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High-performance explosives: Tris(triazolo)benzene was synthesized and converted to its trinitro and trichloro derivatives (see scheme; R=NO(2), Cl). The heats of formation of this "high-nitrogen" compounds were calculated and combined with experimentally determined densities to determine detonation pressures and velocities. They exhibit high density, good thermal stability, high heats of formation, and moderate to good detonation properties., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Bis[3-(5-nitroimino-1,2,4-triazolate)]-based energetic salts were synthesized in a simple, straightforward manner. They exhibit low solubility in available solvents, high hydrolytic stability, excellent thermal stability, high density, positive heat of formation, low shock sensitivity, and excellent detonation properties. The physical and energetic properties of some salts are similar and even superior to those of RDX.

Nitrogen‐rich energetic materials based on five‐membered azoles, such as tetrazoles, triazoles, oxadiazoles, pyrazoles, and imidazoles, have garnered significant attention in recent years due to their environmental compatibility while maintaining high performance. These materials, including explosives, propellants, and pyrotechnics, are designed to release energy rapidly and efficiently while minimizing the release of toxic or hazardous byproducts and have attracted potential applications in the defense and space industries. The presence of extensive NC, NN, and NN high energy bonds in azoles provides high enthalpies of formation and facilitates intermolecular interactions through π‐stacking which may help with reducing sensitivity to external stimuli. Now, we report on the synthesis and energetic properties of N‐(5‐(1H‐tetrazol‐5‐yl)‐1,3,4‐oxadiazol‐2‐yl)nitramide (5) and its energetic salts. These new high nitrogen–oxygen‐containing materials have attractive feature applications of insensitivity and increased performance. [ABSTRACT FROM AUTHOR]

3,6-Diamino-1H-[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 (Td (onset): 261 °C), surpassing its analogues 3,7-diamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole (DATT, 219 °C) and 3,6,7-triamino-7H-[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 1H-[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. [ABSTRACT FROM AUTHOR]

A new approach to the synthesis of 5,5'‐dinitro‐3,3'‐azo‐1H‐1,2,4‐triazole (3) starting from 3,6‐dihydrazinyl‐1,2,4,5‐tetrazine (DHT) was discovered. Nitrogen‐rich energetic salts of 3 were synthesized in high yields. It is unusual that all the salts were less thermally stable than the neutral compound 3. Of all the compounds, the decomposition temperature of 217 °C, as well as being insensitive towards impact and friction, which suggests potential application as an environmentally friendly nitrogen‐rich energetic material. [ABSTRACT FROM AUTHOR]

A class of polyazole energetic compounds (combination of tetrazolyl, dinitromethyl and triazole) was obtained from 4,5-dicyanotriazole. All the new compounds were fully characterized by IR, NMR [1H, 13C{1H}], elemental analysis, and differential scanning calorimetry (DSC). Compounds 5, 6 and 8 were further characterized with single-crystal X-ray diffraction studies. Heats of formation and detonation performances were determined using Gaussian 03 and EXPLO5 v6.01 programs, which show that 5 is a promising green primary explosive and 7 as a secondary explosive has a detonation velocity superior to 1,3,5-trinitrotriazacyclohexane (RDX). [ABSTRACT FROM AUTHOR]

Abstract: 3‐Nitro‐4‐(5‐nitro‐1,2,4‐triazol‐3‐yl)furazan (2), N,N′‐bis(trinitroethyl)‐3,5′‐diamino‐4‐(1,2,4‐triazol‐3‐yl)furazan (3), N,N′‐bis(trinitroethyl)‐3,5′‐dinitramino‐4‐(1,2,4‐triazol‐3‐yl)furazan (4) and eighteen nitrogen‐rich salts (5 a, 5 b, 5 d–5 i, 5 g‐1, 6 a–6 i) were designed and synthesized. These 4‐(1,2,4‐triazole‐5‐yl)furazan derivatives were fully characterized by IR and NMR spectra, elemental analysis, and differential scanning calorimetry (DSC). The solid‐state structures of 2, 5 d, 5 e, 5 h, 5 g‐1, 6 g, and 6 i were confirmed via single crystal X‐ray analysis. Detonation performance (detonation velocities and pressures) of these energetic compounds was evaluated and the impact and friction sensitivities were measured using standard BAM technology. Some of the compounds, for example, 2 (D: 9152 m s−1, P=37.1 GPa) and 4 (D: 9355 m s−1, P=40.1 GPa) exhibit excellent detonation performance, which are comparable to the highly explosive benchmarks such as RDX (D: 8795 m s−1, P=34.9 GPa) and HMX (D: 9144 m s−1, P=39.2 GPa). [ABSTRACT FROM AUTHOR]

