Advancing energetic chemistry: the first synthesis of sulfur-based C-C bonded thiadiazole-pyrazine compounds with a nitrimino moiety.

Sulfur-based energetic materials 3 to 7 were synthesized considering the limited availability of structural combinations of polynitrogen- and oxygen-based organic scaffolds, thereby advancing their limits. All of them were fully characterised using infrared spectroscopy (IR), multinuclear magnetic resonance spectroscopy (NMR), high-resolution mass spectrometry (HRMS), elemental analysis (EA), and differential scanning calorimetry (DSC) studies. Furthermore, the molecular structure of compound 3 was confirmed using single-crystal X-ray diffraction studies (SC-XRD).

Skeletal Editing of Energetic Materials: Acid-Catalyzed One-Step Synthesis of Bridged Triazoles as High-Energy-Density Materials via the Nef Reaction.

Thermally stable insensitive energetic materials have captivated significant attention from the global research community due to their potential impact. In this study, a series of symmetric and asymmetric nitromethyl-bridged triazole compounds were synthesized from pyrimidine moieties via a skeletal editing approach. Additionally, carbonyl-bridged compounds were synthesized in a single step by using acid-catalyzed Nef reactions from their nitromethyl precursors.

Synthesis and Performance Evaluation of Zwitterionic C-N Bonded Triazole-Tetrazole-Based Primary Explosives.

Developing advanced metal-free nitrogen-enriched primary explosives is challenging due to the inherent risks associated with their synthesis and handling. However, there is an urgent need to develop novel lead-free, nitrogen-rich primary explosives that offer balanced energetic properties. C-N bonded bicyclic compound 3-azido-1-(1-tetrazol-5-yl)-1-1,2,4-triazol-5-amine (), its salts, and 3,5-diazido-1-1,2,4-triazole () were synthesized from inexpensive starting materials resulting in a fine blend of sensitivity and stability.

Synthesis of C-C bonded trifluoromethyl-based high-energy density materials the ANRORC mechanism.

A trifluoromethyl group substituted C-C bonded nitrogen rich energetic material 3-(3-nitro-1-pyrazol-4-yl)-5-(trifluoromethyl)-1,2,4-oxadiazole (4), its hydroxyl amine (5) and 3,6,7-triamino-7-[1,2,4]triazolo[4,3-][1,2,4]triazol-2-ium (6) salts and hydrazinium 5-(3-nitro-1-pyrazol-4-yl)-3-(trifluoromethyl)-1,2,4-triazol-1-ide (7) were synthesized and fully characterized using infrared spectroscopy (IR), multinuclear magnetic resonance (NMR) spectroscopy (H, C, and F), high-resolution mass spectrometry (HRMS), elemental analysis (EA) and differential scanning calorimetry (DSC) studies. Furthermore, compounds 4 and 7 were confirmed using single-crystal X-ray diffraction studies (SC-XRD). All compounds possess good density (1.

Two Step One-Pot Synthesis of 7-Azaindole Linked 1,2,3-Triazole Hybrids: In-Vitro and In-Silico Antimicrobial Evaluation.

Herein, we report design, synthesis and characterization of a new library of 7-azaindole N-ethyl linked 1,2,3-triazoles containing ethylene as a spacer unit, and evaluation of all the synthesized compounds for their antimicrobial properties. Antibacterial potential was checked against two Gram positive (B. subtilis and S.

Symmetric Refunctionalization of Diaminodinitropyrazine with Hydrazine and Aminotetrazole: Strategy for Enhancing Detonation Performance and Safety in Energetic Materials.

Two novel nitrogen-rich green energetic compounds were synthesized for the first time from readily available and cost-effective pyrazine starting materials. All newly synthesized molecules were comprehensively characterized, including infrared spectroscopy, nuclear magnetic resonance, elemental analysis, mass spectrometry, and thermogravimetric analysis-differential scanning calorimetry. All compounds have additionally been validated by single-crystal X-ray diffraction analysis.

Exploring the Explosive Potential: Synthesis and Characterization of Ring-Fused Oxadiazolo[3,4-]pyrazine 1-Oxide Polymorphs with Balanced Energetic Properties.

