The reaction of diazotetrazole with nitroacetonitrile led to the isolation of the simple 1,2,4‐triazine‐based energetic 3‐azido‐5‐amino‐6‐nitro‐1,2,4‐triazine. It and related compounds were chemically characterized by NMR, IR, and single‐crystal X‐ray crystallography. Their energetic sensitivities (impact, friction) were experimentally determined and energetic performances calculated. The ability of 3‐azido‐5‐amino‐6‐nitro‐1,2,4‐triazine to form
Synthesis and characterization of the energetic 5,7‐diamino‐2‐nitro‐1,2,4‐triazolo[1,5‐a]‐1,3,5‐triazine
The energetic compound 5,7‐diamino‐2‐nitro‐1,2,4‐triazolo[1,5‐a]‐1,3,5‐triazine (ANTT) was synthesized through the selective nitration of 2,5,7‐triamine‐1,2,4‐triazolo[1,5‐a]‐1,3,5‐triazine (TTT). This facile synthetic strategy yields a highly insensitive energetic nitrogen bicycle with potential for further functionalization. ANTT was chemically characterized by NMR, IR, and single crystal X‐Ray crystallography. Its energetic sensitivities (impact, friction) were experimentally determined, and its energetic performances were calculated for the first time.
more » « less- NSF-PAR ID:
- 10462459
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Propellants, Explosives, Pyrotechnics
- Volume:
- 48
- Issue:
- 10
- ISSN:
- 0721-3115
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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1-Amino-1-hydrazino-2,2-dinitroethylene (HFOX) is a potential reactive intermediate for a new class of energetic materials. Now we describe its condensation with various carbonyl compounds in the presence of acidic and basic catalysts. Condensation of HFOX with α-diones and β-diones gives products of much interest. α-Diones undergo cyclization in the presence of base to form six-membered ring products, while β-diones cyclize to five-membered ring products in the presence of acid. One of the exciting reactions is the formation of ammonium (5,6-dimethyl-1,2,4-triazin-3-yl)dinitromethanide salt, 5c, which was isolated by using aqueous ammonia as a nucleophilic base. All new compounds were fully characterized by advanced spectroscopic techniques. The structures of 5, 5c, 5e, 9, 11, and 12a are supported by single crystal X-ray diffraction analysis. Most of the new six membered ring compounds have good thermostabilities (>200 °C), while the fluorinated five membered ring compound, 12b, has the highest density of 2.04 g cm −3 at 25 °C. Heats of formation and detonation properties were calculated by using Gaussian 03 and EXPLO5 software programs. Nearly all new compounds have very good detonation properties, especially, triazine salts, 5e ( D v = 7513 m s −1 ; P = 24.45 G P a), and 5f ( D v = 7948 m s −1 ; P = 26.27 G P a) as well as azide derivative 11 ( D v = 8166 m s −1 ; P = 25.48 G P a), which are superior to TNT ( D v = 6824 m s −1 ; P = 19.40 G P a). These findings provide a new perspective for the synthesis of novel high performing energetic materials.more » « less
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ABSTRACT In this work, by means of quantum chemistry (Density Functional Theory (DFT), PW6B95/def2-TZVPP; DLPNO-CCSD(T)/CBS), HCN polymerization [(HCN)1 − 4] initiated and catalysed by a siloxyl radical (Si-O•) on a model silica surface is analysed. Linear HCN polymers (pHCN) are obtained by a radical initiated mechanism at a SiO• site and are characterized by a -(HC-N)- skeleton due to radical localization on the terminal N atom and radical attack on the C centre. NC heterocycles are formed by cyclization of the linear SiO-(HCN)3 − 4 and are always thermodynamically preferred over their linear counterparts, acting as thermodynamic sinks. Of particular interest to the astrochemistry community is the formation of the N-heterocycle 1,3,5-triazine that can be released into the gas phase at relatively low T (ΔG† = 23.3 kcal/mol). Full hydrogenation of SiO-(HCN•) follows two reaction channels with products: (a) SiO-CH3 + •NH2 or (b) amino-methanol + Si•, though characterized by slow kinetics. Nucleophilic addition of H2O to the electron-rich SiO-(HCN•) shows an unfavourable thermodynamics as well as a high-activation energy. The cleavage of the linear (HCN)1−4 from the SiO• site also shows a high thermodynamic energy penalty (ΔG≥82.0 kcal/mol). As a consequence, the silicate surface will be passivated by a chemically active ‘pHCN brush’ modifying the surface physico-chemical properties. The prospect of surface-catalysed HCN polymers exhibiting a high degree of chemical reactivity and proposed avenues for the formation of 1,3,5-triazine and amino-methanol opens exciting new chemical pathways to Complex Organic Matter formation in astrochemistry.
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null (Ed.)3,6-Diamino-1 H -[1,2,4]triazolo[4,3- b ][1,2,4]triazole ( 1 ) and its energetic salts ( 2–9 ) were designed and synthesized based on a fused-triazole backbone with two C-amino groups as substituents. Their physicochemical and energetic properties were measured or calculated. Among them, compound 1 exhibits superior thermostability ( T d (onset) : 261 °C), surpassing its analogues 3,7-diamino-7 H -[1,2,4]triazolo[4,3- b ][1,2,4]triazole (DATT, 219 °C) and 3,6,7-triamino-7 H -[1,2,4]triazolo[4,3- b ][1,2,4]triazole (TATOT, 245 °C). The differences in thermal stabilities were further investigated by determining the lowest bond dissociation energies (BDE) where a positive correlation between the stability of the molecules and the lowest BDE values is observed. The results show that 1 with the highest value for the lowest BDE has a superior thermostability in comparison to DATT and TATOT. The energetic salts ( 2–9 ) also exhibit remarkable thermal stabilities as well as low impact and friction sensitivities. The fused-triazole backbone 1 H -[1,2,4]triazolo[4,3- b ][1,2,4]triazole with two C-amino groups as substituents is shown to be a promising building block for construction of very thermally stable energetic materials.more » « less
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