Pressure DSC for energetic materials. Part 2. Switching between evaporation and thermal decomposition of 3,5-dinitropyrazole

Gorn, Margarita V; Моногаров, Константин А.; Далингер, И. Л.; Melnikov, Igor N.; Kiselev, Vitaly G.; Muravyev, Nikita V.

doi:10.1016/j.tca.2020.178697

Cited by 37 publications

(30 citation statements)

References 53 publications

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“…For several compounds under study, the vaporization rate is high and the broad endotherm of evaporation is observed instead of the exothermic peak of thermal decomposition. This behavior is common for energetic materials and previously some of us proposed the pressure DSC method as a convenient tool to suppress the evaporation and observe the sole thermal decomposition process [ 48 , 49 ]. The elevated pressure DSC curves for the isomeric methylnitrofuroxans 1 and 2 are shown in Figure S2 (Supplementary Materials) .…”

Section: Resultsmentioning

confidence: 99%

“…Note that the temperature of the DSC endothermic evaporation peak can be used for semiquantitative estimations. This temperature is generally close to the boiling point of a species [ 49 ] (for a more rigorous determination of the boiling point with DSC, a specific restriction has to be applied to the pan lid orifice along with modified experimental conditions) [ 50 ]. As seen from Figure 8 , the compounds studied are arranged in the following row of this characteristic temperature: 14 (161 °C) ≈ 1 (171 °C) < 4 (206 °C) < TNT (281 °C vs. the estimated boiling point of 300 ± 10 °C [ 51 ]) ≈ DNAN (289 °C).…”

Section: Resultsmentioning

confidence: 99%

“…Most of the experiments were run under atmospheric pressure, but for several highly volatile compounds, the elevated pressure of 2.0 MPa was applied. This methodology (referred to as the pressure DSC) is discussed in detail elsewhere [ 48 , 49 ].…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…All computational approaches for the calculation of

employed in the present work were benchmarked on a series of energetic N-rich heterocycles and exhibited an average “chemical” accuracy (~4 kJ mol −1 ) [ 49 , 54 , 55 ].…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

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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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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…All computational approaches for the calculation of

employed in the present work were benchmarked on a series of energetic N-rich heterocycles and exhibited an average “chemical” accuracy (~4 kJ mol −1 ) [ 49 , 54 , 55 ].…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

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

et al. 2020

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“…The studies of the Sinditskii group have shown that the splitting-off the nitro group from nitropyrazole structure is a possible way to trigger the decomposition of the energetic molecule, meanwhile, the reaction between conjugated nitro and amine groups may also form fused furazan intermediate, whose ring strains will accelerate further decomposition [30]. The studies from the Kiselev and Muravyev group proposed an impressive thermolysis pathway of 3,5-DNP, commencing with the [1,5] sigmatropic hydrogen shift followed by the consequent molecular elimination of N 2 and the radical bond scission yielding •NO 2 [31]. The Prokudin group's study showed that the thermal decomposition of the nitropyrazole derivatives may start from the intramolecular oxidation of the adjacent carbon atom by the nitro group, which proceeds via a strongly polarized cyclic four-membered transition state.…”

Section: 𝐸 = 𝐸 + 𝐸 + 𝐸 + 𝐸 + 𝐸 + 𝐸 + 𝐸 + 𝐸mentioning

confidence: 99%

Comparative Studies on Thermal Decompositions of Dinitropyrazole-Based Energetic Materials

Zhou

Zhang²,

Huo³

et al. 2021

Molecules

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Dinitropyrazole is an important structure for the design and synthesis of energetic materials. In this work, we reported the first comparative thermal studies of two representative dinitropyrazole-based energetic materials, 4-amino-3,5-dinitropyrazole (LLM-116) and its novel trimer derivative (LLM-226). Both the experimental and theoretical results proved the active aromatic N-H moiety would cause incredible variations in the physicochemical characteristics of the obtained energetic materials. Thermal behaviors and kinetic studies of the two related dinitropyrazole-based energetic structures showed that impressive thermal stabilization could be achieved after the trimerization, but also would result in a less concentrated heat-release process. Detailed analysis of condensed-phase systems and the gaseous products during the thermal decomposition processes, and simulation studies based on ReaxFF force field, indicated that the ring opening of LLM-116 was triggered by hydrogen transfer of the active aromatic N-H moiety. In contrast, the initial decomposition of LLM-226 was caused by the rupture of carbon-nitrogen bonds at the diazo moiety.

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(2‐Vinyltetrazolyl)furoxans as New Potential Energetic Monomers

et al. 2022

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A regioselective approach toward the synthesis of a set of new (2-vinyltetrazolyl)furoxans as potential energetic monomers has been realized. All target energetic materials were thoroughly characterized by spectral and analytical methods. Moreover, crystal structures of two representative heterocyclic systems were studied by single-crystal X-ray diffraction. Prepared highenergy substances have high combined nitrogen-oxygen content (63-71 %), high enthalpies of formation and good detonation parameters (D: 6.7-7.8 km s À 1 ; P: 18-28 GPa). Mechanical sensitivities of the synthesized vinyltetrazoles range these explosives from highly sensitive to completely insensitive. Using calculations of molecular electrostatic potentials (ESP), structural factors influencing the impact sensitivity were revealed. Overall, newly synthesized (2-vinyltetrazolyl)furoxans are of interest as promising energetic monomers due to the presence of the vinyl moiety and explosophoric heterocyclic combination, while their performance exceeds that of benchmark explosive TNT.

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Pressure DSC for energetic materials. Part 2. Switching between evaporation and thermal decomposition of 3,5-dinitropyrazole

Cited by 37 publications

References 53 publications

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

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

Comparative Studies on Thermal Decompositions of Dinitropyrazole-Based Energetic Materials

(2‐Vinyltetrazolyl)furoxans as New Potential Energetic Monomers

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