- Synthesis, Characterization, and Properties of Energetic Compounds Based on a CH2-Bridged Dinitromethyl Explosophore
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A series of energetic salts based on the 1,1,3,3-tetranitropropane-1,3-diide (TNP) dianion have been prepared and fully characterized by NMR and IR spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Their thermal stability (Td = 111.0–180.9 °C) and sensitivities to mechanical stimuli (IS = 2–5 J; FS = 80–128 N) have been measured. Additionally, their heats of formation (–369.8 to 347.1 kJ mol–1) and detonation performances (P = 25.0–37.0 GPa; vD = 7675–9104 m s–1) have been calculated.
- Huang, Haifeng,Shi, Yameng,Yu, Yao,Yang, Jun
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- 1,1-Diamino-2,2-dinitroethene (FOX-7) and 1-amino-1-hydrazino-2,2-dinitroethene (HFOX) as amphotères: bases with strong acids
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The exciting discovery of the first cations based on 1,1-diamino-2,2-dinitroethene (FOX-7) and its hydrazine derivative, 1-amino-1-hydrazino-2,2-dinitroethene (HFOX), along with their syntheses and full characterization is described. The oxygen rich content of these cations lends to their potential as promising precursors for energetic salts. A variety of acids including triflic, perchloric, and hydrochloric acids were found to react with FOX-7 and HFOX to give rise to the following salts: 1-amino-2,2-dinitroethaniminium triflate (3a), 1-amino-2,2-dinitroethaniminium perchlorate (3b), 1-amino-1-hydrazino-2,2-dinitroethaniminium triflate (4a), and 1-amino-1-hydrazino-2,2-dinitroethaniminium chloride (5). Additionally, it was also found that HFOX reacts with acetone to generate the corresponding hydrazone derivative, 2,2-dinitro-1-(2-(propan-2-ylidene)hydrazinyl)ethenamine (9). The structures of the salts (except 5) and hydrazone 9 are supported by single crystal X-ray analysis. These compounds have thermal stabilities ranging between 74-147 °C and crystal densities between 1.53 g cm-3 to 1.94 g cm-3. The isolation of these novel FOX-7 and HFOX cations are interestingly important as it: (1) extends the chemistry of FOX-7 and HFOX, (2) demonstrates the amphoteric properties of FOX-7 and HFOX, and (3) gives rise to new forms of FOX-7 and HFOX, which opens the study of their potential as promising precursors for energetic salts. All the salts were found to have energetic properties that exceed that of TNT and some are comparable to FOX-7 and RDX, indicating that the cations of FOX-7 and HFOX may contribute to more energetic salts if parlayed with appropriate counter anions. The significance of this work demonstrates that the chemistry of FOX-7 continues to be profound and worthwhile.
- Vo, Thao T.,Shreeve, Jean'Ne M.
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- Cocrystal structure, thermal behavior, and DFT calculations between FOX–7 and 1,10–Phenanthroline
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Cocrystal of FOX–7 (1,1-diamino-2,2-dinitroethene) and Phen (1,10-Phenanthroline) has been synthesized and characterized by X–ray crystallography. The single crystal results show that FOX–7 and its cocrystal were crystallized in the monoclinic space groups P21/n and P21/c, respectively. Thermal stability of FOX–7 and FOX–7·Phen were studied by DSC, the first exothermic peak temperatures (TP) of FOX–7 and FOX–7·Phen occurs at 223.2 and 232.7 °C, respectively; indicating that FOX–7·Phen is more stable than FOX–7. Thermokinetic parameters such as the activation energy Ea and pre-exponential factor A were 321.4 kJ mol?1 and 1.166 × 1033 s?1, respectively. DFT studies including geometry optimization, HOMO-LUMO analysis, Mulliken charge and UV–visible spectral data were also calculated by DFT-B3LYP/6-31 + G** level.
- Li, Keyao,Ren, Xiangwen,Fu, Shuqin,Zhu, Jiaping
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- 1,1-Diamino-2,2-dinitroethylenes are always zwitterions
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The nitration of tetraiodoethylene (7) yields 1,1-diiodo-2,2- dinitroethylene (8). The latter reacts with alkylamines 9 or alkyldiamines 11 to give the corresponding acyclic 1,1-diamino-2,2-dinitroethylenes 10 or their cyclic analogs 12, respectively. On the basis of liquid and solid-state 13C and 15N NMR data, x-ray analysis and ab initio calculations, we suggest that the title compounds are always zwitterionic and that the CA-CN bond is not a true double bond. Copyright
- Gilinsky-Sharon, Pessia,Gottlieb, Hugo E.,Rajsfus, David E.,Keinan-Adamsky, Keren,Marks, Vered,Aped, Pinchas,Frimer, Aryeh A.
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- A Halogen-Free Green High Energy Density Oxidizer from H-FOX
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Reaction of H-FOX (1-hydrazinyl-2,2-dinitroethenamine) with 2,2,2-trinitroethanol resulted in an unexpected compound, 1,1′-methylenebis[3-(2,2,2-trinitroethyl)urea] (5), which when treated with acetic anhydride and 100 % nitric acid gave an N-NO2 derivative, 1,1′-methylenebis[1-nitro-3-(2,2,2-trinitroethyl)urea] (6) in good yield. Compound 6 exhibits a good oxygen balance (+20.4 %), density (d = 1.87 g/cm3) and excellent detonation performance (vD = 8910 m/s; P = 35.8 GPa) as well as acceptable stability and sensitivity, which suggests it as an attractive replacement for ammonium perchlorate (AP).
- Dharavath, Srinivas,Tang, Yongxing,Kumar, Dheeraj,Mitchell, Lauren A.,Parrish, Damon A.,Shreeve, Jean'ne M.
