole (8), 1‐(2‐nitro‐2‐azapropyl)‐5H‐tetrazole (9), 1‐(2‐nitro‐2‐azapropyl)‐5‐nitriminotetrazole·H2O (10a), 1‐(2‐nitro‐2‐azapropyl)‐5‐nitriminotetrazole·EtOH (10b) 1,5‐bis(2‐nitro‐2‐azapropyl)‐5‐nitraminotetrazole (11), 1‐methyl‐5‐(2‐nitro‐2‐azapropyl)‐5‐nitraminotetrazole (12), 1‐methyl‐4‐(2‐nitro‐2‐azapropyl)‐5‐nitraminotetrazole (13), 1‐methyl‐5‐(2‐nitro‐2‐azapropyl)‐5‐aminotetrazole (14) and 2‐methyl‐5‐(2‐nitro‐2‐azapropyl)‐5‐nitraminotetrazole (15). In addition, the reaction of potassium 1‐methyl‐5‐nitriminotetrazolate with dimethyl sulfate was investigated yielding 1,4‐dimethyl‐5‐nitriminotetrazole (16). All products (8–16) were determined by low temperature single X‐ray diffraction. A comprehensive characterization and description of the chemical properties (IR, Raman, and multinuclear (1H, 13C and 15N) NMR spectroscopy, mass spectrometry, elemental analysis and differential scanning calorimetry) is given. The heats of formation were calculated by heats of combustion measured using bomb calorimetry. With these values and the X‐ray densities, several detonation parameters (e.g. detonation pressure, detonation velocity, heat of explosion) were computed by the EXPLO5 software. In addition, the sensitivities towards impact, friction and electrical discharge were determined.