Energetic <i>C</i>-trinitromethyl-substituted pyrazoles: synthesis and characterization

Zhang, Yiying; Li, Yanan; Hu, Jianjian; Ge, Zhongxue; Sun, Chia‐Chung; Pang, Siping

doi:10.1039/c8dt04712j

Cited by 34 publications

(28 citation statements)

References 25 publications

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“…By incorporating energy-rich functional groups (-NO 2 , -NHNO 2 , -ONO 2 , etc.) into furazan backbones, a large number of energetic materials with excellent detonation properties were successfully developed (Tang et al, 2016;Liu et al, 2018;Zhai et al, 2019;Zhang et al, 2019). Meanwhile, it is noteworthy that an inevitable and inherent contradiction existed SCHEME 1 | (A-C) Electrostatic potential of compounds 6 and 8 [B3LYP/6-31+G** 0.001 electron/b3 isosurface, energy values −0.03 to +0.03 H].…”

Section: Introductionmentioning

confidence: 99%

A Family of Energetic Materials Based on 1,2,4-Oxadiazole and 1,2,5-Oxadiazole Backbones With Low Insensitivity and Good Detonation Performance

Xue¹,

Bi²,

Zhang³

et al. 2020

Front. Chem.

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Design and synthesis of new compounds with both high detonation performances and good safety properties have always been a formidable task in the field of energetic materials. By introducing -ONO 2 and -NHNO 2 moieties into 1,2,4-oxadiazole-and 1,2,5-oxadiazole-based backbones, a new family of energetic materials, including ammonium 3-nitramino-4-(5-hydroxymethyl-1,2,4-oxadiazol-3-yl)-furazan (4), 3,3 ′ -bis[5-nitroxymethyl-1,2,4-oxadiazol-3-yl]-4,4 ′azofuroxan (6), [3-(4-nitroamino-1,2,5-oxadiazol-3-yl)-1,2,4-oxadiazol-5-yl]-methylene nitrate (8), and its energetic ionic salts (10-12), were synthesized and fully characterized. The energetic and physical properties of the materials were investigated through theoretical calculations and experimental determination. The results show that the oxadiazole-based compounds exhibit high enthalpy of formations, good detonation performances, and extraordinary insensitivities. In particular, the hydrazinium salt (11) shows the best energetic properties (11: d =1.821 g cm −3 ; P = 35.1 GPa, v D = 8,822 m s −1 , IS = 40 J, FS > 360 N). The ESP and Hirshfeld surface analysis indicated that a large number of hydrogen bonds as well as π-π stacking interactions within molecules might be the key reason for their low sensitivities and high energy-density levels.

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Section: Introductionmentioning

confidence: 99%

A Family of Energetic Materials Based on 1,2,4-Oxadiazole and 1,2,5-Oxadiazole Backbones With Low Insensitivity and Good Detonation Performance

Xue¹,

Bi²,

Zhang³

et al. 2020

Front. Chem.

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“…In the synthesis pathway of our target compound 3 (Scheme 1), the intermediate, 1-nitro-3-trinitromethylpyrazole ( 2 ), was obtained through our previous procedures, in which 3-pyrazolecarbaldehyde was chosen as the starting material. 17 Then, compound 2 was treated with hydrazine at room temperature to obtain its dinitromethylide salt based on the previous analogical reactions in other azoles. In addition to the successful denitration of the trinitromethyl group, the N–NO 2 group was also observed to migrate to C(5) atom, resulting in the generation of an unexpected product, hydrazinium 5-nitro-3-dinitromethyl-2 H -pyrazole.…”

Section: Resultsmentioning

confidence: 99%

“…16 Previously, we have reported the synthesis of C-trinitromethyl-substituted pyrazoles by the reaction of N 2 O 4 with pyrazolecarbaldehyde oxime. 17 Among them, 1-nitro-3-trinitromethylpyrazole exhibits not only the highest density and detonation performance but also a poor thermal stability and the highest sensitivity to impact and friction, which is the result of the combined effect of trinitromethyl and nitramine groups. 18,19 Given the established instability of trinitromethyl group at high temperature, the dinitromethyl with a coplanar geometric structure is expected to give rise to a better stability as well as a lower sensitivity.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Properties of Energetic Hydrazinium 5-Nitro-3-dinitromethyl-2H-pyrazole by Unexpected Isomerization of N-Nitropyrazole

