Synthesis and Calculation of Properties of N-Difluoroaminoazoles, the Novel Type of Energetic Materials

Abstract

A novel class of energetic materials, N-di¯uoroaminonitroazoles was synthesized. One molecule of these compounds contains simultaneously a nitro group and di¯uoroamine one. A method of synthesizing N-di¯uoroaminonitroazoles incorporates the interaction of N-unsubstituted nitroazoles with O-¯uorosulfonyl-N,N-di¯uorohydroxylamine (F 2 NOSO 2 F) in the presence of bases.To estimate possible prospects of these compounds, energy content, molecular crystal density, some parameters of detonation and combustion were calculated using some well-known methods of computational chemistry, as well as some of our original schemes. In addition, thermostability (by the DTA method) and density were identi®ed experimentally for a cross-section row of the studied compounds. The reasons for relatively low stability of this type of substances were given.

Thermal stability of emerging N6-type energetic materials: kinetic modeling of simultaneous thermal analysis data to explain sensitivity trends

“…4,4′,5,5′-Tetranitro-2 H ,2′ H -3,3′-bipyrazole ( 4 ) was synthesized from oxalyl chloride and ethyl vinyl ether in five steps (62% overall yield) in accordance with the reported procedure. 32,33 1 H NMR (300.1 MHz, acetone-d 6 ): δ = 11.30 ppm; 13 C NMR (75.47 MHz, DMSO-d 6 ): δ = 125.1, 132.2, 149.8 ppm. 14 N NMR (21.69 MHz, DMSO- d 6 ): δ = −28.0 (NO 2 ) ppm.…”

“…As a result, these compounds perform slightly better ( 1 ) than or similar ( 2 ) to the benchmark nitramine high explosive HMX. In addition, we consider another molecule with the N–N–N = N–N–N fragment, 1,2-bis(3-nitro-1 H -1,2,4-triazol-1-yl)diazene ( 3 ), 30,31 as well as two structurally relevant compounds without the N6 bridge, 4,4′,5,5′-tetranitro-2 H ,2′ H -3,3′-bipyrazole ( 4 ) 32,33 and 5,5′-dinitro-2 H ,2′ H -3,3′-bi-1,2,4-triazole ( 5 ). 34 A comparative analysis of the thermal behavior and decomposition kinetics of 1–5 should benefit the understanding of how the N6-fragment contributes to the thermal stability of the materials (Fig.…”

Structural and Theoretical Investigation of 3,4,5-Triamino-1,2,4-Triazolium Salts

“…These 1 H and 13 C shifts have been noted previously in many other high nitrogen heterocyclic systems. [15][16][17][18][19][23][24][25][26][27][28][29][30][31][32][33][34] In the vibrational spectra, there were strong indications of nitrogen protonation, with the appearance of a large broad band from 2500-2900 cm -1 which is typical of N + -H---N interactions in the solid state and has been noted in a wide array of protonated nitrogen systems. 16,[35][36][37][38][39][40][41][42][43] A significant blue shift in a band assignable to a carbon-nitrogen double bond is noted in all of the salts, and is most likely from an exocyclic C=N rather than a ring C=N bond and was noted in all three x-ray structure solutions, which is strong evidence for guanidinium like (N-C(=NH 2 + )-N) resonance structures and has been noted previously in similar systems.…”

Synthesis and investigation of isomeric mono- and dinitro derivatives of 3-methyl-4-(pyrazol-3-yl)furazan

“…1). [26][27][28][29][30] The concept of creating hybrid molecules, 31 combining several heterocycles with different substituents, is widely employed by chemists for the design of compounds, in particular energetic materials with desired properties. 27-29,32−46 This approach allows not only to optimize the desired properties, but also to obtain compounds with new properties, thus increasing their scope of applications.…”