Since highly nitrated nitrogen-rich heterocycles are important motifs in high energy density materials, extensive studies for the development of such novel molecules have been underway. A highly energetic moiety, 3-dinitromethyl-5-nitramino-1,2,4-triazole, which consists of a triazole ring, and nitramino and dinitromethyl groups, has been designed and synthesized. By pairing with nitrogen-rich cations, several ionic derivatives were obtained. Theoretical and experimental studies show that the hydroxylammonium salt ( 7) is highly dense, and has excellent detonation performance with acceptable thermal stablity and sensitivities, which are superior to those of RDX. [ABSTRACT FROM AUTHOR]

3,5-Dinitrimino-1,2,4-triazole ( 2) with three protons has the potential of deprotonation to form energetic salts. Neutralization of 2 with 50 % hydroxylamine in varying molar ratios leads to the formation of the corresponding mono/dihydroxylammonium energetic salts. Additionally compound 5, an ammonia oxide adduct of dihydroxylammonium 3,5-dinitramino-1,2,4-triazolate, was prepared when excess hydroxylamine was used. The structures of 3- 5 are supported by single-crystal X-ray diffraction. The energetic properties of the new materials are competitive. Utilization of ammonia oxide adducts in hydroxylammonium energetic salts could lead to future practical applications as energetic materials. [ABSTRACT FROM AUTHOR]

Using a variety of functionalization strategies, derivatives of 4, 4′-bis(5-nitro-1,2,3-2 H-triazole) were designed, synthesized, and characterized. The isomers were separated, their structures were confirmed with single-crystal X-ray analysis, and their properties were determined by differential scanning calorimetry, density, impact sensitivity, heat of formation, and detonation velocity and pressure (calculated by EXPLO5 V6.01). Those materials were found to exhibit superior detonation performance when compared with the other fully carbon-nitrated bis(azoles). [ABSTRACT FROM AUTHOR]

The synthesis of a series of nitroxy- and azido-functionalized compounds, based on 4-amino-3,5-di(hydroxymethyl)-1,2,4-triazole, for possible use as an energetic plasticizers is described. All compounds were fully characterized. Two of them were further confirmed by X-ray single crystal diffraction. Energetic performance was calculated by using EXPLO5 v6.01 based on calculated heats of formation (Gaussian 03) and experimentally determined densities at 25 °C. The results show that the nitration product 1-nitro-3,5-di(nitroxymethyl)-1,2,4-triazole, containing a nitro group and two nitroxy groups, exhibits good detonation properties ( D=8574 m s−1, P=32.7 GPa). In addition, its low melting point makes it very attractive as an energetic plasticizer in solid propellants. [ABSTRACT FROM AUTHOR]

The straightforward synthesis and energetic properties of a new class of energetic materials, 1,2,3-triazolo- [4,5- e]furazano[3,4- b]pyrazine 6-oxide and its energetic salts are described. They were characterized by IR and multinuclear NMR spectroscopy, elemental analysis, differential scanning calorimetry, and single-crystal X-ray diffraction are given. The X-ray structures show that in the title compound, the hydrogen atom is bonded to the nitrogen in the pyrazine ring; however, in the salts, the negative charge is associated with the triazole nitrogen. Heats of formation for all compounds were calculated with the G2 method and then combined with experimentally determined densities to obtain detonation pressures ( P) and velocities ( D) by using EXPLO5 program. These new materials exhibit good densities and thermal stabilities, high heats of formation, acceptable detonation properties, and are insensitive to impact. [ABSTRACT FROM AUTHOR]

Salts of trinitromethyl-substituted triazoles, 5-nitro- 3-trinitromethyl- 1H-1,2,4-triazole and S,5'-3,3'-azo-1H-1,2,4-triazole (s), form a new class of highly dense energetic materials. Single-crystal X-ray structuring supports the formation of the cocrystal of S with 3,S-diamino-1,2,4-triazole, which was found to be remarkably less impact-sensitive than the azo precursor. The compounds were fully characterized using IR multinuclear NMR spectroscopy, elemental analysis, and differential scanning calorimetry. Based on heats of formation calculated with Gaussian 03 and combined with experimentally determined densities, detonation properties of the energetic materials obtained with the EXPLOS program identify them as potentially explosive compounds. They exhibit high density, moderate to good thermal stability, acceptable oxygen balance, reasonable heat of formation, and excellent detonation properties, which in some cases are superior to those of 1,3,5,-trinitrotriazacyclohexane (RDX). [ABSTRACT FROM AUTHOR]

