Energetic triazinium salts from N-amination of 3,5-diamino-6-nitro-1,2,4-triazine

Abstract

The N-amination of 3,5-diamino-6-nitro-1,2,4-triazine via treatment with O-tosylhydroxylamine (THA) resulted in the formation of the 2,3,5-triamino-6-nitro-1,2,4-triazinium cation as the tosylate salt. The tosylate anion was easily exchanged using ion exchange resin to the chloride salt from which several energetic triazinium salts were synthesized via metathesis reaction. These energetic compounds were chemically and structurally characterized utilizing nuclear magnetic resonance (NMR), infrared spectroscopy (IR), and single-crystal X-ray crystallography. The thermal stabilities were determined by thermal gravimetric analysis (TGA) and energetic sensitivities (impact, friction) were experimentally determined with a BAM Drophammer and BAM friction tester. The energetic performances were calculated with Explo5v6 using Gaussian09 generated heats of formation. The energetic triazinium salts were found to be sensitive high performing energetic materials that have decomposition temperatures less than 200 ​°C. These salts possessed impact sensitivities ≤5 ​J and friction sensitivities generally between 40 ​N and 48 ​N, the exception being the 5,5′-bistetrazole-1,1′-diolate salt whose sensitivity was determined to be ​< ​5 ​N. The calculated detonation pressures range from 26 ​GPa to 34 ​GPa while the detonation velocities range from 8247 ​m·s−1 to 8774 ​m·s−1 similar to PETN (pCJ ​= ​30.8 ​GPa, vD ​= ​8429 ​m·s−1) and TATB (pCJ ​= ​32.4 ​GPa, vD ​= ​8114 ​m·s−1).

Keywords

• N-amination
• 1,2,4-triazine
• Energetic salts
• Nitrogen heterocycles