Isomers of Dinitropyrazoles: Synthesis, Comparison and Tuning of their Physicochemical Properties
- 1 August 2018
- journal article
- research article
- Published by Wiley in Chempluschem
- Vol. 83 (8), 804-811
- https://doi.org/10.1002/cplu.201800318
Abstract
Three isomeric dinitropyrazoles (DNPs) were synthesized starting from readily available 1H-pyrazole by slightly improved methods than described in the literature. 3,4-Dinitropyrazole (3), 1,3-dinitropyrazole (4), and 3,5-dinitropyrazole (5) were obtained and compared to each other with respect to thermal stability, crystallography, sensitivity and energetic performance. Two isomers (3 and 4) show high densities (1.79 and 1.76gcm(-3)) and interesting thermal behavior as melt-castable materials (3: T-melt.=71 degrees C, T-dec.=285 degrees C; 5: T-melt. = 68 degrees C, T-dec.=171 degrees C). Furthermore, eight salts (sodium, potassium, ammonium, hydrazinium, hydroxylammonium, guanidinium, aminoguanidinium and 3,6,7-triamino-[1,2,4]triazolo[4,3-b][1,2,4]triazole (TATOT) of 3 and 5 were synthesized in order to tune performance and sensitivity values. These compounds were characterized using H-1, C-13, N-14, N-15 NMR and IR spectroscopy as well as mass spectrometry, elemental analysis and thermal analysis through differential scanning calorimetry. Crystal structures of 14 compounds were obtained (3-7, 10-12 and 15-20) by low-temperature single crystal X-ray diffraction. Impact, friction and electrostatic discharge (ESD) values were also determined by standard methods. The sensitivity values range between 8.5 and 40J for impact and 240N and 360N for friction and show mainly insensitive character. The energetic performances were determined using recalculated X-ray densities, heats of formation and the EXPLO5 code and support the energetic character of the title compounds. The calculated energetic performances (V-D: 6245-8610ms(-1); p(CJ): 14.1-30.8GPa) were compared to RDX ((O2NNCH2)(3)).Funding Information
- Office of Naval Research (ONR.N00014-16-1-2062)
This publication has 34 references indexed in Scilit:
- (E)‐1,2‐Bis(3,5‐dinitro‐1H‐pyrazol‐4‐yl)diazene – Its 3D Potassium Metal–Organic Framework and Organic Salts with Super‐Heat‐Resistant PropertiesEuropean Journal of Inorganic Chemistry, 2017
- Comparative Study of Various Pyrazole‐based Anions: A Promising Family of Ionic Derivatives as Insensitive Energetic MaterialsChemistry – An Asian Journal, 2017
- ExplosivesPublished by Wiley ,2016
- 3,6,7‐Triamino‐[1,2,4]triazolo[4,3‐b][1,2,4]triazole: A Non‐toxic, High‐Performance Energetic Building Block with Excellent StabilityChemistry – A European Journal, 2015
- Energetic High-Nitrogen Compounds: 5-(Trinitromethyl)-2H-tetrazole and -tetrazolates, Preparation, Characterization, and Conversion into 5-(Dinitromethyl)tetrazolesInorganic Chemistry, 2013
- Assessing the non-cancer risk for RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) using physiologically based pharmacokinetic (PBPK) modelingRegulatory Toxicology and Pharmacology, 2012
- Trinitromethyl-Substituted 5-Nitro- or 3-Azo-1,2,4-triazoles: Synthesis, Characterization, and Energetic PropertiesJournal of the American Chemical Society, 2011
- High Energy Density MaterialsPublished by Springer Science and Business Media LLC ,2007
- Reevaluation of a Twenty-Four-Month Chronic Toxicity/Carcinogenicity Study of Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in the B6C3F1 Hybrid MouseInternational Journal of Toxicology, 2006
- Energetic Salts from N-AminoazolesInorganic Chemistry, 2004