Aiming high: In the pursuit of new high‐nitrogen structures, researchers have synthesized some interesting compounds with highly catenated chains of nitrogen atoms through a strategy of oxidative azo coupling of NNH2 moieties. This strategy opens opportunities for developing longer nitrogen chains in the field of high‐nitrogen compounds. [ABSTRACT FROM AUTHOR]

Abstract: Trifluoromethanesulfonamide-substituted azoles were synthesized by the reaction of 5-aminotetrazole, 3-amino-1,2,4-triazole and 3,5-diamine-1,2,4-triazole with trifluoromethanesulfonyl fluoride to prepare only monosubstituted compounds. All the compounds were fully characterized using (1H, 19F, 13C) NMR spectroscopy, mass spectrometry (MS), and elemental analysis. [Copyright &y& Elsevier]

Energetic Compounds A fused ‐ ring triazole – triazine explosive, TTX, with energetic properties approaching those of RDX but with a higher thermal stability and lower sensitivity towards impact and friction, was synthesized by an easy two ‐ step and high ‐ yield synthesis from the well ‐ known 5 ‐ amino ‐ 3 ‐ nitro ‐ 1H ‐ 1,2,4 ‐ triazole. The planar conjugated structure of TTX, along with strong hydrogen bonds and nitro – π interactions, are the main forces contributing to its thermal stability and insensitivity. For more details, see the Communication by J. Shreeve et al. on page 1743 ff. [ABSTRACT FROM AUTHOR]

Abstract: 1,4-Disubstituted 1,2,3-triazoles containing a pentafluorosulfanylalkyl group were synthesized in good to excellent yields (57–91%) by the click cycloadditions of in situ generated SF5-alkyl azides with aromatic and aliphatic alkynes. Nucleophilic substitution of the SF5 group was observed for the first time in a bench-top reaction. [ABSTRACT FROM AUTHOR]

New energetic salts (2, 3, 9, 10, and 11) were synthesized via the protonation of 4,4′-bi(1,2,4-triazole) or N-4(1,2,4-triazole)-N-3-(4-methyl-1,2,4-triazole)amine with nitric acid or perchloric acid or 5-nitro-tetrazole. The structures of 4,4′-bi(1,2,4-triazolium) nitrate (2), N,N-dimethyl-N′-(5-methyl-tetrazole)methanimidamide (8), and N-4-(1,2,4-triazole)-N-3-(4-methyl-1,2,4-triazolium)amine perchlorate (10) were confirmed by a single-crystal X-ray analysis. The physical properties and heats of combustion of the new ionic salts were measured, and the heats of formation were also determined. [ABSTRACT FROM AUTHOR]

Studies the synthesis and reaction of butane sulfobetaines, zwitterionic oxo perfluorocarboxylates and triazolium bromides. Aim to provide a series of hydrophilic fluorinated and nonfluorinated triazolium compounds; Formation of alternative compound classes from metathesis of fluorinated halides with anions; Compound characterization through spectral analysis; Possibility of high temperature prior to decomposition.

