Exploring the highly dense energetic materials via regiochemical modulation: A comparative study of two fluorodinitromethyl-functionalized herringbone trifuroxans

Zhai, Lianjie; Bi, Fuqiang; Luo, Yu; Sun, Lin; Huo, Huan; Zhang, Jiaheng; Zhang, Junlin; Wang, Bozhou; Chen, Sanping

doi:10.1016/j.cej.2019.123573

Cited by 35 publications

(21 citation statements)

References 58 publications

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“…The 2D fingerprint plots clearly illustrate the different contributions of intermolecular interactions ( Figure 7 d−f), and the comparison of the amounts of close interactions in NTOM, NTOF and NTOA are shown in Figure 7 g. It has been reported that the O…H and N…H interactions tend to decrease sensitivities, while the O…O interactions usually increase the sensitivity of a compound [ 27 ]. The percentage of contribution of O∙∙∙H, N∙∙∙H, N∙∙∙O and N∙∙∙N type interactions in the total Hirshfeld surface of NTOM are 27.6%, 17.5%, 19.2% and 16.4%, respectively.…”

Section: Resultsmentioning

confidence: 88%

5-Nitrotetrazol and 1,2,4-Oxadiazole Methylene-Bridged Energetic Compounds: Synthesis, Crystal Structures and Performances

Zhang

Bi²,

Yang

et al. 2021

Molecules

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A new structural type for melt cast materials was designed by linking nitrotetrazole ring with 1,2,4-oxadiazole through a N-CH2-C bridge for the first time. Three N-CH2-C linkage bridged energetic compounds, including 3-((5-nitro-2H-tetrazol-2-yl) methyl)-1,2,4-oxadiazole (NTOM), 3-((5-nitro-2H-tetrazol-2-yl)methyl)-5-(trifluoromethyl)-1,2,4 -oxadiazole (NTOF) and 3-((5-nitro-2H-tetrazol-2-yl)methyl)-5-amine-1,2,4-oxadiazole (NTOA), were designed and synthesized through a two-step reaction by using 2-(5-nitro-2H-tetrazole -2-yl)acetonitrile as the starting material. The synthesized compounds were fully characterized by NMR (1H, 13C), IR spectroscopy and elemental analysis. The single crystals of NTOM, NTOF and NTOA were successfully obtained and investigated by single-crystal X-ray diffraction. The thermal stabilities of these compounds were evaluated by DSC-TG measurements, and their apparent activation energies were calculated by Kissinger and Ozawa methods. The crystal densities of the three compounds were between 1.66 g/cm3 (NTOA) and 1.87 g/cm3 (NTOF). The impact and friction sensitivities were measured by standard BAM fall-hammer techniques, and their detonation performances were computed using the EXPLO 5 (v. 6.04) program. The detonation velocities of the three compounds are between 7271 m/s (NTOF) and 7909 m/s (NTOM). The impact sensitivities are >40 J, and the friction sensitivities are >360 N. NTOM, NTOF and NTOA are thermally stable, with decomposition points > 240 °C. The melting points of NTOM and NTOF are 82.6 °C and 71.7 °C, respectively. Hence, they possess potential to be used as melt cast materials with good thermal stabilities and better detonation performances than TNT.

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Section: Resultsmentioning

confidence: 88%

5-Nitrotetrazol and 1,2,4-Oxadiazole Methylene-Bridged Energetic Compounds: Synthesis, Crystal Structures and Performances

Zhang

Bi²,

Yang

et al. 2021

Molecules

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“…Theoretical studies proved that replacing one nitro group with a furoxan moiety could increase the density of compounds by (0.06–0.08) g·m −3 and the corresponding detonation velocity by more than 300 m s −1 ( Wang et al, 2021 ). Therefore, the design and synthesis of C–C bonded trifuroxan compounds was an effective method to obtain energetic compounds with outstanding energetic properties ( Zhai, et al, 2019b ).…”

Section: Synthesis Of Nitrogen-rich Energetic Compoundsmentioning

confidence: 99%

Synthetic Strategies Toward Nitrogen-Rich Energetic Compounds Via the Reaction Characteristics of Cyanofurazan/Furoxan

Wang¹,

Zhai²,

She³

et al. 2022

Front. Chem.

