Multipurpose Energetic Materials by Shuffling Nitro Groups on a 3,3'-Bipyrazole Moiety.

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

[1]  T. Klapötke,et al.  Isomers of Dinitropyrazoles: Synthesis, Comparison and Tuning of their Physicochemical Properties. , 2018, ChemPlusChem.

[2]  D. Lempert,et al.  Bipyrazole bearing ten nitro groups – a novel highly dense oxidizer for forward-looking rocket propulsions , 2018 .

[3]  Yong Tian,et al.  Accelerating the discovery of insensitive high-energy-density materials by a materials genome approach , 2018, Nature Communications.

[4]  Chunlin He,et al.  Energetic derivatives of 4,4′,5,5′-tetranitro-2H,2′H-3,3′-bipyrazole (TNBP): synthesis, characterization and promising properties , 2018 .

[5]  W. Li,et al.  Construction of a Thermally Stable and Highly Energetic Metal–Organic Framework as Lead-Free Primary Explosives , 2018 .

[6]  Hongwei Yang,et al.  C8 N26 H4 : An Environmentally Friendly Primary Explosive with High Heat of Formation. , 2018, Angewandte Chemie.

[7]  T. Klapötke,et al.  Flare or strobe: a tunable chlorine-free pyrotechnic system based on lithium nitrate. , 2018, Chemical Communications.

[8]  T. Ghosh,et al.  Emerging Energetic Materials: Synthesis, Physicochemical, and Detonation Properties , 2018 .

[9]  T. Klapötke,et al.  Ein Strontium‐ und Chlor‐freies rotes pyrotechnisches Leuchtsignal mit hoher spektraler Reinheit , 2017 .

[10]  T. Klapötke,et al.  A Strontium- and Chlorine-Free Pyrotechnic Illuminant of High Color Purity. , 2017, Angewandte Chemie.

[11]  Dheeraj Kumar,et al.  Balancing Excellent Performance and High Thermal Stability in a Dinitropyrazole Fused 1,2,3,4-Tetrazine. , 2017, Journal of the American Chemical Society.

[12]  Wenquan Zhang,et al.  Green primary energetic materials based on N-(3-nitro-1-(trinitromethyl)-1H-1,2,4-triazol-5-yl)nitramide , 2017 .

[13]  Dheeraj Kumar,et al.  Aminoacetonitrile as precursor for nitrogen rich stable and insensitive asymmetric N-methylene-C linked tetrazole-based energetic compounds , 2017 .

[14]  P. Yin,et al.  Polynitro-Functionalized Dipyrazolo-1,3,5-triazinanes: Energetic Polycyclization toward High Density and Excellent Molecular Stability. , 2017, Angewandte Chemie.

[15]  P. Yin,et al.  Pushing the Limits of Oxygen Balance in 1,3,4-Oxadiazoles. , 2017, Journal of the American Chemical Society.

[16]  Dheeraj Kumar,et al.  N-Acetonitrile Functionalized Nitropyrazoles: Precursors to Insensitive Asymmetric N-Methylene-C Linked Azoles. , 2017, Chemistry.

[17]  Dheeraj Kumar,et al.  3,4,5-Trinitro-1-(nitromethyl)-1H-pyrazole (TNNMP): a perchlorate free high energy density oxidizer with high thermal stability , 2017 .

[18]  Dheeraj Kumar,et al.  Resolving synthetic challenges faced in the syntheses of asymmetric N,N′-ethylene-bridged energetic compounds , 2017 .

[19]  J. Shreeve,et al.  5-(Dinitromethyl)-3-(trinitromethyl)-1,2,4-triazole and its derivatives: a new application of oxidative nitration towards gem-trinitro-based energetic materials , 2017 .

[20]  Dheeraj Kumar,et al.  A Highly Stable and Insensitive Fused Triazolo-Triazine Explosive (TTX). , 2017, Chemistry.