1,2,4-Triazole was alkylated (alkyl = methyl, butyl, heptyl, decyl) at N-1 in >90% isolated yields. The resulting 1-alkyl triazoles were quaternized at N-4 in >98% isolated yields using fluorinated alkyl halides with >98% isolated yields, under neat reaction conditions at 100-120 °C to form N1-CH[sub 3]-N4-(CH[sub 2])[sub 2]C[sub m]F[sub 2m] + [sub 1]-triazolium (Taz) iodide (m = 1, 6), N1-C[sub 4]H[sub 9]-N[sub 4]-(CH[sub 2])[sub 2]C[sub m]F[sub 2m + 1]-Taz iodide (m = l, 4, 6), N1-C[sub 7]H[sub 15]-N4-(CH[sub 2])[sub 2]C[sub m]F[sub 2m + 1]-Taz iodide (m = 1, 4, 6), N1-C[sub 10]H[sub 21]-N4-(CH[sub 2])[sub 2]C[sub m]F[sub 2m + 1]-Taz iodide (m = 1, 4), and N1-C[sub n]H[sub 2n + 1]-N4-(CH[sub 2])[sub 2]F-Taz bromide (n = 4, 7, 10). Single-crystal X-ray analyses confirmed the structure of [1-CH[sub 3]-4-CH[sub 2]CH[sub 2]CF[sub 3]-Taz][sup +]I[sup -]. It crystallized in the orthorhombic space group Pccn, and the unit cell dimensions were a = 13.8289(9) Å, b = 17.3603(11) Å, c = 9.0587(6) Å (α = β = γ = 90°). Metathesis of these polyfluoroalkyl-substituted triazolium halides with other salts led to the formation of quaternary compounds, some of which comprise ionic liquids, namely, [R(R[sub f])-Taz][sup +]Y[sup -] (Y = NTf[sub 2], BF[sub 4], PF[sub 6], and OTf), in good isolated yields without the need for further purification: N1-CH[sub 3]-N4-(CH[sub 2])[sub 2]C[sub m]F[sub 2m + 1]-Taz Y (m = 1, 6; Y = NTf[sub 2]), N1C[sub 4]H[sub 9]-N4-(CH[sub 2])[sub 2]C[sub m]F[sub 2m + 1]-Taz Y (m = 1, 4, 6; Y = NTf[sub 2]), N1-C[sub 7]H[sub 15]-N4-(CH[sub 2])[sub 2]C[sub m]F[sub 2m + 1]-Taz Y (m = 1, 4, 6; Y = NTf[sub 2]), N1-C[sub 10]H[sub 21]-N4-(CH[sub 2])[sub 2]C[sub m]F[sub 2m + 1]-Taz Y (n = 1, 4; Y = NTf[sub 2]), N1-C[sub n]H[sub 2n + 1]-N4(CH[sub 2])[sub 2]F-Taz Y (n = 7, 10; Y = NTf[sub 2]), N1-C[sub 10]H[sub 21]-N4-(CH[sub 2])[sub 2]F-TazY (Y = OTf), N1-C[sub 7]H[sub 15]-N4-(CH[sub 2])[sub 2]FTazY (Y = BF[sub 4]),... [ABSTRACT FROM AUTHOR]

Molecular modification of known explosives is considered to be an efficient route to design new energetic materials. A new family of energetic salts based on the 3,5-bis(dinitromethyl)-l,2,4-triazole monoanion and dianion were controllably synthesized by using 1- diamino-2,2-dinitroethene as a precursor. X-ray structure de te rmina t ion of monohydrazinium 3,5-bis- (dinitromethyl)-l,2,4-triazolate (5) and monoammonium (6) and diammonium 3,5-bis(dinitromethyl)-l,2,4-triazolate hydrate (8-H20 ) further confirmed the structures of these anions. In addition, as supported by X-ray data, in the monoanion system, the roving proton on the ring nitrogen rather than on the gem-dinitro carbon results in extensive hydrogen-bonding interactions and higher packing coefficients. Interestingly, 5 and 6 possess the highest calculated crystal densities, 1.965 and 1.957 g cm-3 at 150 K, for hydrazinium and ammonium energetic salts, respectively. Energetic evaluation indicates that 5 (detonation velocity vD = 9086 m s-1; detonation pressure P = 38.7 GPa) and 6 (vD, 9271 m s-1; P = 41.0 GPa) exhibit great detonation properties, superior to those of current highly explosive benchmarks, such as 1,3,5-trinitroperhydro- l,3,5-triazine (RDX) and octahydro-l,3,5,7-tetranitro- 1,3,5,7-tetrazocine (HMX). [ABSTRACT FROM AUTHOR]

Energetic salts comprising substituted imidazolium and 1,2,4-triazolium cations and 4,5-dinitro-imidazolate and 5-nitrotetrazolate anions were synthesized and characterized. On the basis of experimentally obtained heats of combustion, the calculated heats of formation range from ΔHf° = 80 (3) to 1071 kJ/mol (13). Imidazolate salts are more dense but have lower heats of formation than their tetrazolate analogues. Salts 4, 5, 8, and 11–14 fall into the ionic liquid class (mp < 100 °C). The structure of 1,2,4-triazolium 5-nitrotetrazolate (10) was confirmed by X-ray analysis. [ABSTRACT FROM AUTHOR]

Studies the quaternary salts of pyridine, N-methyl imidazole, N-propyl triazole and pyridazine that contain pentafluorosulfonyl group. Synthesis and characterization of the salts; Molecular structure; Melting point; Salt density; Phase transition data.

The article presents chemical equations related to the article "1, 2, 3-Triazolo[4,5-e]furazano [3,4-b]pyrazine6-Oxide-A Fused Heterocycle with a Roving Hydrogen Forms a New Class of Insensitive Energetic Materials" by P. Yin, J. Zhang and others, in the "Chemistry: A European Journal" in 2014.