From N‐Nitro to N‐Nitroamino: Preparation of High‐Performance Energetic Materials by Introducing Nitrogen‐Containing Ions

In the design of energetic materials, high energetic performance and good molecular stability are two main goals. Energetic functionalization which strives for maximum energy often results in unstable chemical bonds and causes safety problems in practical production and storage operations. In this work, N‐nitro‐ and N‐nitroamino‐functionalized mono‐ and bis(1,2,4‐triazoles) were synthesized and characterized by infrared, and multinuclear NMR spectra, and elemental analyses. The N‐nitroamino‐functionalization strategy was employed for bis(imidazole), leading to high density compound 14 (2.007 g cm^?3 at 100 K; 1.94 g cm^?3 at room temperature) and energetic salt 15 . While N‐nitro‐functionalized products are thermally unstable and highly moisture sensitive, N‐nitroamino‐functionalized energetic salts, which are comprised of additional nitrogen‐containing ions, exhibit good density, moderate to excellent structural stabilities, and high performance.     

Synthesis of heterocyclic azoxy compounds from C-nitroheterocyclic compounds and metal derivatives oftert-butylamine

The reaction of 3-nitropyrazole and 3(5)-nitro-1,2,4-triazole with t-BuNHMgBr gives the corresponding asymmetrical diazene oxides. Furthermore, 3(5)-(1,1-dimethylethyl)azoxy-1,2,4-triazole was also synthesized by the reaction of 1-trimethylsilyl-3(5)-nitro-1,2,4-triazole with t-BuNHLi.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1653–1654, July, 1992.     

N‐Diazo‐Bridged Nitroazoles: Catenated Nitrogen‐Atom Chains Compatible with Nitro Functionalities

N‐diazo‐bridged azoles were synthesized based on oxidative coupling of N‐aminoazoles. Incorporation of extended catenated nitrogen‐atom chains with nitro groups led to compounds with favorable functional compatibilities. This combination gives rise to a series of high‐density energetic materials (HEDMs) with high heats of formation, enhanced densities, positive oxygen balances, and good detonation properties while retaining excellent thermal stabilities and relatively low impact sensitivities. Calculated and experimental studies showed the delicate balance between the length of the nitrogen atom chain, energetic performance, and inherent stability, thus, providing a promising strategy for designing advanced energetic materials.