Controlling the Energetic Properties of N-Methylene-C-Linked 4-Hydroxy-3,5-dinitropyrazole- and Tetrazole-Based Compounds via a Selective Mono- and Dicationic Salt Formation Strategy

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(21), P. 15085 - 15096

Published: Oct. 17, 2023

In the quest to synthesize high-performing insensitive high-energy density materials (HEDMs), main challenge is establishing an equilibrium between energy and stability. For this purpose, we explored 4-hydroxy-3,5-dinitropyrazole- tetrazole-based energetic scaffolds connected via a N-methylene-C bridge. The hydroxy functionality nitro groups on pyrazole ring promotes physical stability inter- intramolecular hydrogen bonding contributes oxygen balance, supporting better performance. Due two acidic sites (OH NH) with different reactivities, series of monocationic dicationic salts were synthesized, their overall performance was compared. All compounds synthesized in study have high impact sensitivity >40 J friction >360 N. Monocationic generally found thermal respect corresponding salts, which showed salt formation strategy effectively improved 2 (Td = 168 °C), where most decomposition temperatures higher than 220 °C. characterized through IR, multinuclear NMR spectroscopy, high-resolution mass spectrometry (HRMS), elemental analysis. structure-property relationship studied using Hirshfeld surface analysis, noncovalent interaction (NCI) electrostatic potential studies.

Language: Английский

---

Bis(dinitropyrazolyl)methanes spruced up with hydroxyl groups: high performance energetic salts with reduced sensitivity

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(95), P. 14110 - 14113

Published: Jan. 1, 2023

Superior derivatives of bispyrazolylmethanes, bis(4-hydroxy-3,5-dinitropyrazolyl)methane and its high-performance energetic salts, were synthesized characterized.

Language: Английский

---

Taming of 4-azido-3,5-dinitropyrazole based energetic materials

Materials Advances, Journal Year: 2023, Volume and Issue: 5(1), P. 171 - 182

Published: Nov. 1, 2023

Energetic and physicochemical properties of 4-azido-3,5-dinitropyrazole based energetic compounds were fine-tuned by connecting it to 5-nitramino-1,2,4-oxadiazole moieties via N -methylene- C bridges salt formation strategy.

Language: Английский

---

Insights into Structural and Energetic Features of 3,5-Dinitropyrazole-4-carboxylic Acid and Its Energetic Salts

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 24(16), P. 6790 - 6799

Published: July 31, 2024

The dominance of nitro pyrazole-based explosives in the recently reported high-performing energetic materials motivated us to comprehensively investigate energy–stability correlation among different compounds based on 3,5-dinitro pyrazoles employing various computational methods. We also explored and physicochemical properties overlooked compound 3,5-dinitropyrazole-4-carboxylic acid (CDNP). This study revealed that CDNP exhibits highest thermal stability 4-substituted-3,5-dinitropyrazoles, combined with an acceptable performance. These characteristics are attributed its layered packing, strong intermolecular interactions, carbonyl bonds. Furthermore, dicationic salt formation further allowed fine-tune overall performance stability. dihydroxylammonium (5) shows best performance, comparable well-known traditional explosive TATB, good low sensitivity toward impact friction.

Language: Английский

---

Time for mixing: Mixed dicationic energetic salts based on methylene bridged 4-hydroxy-3,5-dinitropyrazole and tetrazole for tunable performance

Energetic Materials Frontiers, Journal Year: 2024, Volume and Issue: 5(2), P. 105 - 111

Published: May 14, 2024

Various types of materials have been explored in the pursuit high energy density (HEDMs) that balanced and stability. Among them, energetic salts show numerous advantages, such as lower vapor pressures, physical stabilities, opportunity for favourable tuning by careful selection cations/anions. Nitrogen-rich bases are generally used cations salt formation. While synthesis with larger lowers sensitivity, smaller aid better performance. A combination both same ionic moieties might help formation a superior explosive. In this work, facile route mixed dicationic based on 1-((1H-tetrazol-5-yl)methyl)-3,5-dinitro-1H-pyrazol-4-ol (compound 1) has various combinations bigger (compounds 4-10). All synthesized showed positive heats formation, performance comparable to TATB, excellent stability towards impact friction, acceptable thermal stabilities. This improved technique will provide an additional option fine-tuning properties HEDMs facilitate exploring role overall compounds.

Language: Английский

---

Multipurpose Energetic Materials by Shuffling Nitro Groups on a 3,3′‐Bipyrazole Moiety

Chemistry - A European Journal, Journal Year: 2018, Volume and Issue: 24(65), P. 17220 - 17224

Published: Sept. 19, 2018

A family of 3,3'-bipyrazole-based energetic compounds having C-NO2 /N-NO2 functionalities was synthesized by using various nitrating conditions. These nitro derivatives bipyrazole are significantly more dense and compared to the corresponding nitropyrazole analogues while maintaining desired thermal stability sensitivity. Depending on number nature groups (C-NO2 ), different classes materials, such as green primary explosives, high-performance secondary explosives heat-resistant were obtained. All thoroughly characterized IR, NMR [1 H, 13 C{1 H}, 15 N], elemental analysis, differential scanning calorimetry (DSC). Four also structurally with single-crystal X-ray diffraction studies. Heats formation detonation performance calculated Gaussian 03 EXPLO5 v6.01 programs, respectively.

Language: Английский

---

Nitratoethyl-5H-tetrazoles: improving the oxygen balance through application of organic nitrates in energetic coordination compounds

Dalton Transactions, Journal Year: 2021, Volume and Issue: 50(31), P. 10811 - 10825

Published: Jan. 1, 2021

The two isomers of nitratoethyl-5H-tetrazole were prepared and combined with different d-block transition metals anions. 20 energetic coordination compounds (ECCs) analyzed the properties determined.

Language: Английский

---

A potential insensitive-highly-energetic material through conjugation-promoted N-oxidation strategy

Chemical Engineering Journal, Journal Year: 2021, Volume and Issue: 436, P. 131990 - 131990

Published: Aug. 25, 2021

Language: Английский

---

Can a heavy trinitromethyl group always result in a higher density?

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(14), P. 1939 - 1942

Published: Jan. 1, 2023

The first case of a decrease in density with the introduction trinitromethyl group.

Language: Английский

---

Combination of N‐amino‐1,2,4‐triazole and 4‐hydroxy‐3,5‐dinitropyrazole for the synthesis of high performing explosives

Journal of Heterocyclic Chemistry, Journal Year: 2024, Volume and Issue: 61(8), P. 1299 - 1305

Published: June 5, 2024

Abstract In an attempt to cultivate energy‐stability balance, a series of nitrogen and oxygen‐rich high energy density materials were synthesized based on N ‐substituted 4‐hydroxy‐3,5‐dinitropyrazole methylene‐linked ‐amino‐1,2,4‐bridges. The hydroxy substituent contributed oxygen content, hydrogen bonding, tunability via salt formation. On the other hand, triazole bridge delivered content thermal stability. All compounds characterized with multinuclear NMR, FTIR, HRMS, elemental analysis, their physicochemical energetic properties analyzed. Energetic 1 – 5 showed detonation performance adequate overall stabilities. Compound exhibited higher (1.84 g/cm 3 ) ( D v = 8103 m/s, P 26.9 GPa) in comparison its reported amino derivative.

Language: Английский

---