A novel fused-ring compound, 5-azido-6-oxo-6,7-dihydro-[1,2,5]oxadiazolo[3,4-]pyrazine 1-oxide (), was synthesized for the first time with simple two-step process and characterized using various spectroscopic techniques such NMR, IR, EA and HRMS. Two polymorphs ( and ) identified by SCXRD differ in crystal packing and noncovalent interactions, demonstrating high density, substantial heat of formation, and superior detonation properties with reduced mechanical sensitivity compared to TNT, TATB, and close to RDX, suggesting their potential as environmentally friendly high energy density materials.

5-Aminoisophthalate-based kojic acid-appended bis-1,2,3-triazole: a fluorescent chemosensor for Cu sensing and study.

A new, easy-to-prepare, and highly selective fluorescent chemosensor, , 5-aminoisophthalate-based kojic acid-appended bis-1,2,3-triazole, was synthesized from an alkyne of 5-aminoisophthalic acid and azido-kojic acid using Cu(i)-catalyzed click chemistry and then successfully characterized. The alkyne structure of 5-aminoisophthalic acid, 1, was supported by the single-crystal X-ray crystallographic data. The fluorescent probe 3 was found to be highly selective for Cu ions supported by the Job's plot with a stoichiometric ligand : metal ratio of 2 : 1, exhibiting almost a two-fold enhancement in the emission intensity upon the addition of Cu ions (0-25 μM) with a detection limit of 8.

Single Step Synthesis of -Dinitro Methyl-1,2,4-triazole and Its Hydroxylamine Salt: An Alternative to the FOX-7 and Other Benchmark Explosives.

-Dinitro methyl based high-energy-density material 5-(dinitromethylene)-4,5-dihydro-1-1,2,4-triazole () and its hydroxylamine salt () were synthesized for the first time in a single step and characterized. Further, the structure of was confirmed by single-crystal X-ray diffraction (SCXRD) studies. Interestengly, both the compounds show excellent density (> 1.

Elaborating NH-Bridged Nitrogen-Rich Energetic Materials via Base-Mediated Dimroth Rearrangement: Synthesis, Characterization, and Performance Study.

The pursuit of heat-resistant energetic materials featuring high thermostability and energy has gained keen interest in recent years owing to their use in coal mining and aerospace domains. In this study, we synthesized 4-((4,6-diamino-1,3,5-triazin-2-yl) amino)-1-1,2,3-triazole-5-carbonitrile () and its perchlorate and nitrate energetic salts ( and ) by incorporating amino bridging (-NH-) using the Dimroth rearrangement (DR) from inexpensive starting materials as a heat-resistant energetic materials. All of the compounds were thoroughly characterized by infrared (IR), NMR, elemental analysis (EA), high-resolution mass spectrometry (HRMS), and thermogravimetric analysis-differential scanning calorimetry (TGA-DSC) studies.

Solvent Free Potassium 3,5-dinitro-6-oxo-1,6-dihydropyrazin-2-olate 3D EMOF as Thermally Stable Energetic Material.

Heat-resistant explosives play a vital role in indispensable applications. For this, we have synthesized a novel, three-dimensional, solvent-free energetic metal-organic framework (EMOF) potassium 3,5-dinitro-6-oxo-1,6-dihydropyrazin-2-olate (KDNODP) straightforwardly. The synthesized EMOF was characterized through IR, NMR spectroscopy, elemental analysis, and differential scanning calorimetry studies.

Highly Dense N-N-Bridged Dinitramino Bistriazole-Based 3D Metal-Organic Frameworks with Balanced Outstanding Energetic Performance.

Due to the inherent conflict between energy and safety, the construction of energetic materials or energetic metal-organic frameworks (E-MOFs) with balanced thermal stability, sensitivity, and high detonation performance is challenging for chemists worldwide. In this regard, in recent times self-assembly of energetic ligands (high nitrogen- and oxygen-containing small molecules) with alkali metals were probed as a promising strategy to build high-energy materials with excellent density, insensitivity, stability, and detonation performance. Herein, based on the nitrogen-rich ,'-([4,4'-bi(1,2,4-triazole)]-3,3'-dial)dinitramide (HBDNBT) energetic ligand, two new environmentally benign E-MOFs including potassium [KBDNBT] K-MOF) and sodium [NaBDNBT] (Na-MOF) have been introduced and characterized by NMR, IR, TGA-DSC, ICP-MS, PXRD, elemental analyses, and SCXRD.

