Energetic Materials Based on 5,5′‐Diamino‐4,4′‐dinitramino‐3,3′‐bi‐1,2,4‐triazole

Abstract

A simple and straightforward synthesis of 5,5'-diamino-4,4'-dinitramino-3,3'-bi-1,2,4-triazole by the selective nitration of 4,4',5,5'-tetraamino-3,3'-bi-1,2,4-triazole is presented. The interaction of the amino and nitramino groups improves the energetic properties of this functionalized bitriazole. For a deeper investigation of these properties, various nitrogen-rich derivatives were synthesized. The new compounds were investigated and characterized by spectroscopy ((1)H and (13)C NMR, IR, Raman), elemental analysis, mass spectrometry, differential thermal analysis (DTA), X-ray analysis, and impact and friction sensitivities (IS, FS). X-ray analyses were performed and deliver insight into structural characteristics with which the stability of the compounds can be explained. The standard enthalpies of formation were calculated for all compounds at the CBS-4M level of theory, revealing highly positive heats of formation. The energetic performance of the new molecules was predicted with the EXPLO5 V6.02 computer. A small-scale shock reactivity test (SSRT) and a toxicity test gave a first impression of the performance and toxicity of selective compounds.

Heats of formation and thermal stability of substituted 1,1′‐Azobis(tetrazole) compounds with an extended nitrogen chain

“…(1) geometry optimization at the B3LYP/cc-pVTZ level followed by a Hessian calculation, (2) second-order Møller-Plesset perturbation theory (MP2) [28,29] energy calculation using the aug-cc-pVTZ basis set, [30] (3) MP2 energy calculation using the aug-cc-pVQZ basis set, [30] (4) relativistic (second-order Douglas-Kroll-Hess) [31] MP2 energy calculation using the cc-pVTZ-DK basis set, [32] (5) all-electron MP2 energy calculation using the aug-cc-pCVTZ basis set, [33] and (6) MP2 and coupled-cluster with singles, doubles, and perturbative triples [CCSD(T)] [34] calculations using the cc-pVTZ basis set. The results from steps (2) and (3) are used to compute the complete basis set (CBS) extrapolated energy.…”

“…These compounds are characterized by their large heats of formation and their relatively high thermal stability. The azole family belongs to this class and in recent years there have been extensive studies on nitrogen‐rich heterocycles such as triazoles and tetrazoles as building blocks for the synthesis of new energetic materials . The energy content of these compounds is derived mostly from their high positive heats of formation, that is, the energy is correlated to the number of nitrogen atoms in the compound.…”

“…The azole family belongs to this class and in recent years there have been extensive studies on nitrogen-rich heterocycles such as triazoles and tetrazoles as building blocks for the synthesis of new energetic materials. [6][7][8][9] The energy content of these compounds is derived mostly from their high positive heats of formation, that is, the energy is correlated to the number of nitrogen atoms in the compound. This is unlike traditional HEDMs such as 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitro-1,3,5-triazinane (RDX), and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) where the energies are derived from the oxidation of the carbon backbone.…”

Ein Strontium‐ und Chlor‐freies rotes pyrotechnisches Leuchtsignal mit hoher spektraler Reinheit

“…4,4',5,5'-Tetraamino-3,3'-bi-1,2,4-triazol (1)u nd 5,5'-Diamino-4,4'-dinitramino-3,3'-bi-1,2,4-triazol (2) sind bereits literaturbekannt, [15] durch Deprotonierung von 2 mit LiOH erhält man das Dilithiumsalz 3. Füre ine reduktive Flammenumgebung ist es zwingend notwendig, die in den äußeren Flammenrändern ablaufenden Oxidationsprozesse zu vermeiden, die mit der Bildung von unerwünschtem LiOH, LiO und kondensierten Verbindungen wie Li 2 Oe inhergehen.…”

“…Dieses Dilithiumsalz ist nicht hygroskopisch und hat eine hohe Zersetzungstemperatur,s odass es als Farbgeber in roten pyrotechnischen Formulierungen untersucht wurde.D ie Synthese von 3 erfolgte einfach in drei Stufen (Schema 1). 4,4',5,5'-Tetraamino-3,3'-bi-1,2,4-triazol (1)u nd 5,5'-Diamino-4,4'-dinitramino-3,3'-bi-1,2,4-triazol (2) sind bereits literaturbekannt, [15] durch Deprotonierung von 2 mit LiOH erhält man das Dilithiumsalz 3.…”