Polynitro-functionalized 4-phenyl-1H-pyrazoles as heat-resistant explosives

Abstract

A new class of heat-resistant explosives was synthesized by coupling N-methyl-3,5-dinitropyrazole with polynitrobenzene moieties through carbon–carbon bonds. Simple Pd(0)-based Suzuki cross-coupling reactions between N-methyl-4-bromo-3,5-dinitropyrazole and 4-chloro/3-hydroxy-phenylboronic acid followed by nitration, amination and oxidation lead to the formation of C–C connected penta-nitro energetic derivatives 6 and 10. Various other energetic derivatives, such as amino (5), azido (7), nitramino (8) and energetic salts (11–14), were also explored to fine-tune their properties. All the compounds were thoroughly characterized using IR, NMR [¹H, ¹³C{¹H}], differential scanning calorimetry (DSC), elemental analysis, and HRMS studies. Compounds 5, 10 and 13 were further characterized through ¹⁵N NMR, and the crystal structures of 6 and 14 were confirmed through single-crystal X-ray diffraction studies. The physicochemical and energetic properties of all the energetic compounds were explored. Most of the synthesized compounds demonstrated high thermal stability (decomposition temperature T_dec > 250 °C), among which compounds 5 and 6 showed excellent thermal stability, having decomposition temperatures above 300 °C. The excellent thermal stability, acceptable sensitivity and good energetic properties of compounds 5, 6, 10 and 13 make them promising heat-resistant explosives. Furthermore, these compounds were found to be more thermally stable than the known N-methyl-3,5-dinitropyrazole-based and C–N coupled 3,4,5-trinitrobenzene-azole-based energetic compounds.