Ruthenium-Induced Decomposition of Hexamethylenetetramine as a Tool for the Acid-Free Sommelet Reaction in Aqueous Medium.

Hexamethylenetetramine (HMTA) is one of the most versatile and most utilized nitrogen-containing heterocyclic compounds in academia and industry. Most of the reactions involving HMTA employ stoichiometric or excess amounts of acid, which hamper the sustainability of the reactions. Herein, we report the first example of the ruthenium-mediated decomposition of HMTA at room temperature, supported by a detailed mechanistic study using thermogravimetric analysis/differential thermal analysis, variable-temperature NMR, UV-vis spectroscopy, and density functional theory techniques.

Bistriazolotriazole-tetramine: commendable energetic moiety and cation.

Context: Various 7H,7'H-[6,6'-bi[1,2,4]triazolo[4,3-b][1,2,4]triazole]-3,3',7,7'-tetramine (A) based nitrogen-rich energetic salts were designed and their properties explored. All energetic salts possess relatively high nitrogen content (> 48%), positive heats of formation (> 429 kJ/mol) and stability owing to a significant contribution from fused backbone. The cationic component shows a very high heat of formation (2516 kJ/mol); therefore, it is highly suitable for enthalpy enhancement in new energetic salts.

Zwitterionic fused pyrazolo-triazole based high performing energetic materials.

A series of nitrogen-rich fused energetic materials were synthesized from commercially available inexpensive starting materials and fully characterized using H and C NMR, IR spectroscopy, elemental analysis, and DSC. The structure of zwitterionic compound 2 was supported by SCXRD data. Among all, 3 and 4 possess excellent detonation velocity (8956 and 9163 m s) and are insensitive towards friction (>360 N) and impact (10 J), having moderate to excellent thermal stability (171-262 °C).

Synthesis of Advanced Pyrazole and N-N-Bridged Bistriazole-Based Secondary High-Energy Materials.

In this work, we have synthesized 3,5-dihydrazinyl-4-nitro-1-pyrazole (), 9-nitro-1-pyrazolo[3,2-:5,1-']bis([1,2,4]triazole)-3,6-diamine (), and N-N-bonded ,'-{[4,4'-bi(1,2,4-triazole)]-3,3'-diyl}dinitramide () and its stable nitrogen-rich energetic salts in one and two steps in quantitative yields from commercially available inexpensive starting material 4,6-dichloro-5-nitropyrimidine (). Along with characterization via nuclear magnetic resonance, infrared, differential scanning calorimetry, and elemental analysis, the structures of and were confirmed by single-crystal X-ray diffraction. Interestingly, show excellent thermal stability (242, 221, 250, and 242 °C, respectively) compared to that of RDX (210 °C).

Azo-Bridged Triazole Macrocycles: Computational Design, Energy Content, Performance, and Stability Assessment.

Oxadiazole and triazole are extensively investigated heterocyclic scaffolds in the development of energetic materials. New energetic molecules were designed by replacing 1,2,5-oxadiazole with 2-1,2,3-triazole in the reported conjugated macrocyclic systems to assess the influence on the energetic properties and stability. In addition, nitro groups were introduced in triazole units (N-functionalization) to improve the energetic performance.

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

In the quest to synthesize high-performing insensitive high-energy density materials (HEDMs), the main challenge is establishing an equilibrium between energy and stability. For this purpose, we explored 4-hydroxy-3,5-dinitropyrazole- and tetrazole-based energetic scaffolds connected via a -methylene-C bridge. The hydroxy functionality between nitro groups on the pyrazole ring promotes physical stability via inter- and intramolecular hydrogen bonding and contributes to oxygen balance, supporting better energetic performance.

Straightforward Synthesis of Insensitive 2-(1-Hydroxy-2,2-dinitrovinyl)guanidine and Its Guanidinium Dinitromethanide Salt as a High Energy Density Material.

High energetic 2-(1-hydroxy-2,2-dinitrovinyl)guanidine and guanidinium dinitromethanide () salt were synthesized in one and two steps using a simple and cost-effective methodology from commercially available inexpensive starting materials with a high yield. NMR, IR spectroscopy, elemental analysis, and differential scanning calorimetry studies were used to characterize compound and salt. Single-crystal XRD, Hirshfeld surface analysis, and SEM analysis were used to study the crystal structure, hydrogen-bonding/noncovalent interactions, and morphology of the salt, respectively.

