Tetrazole Azasydnone (C2N7O2H) And Its Salts: High-Performing Zwitterionic Energetic Materials Containing A Unique Explosophore.

We report the first compound containing both a tetrazole and an azasydnone ring, a unique energetic material.   Several energetic salts of the tetrazole azasydnone were synthesized and characterized, leading to the creation of new secondary and primary explosives. Molecular structures are confirmed by 1 H and 13 C NMR, IR spectroscopy, and X-ray crystallographic analysis. The high heats of formation, fast detonation velocities, and straight-forward synthesis of energetic azasydnones should capture the attention of future energetics research.

[1]  M. Zeller,et al.  Sensitive Energetics from the N‐Amination of 4‐Nitro‐1,2,3‐Triazole , 2020, ChemistryOpen.

[2]  A. B. Sheremetev,et al.  Reactivity of Azasydnones: Unusual Diversity in Reactions of Chloro‐ and Nitrophenyl Derivatives with Nitrogen Nucleophiles , 2020 .

[3]  Guojie Zhang,et al.  A novel energetic framework combining the advantages of furazan and triazole: a design for high-performance insensitive explosives. , 2020, Dalton transactions.

[4]  Zijun Wang,et al.  A Family of Energetic Materials Based on 1,2,4-Oxadiazole and 1,2,5-Oxadiazole Backbones With Low Insensitivity and Good Detonation Performance , 2020, Frontiers in Chemistry.

[5]  L. Fershtat,et al.  Straightforward Access to the NO-Donor Azasydnone Scaffold by Cascade Reactions of Amines. , 2019, Chemistry.

[6]  M. Zeller,et al.  Synthesis and Characterization of Salts of the 3,6‐Dinitro‐[1,2,4]triazolo[4,3‐b][1,2,4]triazolate Anion: Insensitive Energetic Materials Available From Economical Precursors , 2019, Zeitschrift für anorganische und allgemeine Chemie.

[7]  N. Muravyev,et al.  An Energetic (Nitro-NNO -azoxy)triazolo-1,2,4-triazine , 2019, European Journal of Organic Chemistry.

[8]  A. B. Sheremetev,et al.  Nitration of Azasydnones and Azasydnonimines: A Method for the Functionalization of Aryl Derivatives. , 2019, ChemPlusChem.

[9]  Robert Routledge.  Explosives , 2018, Discoveries and Inventions of the Ninteenth Century.

[10]  Chunlin He,et al.  Asymmetric nitrogen-rich energetic materials resulting from the combination of tetrazolyl, dinitromethyl and (1,2,4-oxadiazol-5-yl)nitroamino groups with furoxan. , 2018, Dalton transactions.

[11]  Rahul Bhowmick,et al.  Nitric Oxide Sensing through 1,2,3,4-Oxatriazole Formation from Acylhydrazide: A Kinetic Study. , 2018, The Journal of organic chemistry.

[12]  E. A. Miroshnichenko,et al.  Azasydnone – Novel 'green' building block for designing high energetic compounds , 2018 .

[13]  E. Byrd,et al.  Bis(1,2,4-oxadiazole)bis(methylene) Dinitrate: A High-Energy Melt-Castable Explosive and Energetic Propellant Plasticizing Ingredient , 2018 .

[14]  I. Gospodinov,et al.  Energetic Compounds Based on 3,4‐Bis(4‐nitramino‐ 1,2,5‐oxadiazol‐3‐yl)‐1,2,5‐furoxan (BNAFF) , 2018 .

[15]  P. Yin,et al.  Efficient Construction of Energetic Materials via Nonmetallic Catalytic Carbon-Carbon Cleavage/Oxime-Release-Coupling Reactions. , 2018, Journal of the American Chemical Society.

[16]  S. A. Filatov,et al.  THERMAL STABILITY AND COMBUSTION BEHAVIORS OF ENERGETIC MATERIALS BASED ON A NEW HETEROCYCLE AZASYDNONE , 2018 .

[17]  C. L. Coon,et al.  Synthetic Studies of 2,6‐Diamino‐3,5‐Dinitropyrazine‐ 1‐Oxide (LLM‐105) from Discovery to Multi‐Kilogram Scale , 2018 .

[18]  A. Wagner,et al.  Bioorthogonal Click and Release Reaction of Iminosydnones with Cycloalkynes. , 2017, Angewandte Chemie.

[19]  Gregory H. Imler,et al.  Azido and Tetrazolo 1,2,4,5-Tetrazine N-Oxides. , 2017, Angewandte Chemie.

[20]  K. Lyssenko,et al.  Synthesis of Tetrazino-tetrazine 1,3,6,8-Tetraoxide (TTTO). , 2016, Angewandte Chemie.

[21]  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.

[22]  Karl D. Oyler,et al.  Recent Advances in the Synthesis of High Explosive Materials , 2015 .

[23]  D. Parrish,et al.  Synthesis and Thermal Behavior of a Fused, Tricyclic 1,2,3,4-Tetrazine Ring System. , 2015, Angewandte Chemie.

