Tris(triazolo)benzene and Its Derivatives: High‐Density Energetic Materials

Thottempudi, Venugopal; Forohor, Farhad; Parrish, Damon A.; Shreeve, Jean’ne M.

doi:10.1002/ange.201205134

Cited by 38 publications

(13 citation statements)

References 36 publications

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“…54 The N-nitration of tris(triazolo)benzene, using concentrated nitric acid and acetic anhydride, formed N-nitro functionalized tris(triazolo)benzene with good energetic performance (4-1). With sodium hypochlorite and acetic acid, the N-chloro functionalized product (4-2) was obtained in good yield.…”

Section: Involving An N−halogen and N−b Functionalization Strategymentioning

confidence: 99%

“…Earlier the synthesis of N-nitro and N-chloro functionalized tris(triazolo)benzene derivatives as high-density energetic materials was initiated (Scheme 16). 54 The N-nitration of tris(triazolo)benzene, using concentrated nitric acid and acetic anhydride, formed N-nitro functionalized tris(triazolo)benzene with good energetic performance (4-1). With sodium hypochlorite and acetic acid, the N-chloro functionalized product (4-2) was obtained in good yield.…”

Section: ■ Introductionmentioning

confidence: 99%

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Dancing with Energetic Nitrogen Atoms: Versatile N-Functionalization Strategies for N-Heterocyclic Frameworks in High Energy Density Materials

2015

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Nitrogen-rich heterocycles represent a unique class of energetic frameworks featuring high heats of formation and high nitrogen content, which have generated considerable research interest in the field of high energy density materials (HEDMs). Although traditional C-functionalization methodology of aromatic hydrocarbons has been fully established, studies on N-functionalization strategies of nitrogen-containing heterocycles still have great potential to be exploited by virtue of forming diverse N-X bonds (X = C, N, O, B, halogen, etc.), which are capable of regulating energy performance and the stability of the resulting energetic compounds. In this sense, versatile N-functionalization of N-heterocyclic frameworks offers a flexible strategy to meet the requirements of developing new-generation HEDMs. In this Account, the role of strategic N-functionalization in designing new energetic frameworks, including the formation of N-C, N-N, N-O, N-B and N-halogen bonds, is emphasized. In the family of N-functionalized HEDMs, energetic derivatives, by virtue of forming N-C bonds, are the most widely used type due to the good nucleophilic capacity of most heterocyclic backbones. Although introduction of carbon tends to decrease energetic performance, significant improvement in material sensitivity makes this strategy attractive for safety concerns. More importantly, most "explosophores" can be readily introduced into the N-C linkage, thus providing a promising route to various HEDMs. Formation of additional N-N bonds typically gives rise to higher heats of formation, implying the potential enhancement in detonation performance. In many cases, the increased hydrogen bonding interactions within N-N functionalized heterocycles also improve thermal stability accordingly. Introduction of a single N,N'-azo bridge into several azole moieties leads to an extended nitrogen chain, demonstrating a new strategy for designing high-nitrogen compounds. The strategy of N-O functionalization has become an increasingly efficient tool for exploring new HEDMs with both high energy and low sensitivity. As a highly dense building block, introduction of oxygen not only improves density significantly but also gives rise to a better oxygen balance. Furthermore, the N-O functionalized strategy is highly suitable for a broad variety of N-heterocycles including five-membered azoles and six-membered azines. Newly explored N-halogen and N-B functionalization strategies have endowed the resulting HEDMs with some new energetic characteristics. Typical examples include the N-halogenated fused triazole and FOX-7 as potential hypergolic oxidizers with very short ignition delay times. In addition, some exploratory studies of N-B functionalized heterocycles have expanded energetic applications as hypergolic ionic liquids, green pyrotechnic colorants, and high-oxygen carriers. Overall, flexible N-functionalization methodologies involving different N-X bond formation have not only provided an efficient approach to diverse energetic ingredients but also expanded...