Zhang

et al. 2019

ACS Omega

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A new energetic salt, hydrazinium 5-nitro-3-dinitromethyl-2H-pyrazole, was synthesized using 1-nitro-3-trinitromethylpyrazole and hydrazine as raw materials and fully characterized by IR and NMR spectroscopy, elemental analysis, and X-ray crystallography. The isomerization of N-nitropyrazole in the reaction condition was first reported and the possible mechanism was explained by the density functional theory method. The salt has good density, high positive enthalpy of formation superior to those of the RDX and HMX, and good detonation properties comparable to those of RDX. By denitration and isomerization reactions, the salt gains a better thermal stability and lower sensitivity toward impact and friction compared with its parent compound. Based on an overall energetic evaluation, the salt has a promising future as an alternative explosive. The research also contributes to the synthesis and application of polynitro-substituted N-heterocyclic compounds as energetic materials.

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“…The introduction of a polynitromethyl group into a heterocyclic compound is interesting for energetic field, because it can increase the oxygen content and improve the energetic properties of energetic material. Generally, the incorporation of a polynitromethyl group (trinitromethyl and dinitromethyl) to nitropyrazoles is essentially equivalent to introducing at least one -NO 2 (since one -NO 2 is used for the complete oxidation of the C atom in -CH 3 ) [56]. For the trinitromethyl group, it can be incorporated into N position or C position of nitropyrazoles with different energetic properties.…”

Section: Mononitropyrazoles and Their Derivativesmentioning

confidence: 99%

“…To explore new high-performance EM, several C-trinitromethyl-substituted mononitropyrazoles have been reported. In 2018, Zhang and co-authors [56] first synthesized the C-trinitromethyl-substituted nitropyrazole (Figure 4, Scheme A). The reaction of 3-pyrazolecarbaldehyde oxime with N 2 O 4 produced the 3-trinitromethylpyrazole and 1-nitro-3-trinitromethylpyrazole (3).…”

Section: Mononitropyrazoles and Their Derivativesmentioning

confidence: 99%

Recent Advances in Synthesis and Properties of Nitrated-Pyrazoles Based Energetic Compounds

et al. 2020

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Nitrated-pyrazole-based energetic compounds have attracted wide publicity in the field of energetic materials (EMs) due to their high heat of formation, high density, tailored thermal stability, and detonation performance. Many nitrated-pyrazole-based energetic compounds have been developed to meet the increasing demands of high power, low sensitivity, and eco-friendly environment, and they have good applications in explosives, propellants, and pyrotechnics. Continuous and growing efforts have been committed to promote the rapid development of nitrated-pyrazole-based EMs in the last decade, especially through large amounts of Chinese research. Some of the ultimate aims of nitrated-pyrazole-based materials are to develop potential candidates of castable explosives, explore novel insensitive high energy materials, search for low cost synthesis strategies, high efficiency, and green environmental protection, and further widen the applications of EMs. This review article aims to present the recent processes in the synthesis and physical and explosive performances of the nitrated-pyrazole-based Ems, including monopyrazoles with nitro, bispyrazoles with nitro, nitropyrazolo[4,3-c]pyrazoles, and their derivatives, and to comb the development trend of these compounds. This review intends to prompt fresh concepts for designing prominent high-performance nitropyrazole-based EMs.

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Energetic C-trinitromethyl-substituted pyrazoles: synthesis and characterization

Abstract: Three novel C-trinitromethyl-substituted pyrazoles with positive oxygen balances and good detonation properties are reported.

Cited by 34 publications

References 25 publications

A Family of Energetic Materials Based on 1,2,4-Oxadiazole and 1,2,5-Oxadiazole Backbones With Low Insensitivity and Good Detonation Performance

A Family of Energetic Materials Based on 1,2,4-Oxadiazole and 1,2,5-Oxadiazole Backbones With Low Insensitivity and Good Detonation Performance

Synthesis and Properties of Energetic Hydrazinium 5-Nitro-3-dinitromethyl-2H-pyrazole by Unexpected Isomerization of N-Nitropyrazole

Recent Advances in Synthesis and Properties of Nitrated-Pyrazoles Based Energetic Compounds

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