Impact of regiochemistry in energetic materials science: a case of (nitratomethyl-1,2,3-triazolyl)furazans

Dalton Transactions, Год журнала: 2023, Номер 52(22), С. 7673 - 7683

Опубликована: Янв. 1, 2023

The preparation of multipurpose high-energy materials for space technologies remains a challenging task and such usually require special precautions fine tunability their functional properties. To unveil new opportunities en route to high-performance energetic materials, novel potential melt-castable explosives plasticizers incorporating (1,2,3-triazolyl)furazan scaffold enriched with nitro nitratomethyl explosophoric functionalities were synthesized. successful implementation the regiodivergent approach enabled regioisomeric (nitratomethyltriazolyl)furazans that possessed significantly different physicochemical properties classifying target as substances or plasticizers. Hirshfeld surface calculations supported by energy framework plots also performed better understand relationship between molecular structure sensitivity. All prepared (1,2,3-triazolyl)furazans show high nitrogen-oxygen contents (76-77%), good experimental densities (up 1.72 g cm-3) positive enthalpies formation (180-318 kJ mol-1) resulting in detonation performances (D = 7.1-8.0 km s-1; P 21-29 GPa). Overall, this work unveils strategies construction balanced various applications.

Язык: Английский

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Energetic 1,2,4-oxadiazoles: synthesis and properties

Russian Chemical Reviews, Год журнала: 2024, Номер 93(2), С. RCR5109 - RCR5109

Опубликована: Янв. 16, 2024

The study of high-energy materials based on poly nitrogen- and nitrogen-oxygen-containing heterocycles is one the most important relevant modern interdisciplinary research areas at intersection organic physical chemistry science. Among such heterocycles, 1,2,4-oxadiazole ring a rather interesting building block for synthesis new energetic compounds. Although 1,2,4-oxadiazoles has been developed more than 100 years, these have only recently become known are currently "hot spots" in this field This review systematizes published methods features reactivity 1,2,4-oxadiazole-based Mono- bis(1,2,4-oxadiazoles) as well structures containing other azoles pyrazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-triazole, 1,2,4-triazole tetrazole considered. For series structurally similar compounds, their physicochemical properties summarized factors affecting particular parameter discussed.<br> Bibliography — 123 references.

Язык: Английский

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Design and Synthesis of Nitrogen‐Rich Azo‐Bridged Furoxanylazoles as High‐Performance Energetic Materials

Chemistry - A European Journal, Год журнала: 2021, Номер 27(59), С. 14628 - 14637

Опубликована: Июль 29, 2021

A series of novel energetic materials comprising azo-bridged furoxanylazoles enriched with functionalities was designed and synthesized. These high-energy were thoroughly characterized by IR multinuclear NMR (1 H, 13 C, 14 N) spectroscopy, high-resolution mass spectrometry, elemental analysis, differential scanning calorimetry (DSC). The molecular structures representative amino azo oxadiazole assemblies additionally confirmed single-crystal X-ray diffraction powder diffraction. comparison contributions explosophoric moieties into the density revealed that furoxan 1,2,4-oxadiazole rings are densest motifs while substitution azide fragments on nitro ones leads to an increase density. Azo bridged have high nitrogen-oxygen contents (68.8-76.9 %) thermal stability. synthesized compounds exhibit good experimental densities (1.62-1.88 g cm-3 ), very enthalpies formation (846-1720 kJ mol-1 and, as a result, excellent detonation performance (detonation velocities 7.66-9.09 km s-1 pressures 25.0-37.7 GPa). From application perspective, parameters exceed those benchmark explosive RDX, combination acceptable friction sensitivity azo(1,2,4-triazolylfuroxan) make it promising potential alternative PETN.

Язык: Английский

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Recent Advances in the Synthesis and Biomedical Applications of Heterocyclic NO-Donors

Molecules, Год журнала: 2021, Номер 26(18), С. 5705 - 5705

Опубликована: Сен. 21, 2021

Nitric oxide (NO) is a key signaling molecule that acts in various physiological processes such as cellular metabolism, vasodilation and transmission of nerve impulses. A wide number vascular diseases well immune neurodegenerative disorders were found to be directly associated with disruption NO production living organisms. These issues justify constant search novel NO-donors improved pharmacokinetic profiles prolonged action. In series known structural classes capable release, heterocyclic are special importance due their increased hydrolytic stability low toxicity. It no wonder synthetic biochemical investigations have emerged significantly recent years. this review, we summarized advances the synthesis, reactivity biomedical applications promising (furoxans, sydnone imines, pyridazine dioxides, azasydnones). The potential each system along mechanisms action emphasized.