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Section: Involving An N−halogen and N−b Functionalization Strategymentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Dancing with Energetic Nitrogen Atoms: Versatile N-Functionalization Strategies for N-Heterocyclic Frameworks in High Energy Density Materials

2015

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“…6 The most commonly used cations in the development of energetic salts can be mainly divided into the following sections: (1) acyclic nitrogen-containing cations, e.g., guanidine and hydroxylamine; 7 (2) nitrogen-containing monoheterocyclic cations, e.g., 3,4,5-triamino-1,2,4-triazole, 5amino-1,2,3,4-tetrazole; 8−10 (3) bridged nitrogen-containing cations, e.g., 3,3′-diamino-4,4′-azobis(1,2,4-triazole), 4H, 4′H-[3,3′-bi(1,2,4-triazole)]-4,4′,5,5′-tetraamine; 11 (4) fused heterocyclic cations, e.g., 3,6,7-triamino- [1,2,4]triazole [4,3-b]- [1,2,4]triazole (TATOT), 3,7-diamino-7H- [1,2,4]triazole [4,3b] [1,2,4]triazole. 12 In contrast to acyclic and monoheterocyclic nitrogencontaining cations, fused heterocyclic cations consist of a larger π-conjugated system which is of benefit to the structural stability through electron delocalization and the π−π stacking because of their improved planarity, as was already well-known during the study of strategies in increasing crystal density and lowering sensitivity. 13 In addition, nitrogen-rich fused heterocyclic cations exhibit high nitrogen content and generate nitrogen molecules during the explosion, which not only provides thrust but also meets environmental protection requirements.…”

Section: ■ Introductionmentioning

confidence: 99%

Energetic 1H-Imidazo[4,5-d]pyridazine-2,4,7-triamine: A Novel Nitrogen-rich Fused Heterocyclic Cation with High Density

Jia

Zhang

et al. 2020

Crystal Growth & Design

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Fused heterocyclic energetic cation was rarely reported despite the development of energetic cation has attracted increasing attention in recent years. In this work, a new 1H-imidazo[4,5-d]pyridazine-2,4,7-triamine was synthesized in a one-step reaction, which was used as a cation to prepare 1H-imidazo[4,5-d]pyridazine-2,4,7-triamine perchlorate. Interestingly, when the synthesis was accomplished in different conditions, two crystal forms of perchlorate α-4 and β-4 were obtained, which were further confirmed by X-ray single crystal diffraction, X-ray powder diffractograms, infrared and multinuclear NMR spectra. These salts showed high density (1.88–1.93 g cm–3 at 293(2) K), moderate detonation performance (D, 8128–8437 m s–1; P, 29.4–32.86 GPa) and good thermal stability (T d: 272–274 °C). Compared with those known energetic perchlorates, the density and sensitivity (IS, 14–20 J; FS, 144–168 J) of 4 were also significantly improved. Through theoretical calculations and experiment results, the explanations for the differences in physicochemical properties of these two crystal forms were illustrated. Density overlap indicator (DORI) analysis was also employed to perform the necessary visualization and quantification of covalent and noncovalent interactions. It is evident that ionic bonds, hydrogen bonds, and π–π interactions are responsible for the high density and excellent performance of 1H-imidazo[4,5-d]pyridazine-2,4,7-triamine perchlorate, indicating that as-synthesized new material is a very promising cation in the construction of low-sensitivity high-energy compounds.

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“…In addition, the extensive energetic bonds N−N and C−N in the molecules could provide a lot of energy . Most high‐nitrogen heterocycles possess aromatic structures compared with the noncyclic nitrogen‐rich compounds, thereby resulting in some special properties, like high heats of formation, and high density .…”

Section: Introductionmentioning

confidence: 99%

Coplanar Fused Heterocycle‐Based Energetic Materials

2019

Propellants Explo Pyrotec

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The fused nitrogen‐rich heterocycles, particularly planar structures, possess many advantages over conventional single‐ring energetic compounds. The planar π‐π stacked structures result in enhanced safety. Meanwhile, their conjugated systems give rise to good energetic properties. This review focused on the syntheses, properties, and potential applications of energetic materials based on the coplanar fused nitrogen‐rich heterocycles. Most of these compounds exhibit excellent detonation characteristics along with low mechanical sensitivity which makes them very promising candidates for highly energetic materials for civilian or military applications.

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Tris(triazolo)benzene and Its Derivatives: High‐Density Energetic Materials

Abstract: This work was supported by the Office of Naval Research (N00014-10-1-0097 to V.T. and J.M.S.; N00014-11-AF-0-0002 to D.A.P.).

Cited by 38 publications

References 36 publications

Dancing with Energetic Nitrogen Atoms: Versatile N-Functionalization Strategies for N-Heterocyclic Frameworks in High Energy Density Materials

Dancing with Energetic Nitrogen Atoms: Versatile N-Functionalization Strategies for N-Heterocyclic Frameworks in High Energy Density Materials

Energetic 1H-Imidazo[4,5-d]pyridazine-2,4,7-triamine: A Novel Nitrogen-rich Fused Heterocyclic Cation with High Density

Coplanar Fused Heterocycle‐Based Energetic Materials

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