2038-44-0Relevant articles and documents
Optimization Studies on Synthesis of TKX-50
Golenko, Yulia D.,Topchiy, Maxim A.,Asachenko, Andrey F.,Nechaev, Mikhail S.,Pleshakov, Dmitriy V.
, p. 98 - 102 (2017)
A systematic study of TKX-50 and ABTOX synthesis using both Klap?tke and Tselinskii modified procedures is described. The influence of temperature, moisture, acid amount and nature on the most critical synthesis step – diazidoglyoxime cyclization is shown. Experimental results show that presence of moisture in reaction mixture leads to product yield decreasing. The reaction temperature is another key parameter affecting product yield. High reaction temperature shows negative influence on the product yield in Klap?tke method. In Tselinskii procedure the yield of product grows with the reaction temperature increasing. For Klap?tke one-pot method, combination of N-methyl-2-pyrrolidone with 1,4-dioxane is the best solvent, whereas Tselinskii one-pot procedure gives high yield of product when combination of toluene with 0.5 equiv. of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is used. Using optimized conditions one-pot five-step synthesis of TKX-50 starting from glyoxime is successfully performed and scaled up to 50 g.
Synthesis of bis-Isoxazole-bis-Methylene Dinitrate: A Potential Nitrate Plasticizer and Melt-Castable Energetic Material
Wingard, Leah A.,Guzmán, Pablo E.,Johnson, Eric C.,Sabatini, Jesse J.,Drake, Gregory W.,Byrd, Edward F. C.
, p. 195 - 198 (2017)
The efficient and scalable synthesis of 3,3′-bis-isoxazole-5,5′-bis-methylene dinitrate and its energetic properties are described. The material has favorable sensitivity properties; energetic properties point toward its potential as both a melt-castable secondary explosive and as a propellant plasticizer.
Nitrogen-rich energetic salts of 1: H,1′ H -5,5′-bistetrazole-1,1′-diolate: Synthesis, characterization, and thermal behaviors
Shang, Yu,Jin, Bo,Peng, Rufang,Guo, Zhicheng,Liu, Qiangqiang,Zhao, Jun,Zhang, Qingchun
, p. 48590 - 48598 (2016)
A series of nitrogen-rich heterocyclic 1H,1′H-5,5′-bistetrazole-1,1′-diolate salts, namely, 1,2,4-triazolium (2), 3-amino-1,2,4-triazolium (3), 4-amino-1,2,4-triazolium (4), 3,5-diamino-1,2,4-triazolium (5), 2-methylimidazolium (6), imidazolium (7), pyrazolium (8), 3-amino-5-hydroxypyrazolium (9), dicyandiamidine (10), and 2,4-diamino-6-methyl-1,3,5-triazin (11), was synthesized with cations. These energetic salts were fully characterized through FT-IR, 1H NMR, 13C NMR, and elemental analysis. The structures of 2, 3·7H2O, 6·2H2O, 8, and 10·4H2O were further confirmed through single crystal X-ray diffraction. Their thermal stabilities were investigated through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results indicated that all of the salts possess excellent thermal stabilities with decomposition temperatures ranging from 225.7 °C to 314.0 °C. On the basis of the Kamlet-Jacobs formula, we carefully calculated their detonation velocities and detonation pressures. All of the salts, except 11, exhibit promising detonation performances with a detonation pressure of 20.23-28.69 GPa and a detonation velocity of 7050-8218 m s-1. These values are much higher than those of TNT. The impact sensitivities of the compounds were determined via a Fall hammer test. All of the compounds show excellent impact sensitivities of >50 J, and this finding is higher than that of TATB (50 J). Therefore, these ionic salts with excellent energetic properties could be applied as new energetic materials.