[24]  T. Klapötke,et al.  An Energetic N‐Oxide and N‐Amino Heterocycle and its Transformation to 1,2,3,4‐Tetrazine‐1‐oxide , 2015 .

[25]  Jianguo Zhang,et al.  Multi-stage decomposition of 5-aminotetrazole derivatives: kinetics and reaction channels for the rate-limiting steps. , 2014, Physical chemistry chemical physics : PCCP.

[26]  Ralf Haiges,et al.  Energetic high-nitrogen compounds: 5-(trinitromethyl)-2H-tetrazole and -tetrazolates, preparation, characterization, and conversion into 5-(dinitromethyl)tetrazoles. , 2013, Inorganic chemistry.

[27]  T. Klapötke,et al.  1,3-Bis(nitroimido)-1,2,3-triazolate anion, the N-nitroimide moiety, and the strategy of alternating positive and negative charges in the design of energetic materials. , 2012, Journal of the American Chemical Society.

[28]  T. Klapötke,et al.  The Synthesis and Energetic Properties of 5,7‐Dinitrobenzo‐1,2,3,4‐tetrazine‐1,3‐dioxide (DNBTDO) , 2012 .

[29]  T. Klapötke,et al.  Copper Salts of Halo Tetrazoles: Laser-Ignitable Primary Explosives , 2012 .

[30]  T. Klapötke,et al.  The taming of CN7(-): the azidotetrazolate 2-oxide anion. , 2011, Chemistry.

[31]  T. Klapötke,et al.  1,1'-azobis(tetrazole): a highly energetic nitrogen-rich compound with a N10 chain. , 2011, Inorganic chemistry.

[32]  Y. Wang,et al.  A novel stable high-nitrogen energetic material: 4,4′-azobis(1,2,4-triazole) , 2011 .

[33]  M. Göbel,et al.  Nitrotetrazolate-2N-oxides and the strategy of N-oxide introduction. , 2010, Journal of the American Chemical Society.

[34]  T. Klapötke,et al.  Nitrogen-Rich Salts Based on the Energetic 5,5'-(Hydrazine-1,2-diyl)bis-[1H-tetrazolide] Anion , 2009 .

[35]  T. Klapötke,et al.  Safe 5-nitrotetrazolate anion transfer reagents. , 2009, Dalton transactions.

[36]  T. Klapötke,et al.  The CN7(-) anion. , 2009, Journal of the American Chemical Society.

[37]  T. Klapötke,et al.  Investigations of bis(methyltetrazolyl)triazenes as nitrogen-rich ingredients in solid rocket propellants – Synthesis, characterization and properties , 2009 .

[38]  T. Klapötke,et al.  Neutral 5-nitrotetrazoles: easy initiation with low pollution , 2009 .

[39]  T. Klapötke,et al.  Salts of 1H‐Tetrazole – Synthesis, Characterization and Properties , 2008 .

[40]  J. Welch,et al.  Simple, nitrogen-rich, energetic salts of 5-nitrotetrazole. , 2008, Inorganic chemistry.

[41]  T. Klapötke,et al.  5-Azido-1H-tetrazole – Improved Synthesis, Crystal Structure and Sensitivity Data , 2008 .

[42]  J. Welch,et al.  Salts of methylated 5-aminotetrazoles with energetic anions. , 2008, Inorganic chemistry.

[43]  T. Kolev,et al.  Zwitterionic 2-guanidinium-1-amino­carboxyl­ate monohydrate , 2003 .

[44]  T. Klapötke,et al.  Tetrazolylpentazoles: nitrogen-rich compounds. , 2002, Inorganic chemistry.

[45]  T. Klapötke,et al.  [N2H5]+2[N4C−NN−CN4]2-: A New High-Nitrogen High-Energetic Material , 2001 .

[46]  B. Ugrak,et al.  Synthesis of mesoionic 3-aryl(hetaryl)-1,2,3,4-oxatriazol-5-ones b based on N-aryl-and N-hetarylhydrazones of bromonitroformaldehyde , 1999 .

[47]  S. Shevelev,et al.  Synthesis of mesoionic 3-aryl- and 3-hetaryl-1,2,3,4-oxatriazol-5-ones , 1997 .

[48]  S. Ioffe,et al.  Synthesis of l-aryl-2-nitrodiazene 1-N-oxides , 1996 .

[49]  B. Clinton.  Executive Order 12856: Federal Compliance with Right-to-Know Laws and Pollution Prevention Requirements , 1993 .

[50]  J. H. Boyer,et al.  Mesoionic oxadiazolium-olates and oxatriazolium-olates from aryl isocyanides and nitroform , 1983 .

[51]  L. Kier,et al.  Preliminary studies of mesoionic 3-(substituted-aryl)-psi-oxatriazoles as potential antihypertensive agents. , 1982, Journal of medicinal chemistry.

[52]  V. G. Yashunskii,et al.  Reactions involving the formation of five-membered mesoionic heterocycles (review) , 1981 .

[53]  J. Tillett,et al.  Acid-catalyzed hydrolysis of 3-isopropyl-4 azasydnone , 1976 .