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The structural units of amino-/cyano-substituted furazans and furoxans played significant roles in the synthesis of nitrogen-rich energetic compounds. This account focused on the synthetic strategies toward nitrogen-rich energetic compounds through the transformations based on cyanofurazan/furoxan structures, including 3-amino-4-cyanofurazan, 4-amino-3-cyano furoxan, 3,4-dicyanofurazan, and 3,4-dicyanofuroxan. The synthetic strategies toward seven kinds of nitrogen-rich energetic compounds, such as azo (azoxy)-bridged, ether-bridged, methylene-bridged, hybrid furazan/furoxan-tetrazole–based, tandem furoxan–based, hybrid furazan-isofurazan–based, hybrid furoxan-isoxazole–based and fused framework–based energetic compounds were fully reviewed, with the corresponding reaction mechanisms toward the nitrogen-rich aromatic frameworks and examples of using the frameworks to create high energetic substances highlighted and discussed. The energetic properties of typical nitrogen-rich energetic compounds had also been compared and summarized.

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“…Among a variety of energetic patterns considered for further functionalization, the 1,2,5-oxadiazole-2-oxide (often referred to as furoxan) ring is indeed prominent due to its attractive oxygen balance, high density of energetic derivatives, and high positive enthalpy of formation [ 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 ]. Although only two positions in the furoxan ring are available for the introduction of energetic substituents, the N -oxide regioisomerism is a promising strategy for tuning the detonation performance of furoxan-based energetic materials [ 19 , 20 , 21 , 22 ].…”

Section: Introductionmentioning

confidence: 99%

“…The parent furoxan species(21), its nitro derivatives(22,23), and bis-(24,25) and azobis bicyclic derivatives(26,27) considered in the thermochemical calculations.…”

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confidence: 99%

Nitro-, Cyano-, and Methylfuroxans, and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives

et al. 2020

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In the present work, we studied in detail the thermochemistry, thermal stability, mechanical sensitivity, and detonation performance for 20 nitro-, cyano-, and methyl derivatives of 1,2,5-oxadiazole-2-oxide (furoxan), along with their bis-derivatives. For all species studied, we also determined the reliable values of the gas-phase formation enthalpies using highly accurate multilevel procedures W2-F12 and/or W1-F12 in conjunction with the atomization energy approach and isodesmic reactions with the domain-based local pair natural orbital (DLPNO) modifications of the coupled-cluster techniques. Apart from this, we proposed reliable benchmark values of the formation enthalpies of furoxan and a number of its (azo)bis-derivatives. Additionally, we reported the previously unknown crystal structure of 3-cyano-4-nitrofuroxan. Among the monocyclic compounds, 3-nitro-4-cyclopropyl and dicyano derivatives of furoxan outperformed trinitrotoluene, a benchmark melt-cast explosive, exhibited decent thermal stability (decomposition temperature >200 °C) and insensitivity to mechanical stimuli while having notable volatility and low melting points. In turn, 4,4′-azobis-dicarbamoyl furoxan is proposed as a substitute of pentaerythritol tetranitrate, a benchmark brisant high explosive. Finally, the application prospects of 3,3′-azobis-dinitro furoxan, one of the most powerful energetic materials synthesized up to date, are limited due to the tremendously high mechanical sensitivity of this compound. Overall, the investigated derivatives of furoxan comprise multipurpose green energetic materials, including primary, secondary, melt-cast, low-sensitive explosives, and an energetic liquid.

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Exploring the highly dense energetic materials via regiochemical modulation: A comparative study of two fluorodinitromethyl-functionalized herringbone trifuroxans

Cited by 35 publications

References 58 publications

5-Nitrotetrazol and 1,2,4-Oxadiazole Methylene-Bridged Energetic Compounds: Synthesis, Crystal Structures and Performances

5-Nitrotetrazol and 1,2,4-Oxadiazole Methylene-Bridged Energetic Compounds: Synthesis, Crystal Structures and Performances

Synthetic Strategies Toward Nitrogen-Rich Energetic Compounds Via the Reaction Characteristics of Cyanofurazan/Furoxan

Nitro-, Cyano-, and Methylfuroxans, and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives

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