Energetic coordination compounds: self-assembled from the nitrogen-rich energetic C-C bonded pyrazoles and triazoles.

In energetic materials research, energetic coordination compounds (ECCs) have received much attention due to their high thermal stability and insensitivity to mechanical stimuli. The energetic characteristics of ECCs can be modified by combining various metal cations, potent anions, and ligands. In this study, we have synthesized two energetic ligands, 5-(4-nitro-1-pyrazol-3-yl)-1-1,2,4-triazol-3-amine (NPTA) and ()--(5-(4-nitro-1-pyrazol-3-yl)-2,4-dihydro-3-1,2,4-triazol-3-ylidene)nitramide (NPTN), from a commercially viable starting material and reacted them with nitrate salts of various 3d metals (, Ni, Co, Zn) to obtain six new ECCs, [Ni(NPTA)(HO)]·2NO (1), [Co(NPTA)(HO)]·2NO (2), [Zn(NPTA)(HO)]·2NO (3), [Ni(NPTN)(HO)] (4), [Co(NPTN)(HO)] (5), and [Zn(NPTN)(HO)] (6) under ambient conditions.

Polynitro-functionalized 4-phenyl-1-pyrazoles as heat-resistant explosives.

A new class of heat-resistant explosives was synthesized by coupling -methyl-3,5-dinitropyrazole with polynitrobenzene moieties through carbon-carbon bonds. Simple Pd(0)-based Suzuki cross-coupling reactions between -methyl-4-bromo-3,5-dinitropyrazole and 4-chloro/3-hydroxy-phenylboronic acid followed by nitration, amination and oxidation lead to the formation of C-C connected penta-nitro energetic derivatives 6 and 10. Various other energetic derivatives, such as amino (5), azido (7), nitramino (8) and energetic salts (11-14), were also explored to fine-tune their properties.

Computational Manifestation of Nitro-Substituted Tris(triazole): Understanding the Impact of Isomerism on Performance-Stability Parameters.

Density functional theory (DFT) methods were used to design a series of energetic dinitro-tris(triazole) isomers by altering the triazole rings and -NO groups. The impact of three nitrogen atoms' position in the tris(triazole) scaffold on energy content, performance, and stability was discussed. Based on computed heats of formation and densities, the detonation properties were predicted using the thermochemical EXPLO5 (v6.

Poly Tetrazole Containing Thermally Stable and Insensitive Alkali Metal-Based 3D Energetic Metal-Organic Frameworks.

Poly tetrazole-containing thermally stable and insensitive alkali metal-based 3D energetic metal-organic frameworks (EMOFs) are promising high energy density materials to balance the sensitivity, stability, and detonation performance of explosives in defense, space, and civilian applications. Herein, the self-assembly of L ligand with alkali metals Na(I) and K(I) was prepared at ambient conditions, introducing two new EMOFs, [Na(L)(HO)] () and [K(L)(HO)] (). Single crystal analysis reveals that exhibited a 3D wave-like supramolecular structure with significant hydrogen bonding among the layers, while also featured a 3D framework.

High-performing, insensitive and thermally stable energetic materials from zwitterionic -dinitromethyl substituted C-C bonded 1,2,4-triazole and 1,3,4-oxadiazole.

A series of -dinitromethyl substituted zwitterionic C-C bonded azole based energetic materials (3-8) were designed, synthesized, and characterized through NMR, IR, EA, and DSC studies. Further, the structure of 5 was confirmed with SCXRD and those of 6 and 8 with N NMR. All the newly synthesized energetic molecules exhibited higher density, good thermal stability, excellent detonation performance, and low mechanical sensitivity to external stimuli such as impact and friction.

Facile synthesis of thermally stable tetrazolo[1,5-][1,2,4]triazine substituted energetic materials: synthesis and characterization.

Various thermally stable energetic materials with high nitrogen content, low sensitivity and better detonation performance were synthesized. The versatile functionalization of 1,2,4-triazine involving the introduction of oxadiazole and tetrazole is discussed. All the compounds were fully characterized using IR, multinuclear NMR spectroscopy, elemental analysis, and high-resolution mass spectrometry.