Язык: Английский

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First Example of 1,2,5‐Oxadiazole‐Based Hypergolic Ionic Liquids: A New Class of Potential Energetic Fuels

Chemistry - A European Journal, Год журнала: 2023, Номер 29(44)

Опубликована: Май 22, 2023

The development of liquid energetic fuels with improved properties is an important topic in space propulsion technologies. In this manuscript, a series ionic liquids incorporating 1,2,5-oxadiazole ring and nitrate, dicyanamide or dinitramide anion was synthesized their physicochemical were evaluated. compounds fully characterized found to have good thermal stabilities (up 219 °C) experimental densities (1.21-1.47 g cm-3 ). Advantageously, 1,2,5-oxadiazole-based high combined nitrogen-oxygen contents 64.4 %), while detonation velocities are on the level known explosive TNT, combustion performance exceeds those benchmark 2-hydroxyethylhydrazinium nitrate. Considering established hypergolicity H2 O2 presence catalyst, insensitivity impact, strong application potential as for

Язык: Английский

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Improvement of Thermal Stability and Sensitivity of Furazan/Furoxan via Ring Closure Generation of Vicinal Amino-Nitro Structure

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(7), С. 4444 - 4452

Опубликована: Март 19, 2024

Energetic compounds that display high thermal stability and insensitivity properties are essential for applications in mining, gas drilling, etc. In this work, a novel 4-nitro-5-aminoisoxazole energetic moiety oriented to enhance decrease the sensitivity of furazan/furoxan analogues was constructed. The generation vicinal amino-nitro structure can be effectively realized one step by green mild ring-closing reaction nitroacetonitrile potassium salt with chloroxime aqueous solution. Seven new good (Td: 155.8∼270.3 °C) low (IS: >40 J, FS: 96∼192 N) were synthesized. nitro-furazan isoxazole combined product exhibits advantages both skeletons, (Dv = 8350 m s–1, P 30.1 GPa) may find value insensitive materials. This strategy promises achieve balance between energy levels offers way design synthesis highly thermally stable meet special applications.

Язык: Английский

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Simple and energetic: Novel combination of furoxan and 1,2,4-triazole rings in the synthesis of energetic materials

Energetic Materials Frontiers, Год журнала: 2022, Номер 3(3), С. 146 - 153

Опубликована: Авг. 17, 2022

Two novel representatives of energetic (1,2,4-triazolyl)furoxans were prepared from the readily available (furoxanyl)amidrazones. Synthesized compounds thoroughly characterized with IR and multinuclear NMR spectroscopy, elemental analysis X-ray diffraction data. Analysis structural features supported by quantum-chemical calculations revealed main reasons for experimentally observed difference in thermal stability mechanical sensitivity both compounds. It was found that 3-cyano-4-(1H-1,2,4-triazol-3-yl)furoxan is more thermally stable (Td: 229 ​°C) than 4-azido-3-(1H-1,2,4-triazol-3-yl)furoxan 154 latter compound also sensitive to impact friction. In addition, heterocyclic assemblies have high detonation parameters (vD: 7.0–8.0 ​km·s−1; p: 22–29 ​GPa) exceeding those benchmark explosives trinitrotoluene hexanitrostilbene which enable their usability various applications.

Язык: Английский

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Novel energetic oxadiazole assemblies

Mendeleev Communications, Год журнала: 2022, Номер 32(1), С. 111 - 113

Опубликована: Янв. 1, 2022

Язык: Английский

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Exploring the energetic potential of 2,5-disubstituted tetrazoles: a case of 2,5-bis(oxadiazolyl)tetrazoles

Dalton Transactions, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The preparation of new energetic materials comprising the poorly explored 2,5-disubstituted tetrazole scaffold as a central structural motif coupled with oxadiazole rings is reported.

Язык: Английский

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

Molecules, Год журнала: 2020, Номер 25(24), С. 5836 - 5836

Опубликована: Дек. 10, 2020

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

Язык: Английский

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