Synthesis and Properties of Alkylnitramino-1,2,4,5-Tetrazines

Rudakov, Gennady F.; Ustinova, T. V.; Kozlov, I.B.; Zhilin, V. F.

doi:10.1007/s10593-014-1448-9

Cited by 10 publications

(2 citation statements)

References 20 publications

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“…8 Many high-energy materials utilizing dinitroamine-based compounds often demonstrate higher detonation performance. Three kinds of structures can possess two nitroamines (Figure 1), for example, (1) two nitroamine groups bonded to a single ring, such as triazole, 9 tetrazole, 10 tetrazine, 11 or furazan 12 and (2) two nitroamine groups separately on two joined single rings 13 or bridged with azo, 14 methylene, 15 or other rings. 16 Many compounds with this structure provide a route to highly energetic materials.…”

Section: ■ Introductionmentioning

confidence: 99%

Conjugated Energetic Salts Based on Fused Rings: Insensitive and Highly Dense Materials

et al. 2018

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Nitroamino-functionalized 1,2,4-triazolo[4,3-b][1,2,4,5]tetrazine (1), when combined with intermolecular hydrogen bonds (HBs) and strong noncovalent interactions between layers, results, for example, in an interlayer distance of 2.9 Å for dihydroxylammonium 3,6-dinitramino-1,2,4-triazolo[4,3-b][1,2,4,5]tetrazine (2c) with a packing coefficient of 0.805. For dihydroxylammonium 6,6′-dinitramino-3,3′-azo-1,2,4-triazolo[4,3-b][1,2,4,5]tetrazine (3b), two fused rings are linked by an azo group, which expands the conjugated system resulting in an even shorter interlayer distance of 2.7 Å and a higher packing coefficient of 0.807. These values appear to be the shortest interlayer distances and the highest packing coefficients reported for tetrazine energetic materials. With high packing coefficients, both possess high densities of 1.92 g cm–3 and 1.99 g cm–3 at 293 K, respectively. Compared with its precursor, the hydroxylammonium moiety serves as a buffer chain (H–N–O–H), connecting the anion and cation through hydrogen bonds, giving rise to more favorable stacking, and resulting in higher density and lower sensitivity. The sensitivities of all the hydroxylammonium salts are lower than that of their neutral precursors, such as compound 2 (3 J, >5 N) and compound 2c (25 J, 360 N). The detonation properties of 2c (detonation velocity vD = 9712 m s–1 and detonation pressure P = 43 GPa) and 3b (vD = 10233 m s–1; P = 49 GPa) exceed those of present high explosive benchmarks, such as octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and hexanitrohexaazaisowurzitane (CL-20). The molecular structures of several of these new energetic materials are confirmed by single-crystal X-ray diffraction measurements. Using calculated and experimental results, the fused ring with a planar large π-conjugated system results in a compromise between desirable stabilities and high detonation properties, thus enhancing future utilization in the design of energetic materials.

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Section: ■ Introductionmentioning

confidence: 99%

Conjugated Energetic Salts Based on Fused Rings: Insensitive and Highly Dense Materials

et al. 2018

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“…Thus, heat-resistant, low-sensitivity and fast-burning compounds have been obtained. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] Despite the fact that many energetic materials have been synthesized in the series of 1,2,4-triazole, [15][16][17][18][19][20][21][22][23][24][25][26] currently only a few examples of their use in reactions with tetrazine derivatives are known. [27][28][29][30][31][32] These include both symmetrically and unsymmetrically substituted s-tetrazines, linked to the triazole ring (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Physicochemical Properties of Energetic 1,2,4,5‐Tetrazinyl Derivatives of 5‐Nitro‐2,4‐dihydro‐1,2,4‐triazol‐3‐one

et al. 2021

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By replacing the pyrazolyl fragment in 3,6-bis(3,5-dimethyl-1Hpyrazol-1-yl)-1,2,4,5-tetrazine with 3-nitro-1,2,4-triazol-5-one (NTO), both mono-and disubstitution products have been synthesized. Further interaction of the obtained compounds with O-and N-nucleophiles led to the preparation of a number of polynitrogen tetrazine derivatives, including 2-[6-amino-1,2,4,5-tetrazin-3-yl]-5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one and 5-nitro-2-[6-(1H-tetrazol-5-ylamino)-1,2,4,5-tetrazine-3-yl]-2,4-dihydro-3H-1,2,4-triazol-3-one. The reactions of nucleophilic substitution of symmetrically substituted tetrazine were shown to proceed more selectively. The resulting compounds were identified using 1 H, 13 CNMR spectroscopy, FTIR, LC-MS, and elemental analysis, as well as using X-ray diffraction analysis. The thermal stability of the new compounds was evaluated under isothermal and non-isothermal conditions and their energy characteristics were calculated. An unusual drop in stability was found on going from symmetrically substituted tetrazines to asymmetric ones.

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Synthesis of 4,8‐Dinitraminodifurazano[3, 4‐b,e]pyrazine Derived Nitrogen‐Rich Salts as Potential Energetic Materials

Tian

et al. 2018

ChemistrySelect

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A series of new energetic compounds based on 4,8‐dinitraminodifurazano[3, 4‐b,e]pyrazine were synthesised and fully characterized by NMR and IR spectroscopy, and elemental analysis. The structures of compounds 3‐a, 3‐c, 3‐f, and 3‐g were determined by single‐crystal X‐ray diffraction analysis. The physicochemical and energetic properties of these energetic compounds including density, thermal stability, and energetic performance (e. g., detonation velocities and detonation pressures) were investigated. The combination of nitrogen‐rich 4,8‐dihydrodifurazano[3, 4‐b,e]pyrazine framework with highly energetic nitramino moieties endowed these as‐synthesised compounds with excellent detonation performance. Among these as‐synthesised compounds, five energetic salts (3‐a, 3‐b, 3‐c, 3‐f, and 3‐g) exhibited satisfactory calculated detonation velocities (8921–9413 m s‐1), which were superior to cyclo‐1,3,5‐trimethylene‐2,4,6‐trinitamine (RDX) (8878 m s‐1). Notably, compound 3‐f exhibits an excellent calculated detonation velocity of 9166 m s‐1 and also acceptable impact and friction sensitivities (IS=8 J, FS=108 N). The prominent detonation performance with moderate sensitivities indicates that compound 3‐f has the potential to compete with traditional high explosives.

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Synthesis and Properties of Alkylnitramino-1,2,4,5-Tetrazines

Cited by 10 publications

References 20 publications

Conjugated Energetic Salts Based on Fused Rings: Insensitive and Highly Dense Materials

Conjugated Energetic Salts Based on Fused Rings: Insensitive and Highly Dense Materials

Synthesis and Physicochemical Properties of Energetic 1,2,4,5‐Tetrazinyl Derivatives of 5‐Nitro‐2,4‐dihydro‐1,2,4‐triazol‐3‐one

Synthesis of 4,8‐Dinitraminodifurazano[3, 4‐b,e]pyrazine Derived Nitrogen‐Rich Salts as Potential Energetic Materials

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