Nitrogen-rich salts of 1H,1′H-5,5′-Bitetrazole-1,1′-diol: Energetic materials with high thermal stability
Fischer, Niko,Klapoetke, Thomas M.,Reymann, Marius,Stierstorfer, Joerg
, p. 2167 - 2180 (2013)
1H,1′H-5,5′-Bitetrazole-1,1′-diol was synthesized starting from glyoxal, which is converted to glyoxime after treatment with hydroxylamine. Chlorination of glyoxime with Cl2 gas in ethanol and following chloro/azido exchange yields diazidoglyoxime, which is cyclized under acidic conditions (HCl gas in diethyl ether) to give 1H,1′H-5,5′- bitetrazole-1,1′-diol dihydrate (1). A large variety of nitrogen-rich salts of 1 such as the diammonium (2), the dihydrazinium (3), the bis-guanidinium (4), the bis(aminoguanidinium) (5), the diaminoguanidinium salt monohydrate (6), the triaminoguanidinium salt monohydrate (7), the 1-amino-3-nitroguanidinium salt dihydrate (8), the diaminouronium salt monohydrate (9), the bis(oxalyldihydrazidinium) (10), the oxalyldihydrazidinium salt dihydrate (11), the 3,6-dihydrazino-1,2,4,5-tetrazinium (12), the 5-aminotetrazolium (13), the bis(5-amino-1-methyl-1H-tetrazolium) salt (14), the bis(5-amino-2-methyl-2H-tetrazole) adduct (15), and the 1,5-diaminotetrazolium salt (16) were synthesized by means of Bronsted acid-base or metathesis reactions. All compounds were fully characterized by vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, elemental analysis, and differential scanning calorimetry (DSC) measurements. The crystal structures of 1-16 could be determined by using single-crystal X-ray diffraction. The heats of formation of 1-16 were calculated by using the atomization method on the basis of CBS-4M enthalpies. With regard to their potential use as cyclotrimethylene trinitramine (RDX) or hexanitrostilbene (HNS) replacements, several detonation parameters such as the detonation pressure, detonation velocity, explosion energy, and explosion temperature were computed using the EXPLO5 code on the basis of the experimental (X-ray) densities and calculated heats of formation. In addition, the sensitivities towards impact, friction, and electrical discharge were tested using the BAM drop hammer, a friction tester, as well as a small-scale electrical discharge device. Copyright
Preparation and characterization of nitrogen-rich bis-1-methylimidazole1H,1′H-5,5′-bistetrazole-1,1′-diolate energetic salt
Luo, Liqiong,Jin, Bo,Peng, Rufang,Shang, Yu,Xiao, Lipengcheng,Chu, Shijin
, p. 1 - 9 (2018)
A new nitrogen-rich energetic salt of bis-1-methylimidazole 1H,1′H-5,5′-bistetrazole-1,1′-diolate salt, (1-M)2BTO, was synthesized and characterized (FT-IR, 1H NMR, 13C NMR, elemental analysis, and X-ray single-crystal diffraction). Results indicated that (1-M)2BTO crystallizes in the triclinic space group P-1. The thermal decomposition behavior of (1-M)2BTO was determined by differential scanning calorimetry (DSC) and thermogravimetric tandem infrared spectroscopy. The decomposition peak temperature of (1-M)2BTO was 530 K, which suggested that the salt is strong heat resistance. The apparent activation energies were 130.56 kJ mol?1 (Kissinger’s method) and 132.50 kJ mol?1 (Ozawa’s method), respectively. The enthalpy of formation for the salt was calculated as 917.3 kJ mol?1. The detonation velocity and detonation pressure of (1-M)2BTO were 7448 m s?1 and 20.7 GPa, respectively, using the Kamlet-Jacobs equation. Furthermore, the sensitivity test results showed that its impact sensitivity is greater than 50 J and friction sensitivity is 180 N, indicating that it has a lower sensitivity.
METHOD FOR SYNTHESIS OF TKX-50 USING INSENSITIVE INTERMEDIATE
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Paragraph 0066, (2021/06/04)
The present invention relates to a method for synthesis of TKX-50 using an insensitive intermediate and, more specifically, to a method for producing TKX-50, the method comprising the steps of: preparing DCG as a starting material; forming a THP-DAG intermediate from the DCG; and synthesizing TKX-50 through the THP-DAG intermediate.
Method for preparation of insensitive high explosive
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Page/Page column 7-10, (2021/11/03)
The present invention provides a method for the preparation of an insensitive high enthalpy explosive Dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50) in the presence of N,N-dimethylformamide, N,N-dimethylacetamide, or N-Methyl-2-pyrrolidone as a solvent via a four-step, one-pot reaction route to obtain a final product after four reaction steps. The more dangerous intermediate diazidoglyoxime may be solved by the one-pot method without the need of isolation. Further, the cyclization reaction is carried out in the presence of dropwisely added concentrated sulfuric acid to replace hydrochloric gas so no hydrochloric gas generator is needed to greatly reduce the amount of waste acid so as to effectively reduce the cost by avoiding using hydrochloric gas steel cylinders which require much safety equipment.