[21]  Chengguo Sun,et al.  Synthesis and characterization of the pentazolate anion cyclo-N5ˉ in (N5)6(H3O)3(NH4)4Cl , 2017, Science.

[22]  T. Klapötke,et al.  Synthesis and Investigation of Advanced Energetic Materials Based on Bispyrazolylmethanes. , 2016, Angewandte Chemie.

[23]  Lauren A. Mitchell,et al.  3,6-Dinitropyrazolo[4,3-c]pyrazole-Based Multipurpose Energetic Materials through Versatile N-Functionalization Strategies. , 2016, Angewandte Chemie.

[24]  Lauren A. Mitchell,et al.  Asymmetric N,N′-ethylene-bridged azole-based compounds: Two way control of the energetic properties of compounds , 2016 .

[25]  Lauren A. Mitchell,et al.  Energetic Salts Based on 3,5-Bis(dinitromethyl)-1,2,4-triazole Monoanion and Dianion: Controllable Preparation, Characterization, and High Performance. , 2016, Journal of the American Chemical Society.

[26]  Lauren A. Mitchell,et al.  Connecting energetic nitropyrazole and aminotetrazole moieties with N,N′-ethylene bridges: A promising approach for fine tuning energetic properties , 2016 .

[27]  P. Yin,et al.  Fully C/N-Polynitro-Functionalized 2,2'-Biimidazole Derivatives as Nitrogen- and Oxygen-Rich Energetic Salts. , 2016, Chemistry.

[28]  P. Yin,et al.  Dancing with Energetic Nitrogen Atoms: Versatile N-Functionalization Strategies for N-Heterocyclic Frameworks in High Energy Density Materials. , 2016, Accounts of chemical research.

[29]  Chunlin He,et al.  Potassium 4,5-Bis(dinitromethyl)furoxanate: A Green Primary Explosive with a Positive Oxygen Balance. , 2016, Angewandte Chemie.

[30]  A. Paraskos,et al.  Bishydrazinium and Diammonium Salts of 4,4′,5,5′‐Tetranitro‐2,2′‐biimidazolate (TNBI): Synthesis and Properties , 2015 .

[31]  J. Shreeve,et al.  Tetranitroacetimidic acid: a high oxygen oxidizer and potential replacement for ammonium perchlorate. , 2014, Journal of the American Chemical Society.

[32]  R. Matyáš,et al.  Primary Explosives , 2013 .

[33]  T. Klapötke,et al.  Pushing the limits of energetic materials – the synthesis and characterization of dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate , 2012 .

[34]  T. Klapötke,et al.  Energetic Derivatives of 4, 4′,5, 5′‐Tetranitro‐2, 2′‐bisimidazole (TNBI) , 2012 .

[35]  Yanqiang Zhang,et al.  Synthesis and properties of 3,4,5-trinitropyrazole-1-ol and its energetic salts , 2012 .

[36]  J. Agrawal,et al.  High Energy Materials , 2010 .

[37]  T. Klapötke,et al.  Synthesis and properties of 5-nitrotetrazole derivatives as new energetic materials , 2009 .

[38]  B. Twamley,et al.  2,4,5-trinitroimidazole-based energetic salts. , 2007, Chemistry.

[39]  Thomas M. Klapötke,et al.  High energy density materials , 2007 .

[40]  S. Cho,et al.  Synthesis and Characterization of 4,4′,5,5′‐Tetranitro‐2,2′‐Bi‐1H‐imidazole (TNBI) , 2005 .

[41]  J. Hawari,et al.  TNT, RDX, and HMX Decrease Earthworm (Eisenia andrei) Life-Cycle Responses in a Spiked Natural Forest Soil , 2002, Archives of environmental contamination and toxicology.

[42]  R. C. Bowers,et al.  Mechanisms Involved in Impact Sensitivity and Desensitization of RDX , 1973 .

[43]  F. Effenberger.  Enoläther, II: Synthese und Reaktionen von 1.4‐Bis‐äthoxymethylen‐butandion‐(2.3) , 1965 .