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- Desensitization of the dinitromethyl group: Molecular/crystalline factors that affect the sensitivities of energetic materials
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The dinitromethyl group has attracted considerable attention because of its high nitrogen and oxygen content, positive oxygen balance and high energy. Although most dinitromethyl-functionalized compounds suffer from sensitivity to mechanical stimuli, a series of 3-dinitromethanide-1,2,4-triazolone-based energetic salts have now been synthesized and fully characterized. Of these, the ammonium salt is insensitive to impact and friction. X-ray single crystal analysis shows that the ammonium moiety arranges through a close layer-by-layer assembly, which is helpful in decreasing sensitivity. In addition, intramolecular hydrogen-bonding interactions, and intense π-π interactions also are stabilizing factors which impact the sensitivity of the ammonium salt. The enthalpies of formation and energetic properties of the series of salts were determined in order to reach the conclusion that these multiple stabilization factors are effective tools in decreasing the sensitivity of dinitromethyl-based energetic materials.
- Zhang, Jichuan,Zhang, Jiaheng,Parrish, Damon A.,Shreeve, Jean'Ne M.
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- On the synthesis of 1,1-diamino-2,2-dinitroethene (FOX-7) by nitration of 4,6-dihydroxy-2-methylpyrimidine
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The synthesis of 1,1-diamino-2,2-dinitroethene (FOX-7) by nitration of 4,6-dihydroxy-2-methylpyrimidine and hydrolysis of the resulting intermediate 2-dinitromethylene-5,5-dinitropy-rimidine-4,6-dione has been studied. By varying the reaction parameters the optimal conditions for the synthesis of FOX-7 have been identified and gave a >90% yield of the pure product. The optimised process allowed the spent acid to be recycled without loss of yield, with almost stoichiometric consumption of nitric acid. The purity of the FOX-7 has been determined using a newly developed HPLC method
- Latypov, Nikolaj V.,Johansson, Martin,Holmgren, Erik,Sizova, Ekaterina V.,Sizov, Vladimir V.,Bellamy, Anthony J.
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- Some specific features of acid nitration of 2-substituted 4,6-dihydroxypyrimidines. Nucleophilic cleavage of the nitration products
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The nitration of 2-substituted 4,6-dihydroxypyrimidines in concentrated sulfuric acid yields the corresponding 5,5-dinitro derivatives. When the substituent in position 2 is an alkyl group, the nitration occurs both at position 5 and at the α-carbon atom of the side chain. Hydrolysis of 2-substituted 4,6-dihydroxy-5,5-dinitropyrimidines leads to formation of 1,1-diamino-2-R-2-nitroethylene derivatives. 1,1-Diamino-2,2-dinitroethylene was obtained by nitration of 4,6-dihydroxy-2-methylpyrimidine and subsequent hydrolysis of 4,6-dihydroxy-5,5-dinitro-2-(dinitromethylene)-2,5-dihydropyrimidine.
- Astrat'ev,Dashko,Mershin,Stepanov,Urazgil'deev
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- The unimolecular chemistry of protonated and deprotonated 2, 2-dinitroethene-1, 1-diamine (FOX-7) studied by tandem mass spectrometry and computational chemistry
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2, 2-Dinitroethene-1, 1-diamine (FOX-7) was studied by means of electrospray ionization (ESI) and chemical ionization (CI) mass spectrometry in both positive and negative ion mode. Detailed mechanisms of unimolecular fragmentations of protonated and deprotonated FOX-7 were investigated using high- and low-energy collision-induced dissociation (CID) mass spectrometry, neutral fragment reionization mass spectrometry and quantum chemistry calculations. In deprotonated FOX-7, elimination of the carbodiimide molecule was identified as the energetically most favored fragmentation channel, closely resembling the base hydrolysis of FOX-7. The dinitromethanide ion is formed during this fragmentation as revealed by comparison with CID mass spectra of an isobaric ion prepared by the ESI of authentic sodium dinitromethanide. The proton affinity of FOX-7 was estimated as 855 kJ mol-1 by high-accuracy quantum chemistry calculations. This value corresponds to protonation at the C-2 position, though the oxygen-protonated tautomer was found to be nearly isoenergetic in the gas phase. In acetonitrile, the nitro group-protonated FOX-7 was found to be significantly less stable then its C-2 tautomer. These theoretical findings are clearly reflected in differences in fragmentations of ESI- and CI-generated [M + H]+ ions. Interestingly, the consecutive losses of OH· and NO2 · radicals instead of a whole HNO3 molecule were found to account for the most abundant fragment ion in the positive ESI CID mass spectra. In the CI-generated [M + H]+1 and [M+D]+ ions, substantial internal energy effects upon the CID were observed.
- Zabka, Jan,Simkova, Ludmila,Jalovy, Zdenek,Polasek, Miroslav
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- Predicting the impact sensitivity of a polymorphic high explosive: The curious case of FOX-7
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The impact sensitivity (IS) of FOX-7 polymorphs is predicted by phonon up-pumping to decrease as layers of FOX-7 molecules flatten. Experimental validation proved anomalous owing to a phase transition during testing, raising questions regarding impact sensitivity measurement and highlighting the need for models to predict IS of polymorphic energetic materials.
- Michalchuk, Adam A. L.,Morrison, Carole A.,Pulham, Colin R.,Rudi?, Svemir
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supporting information
p. 11213 - 11216
(2021/11/03)
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- Application of [PVI-SO3H]NO3as a novel polymeric nitrating agent with ionic tags in preparation of high-energetic materials
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In this paper, poly(vinyl imidazole) sulfonic acid nitrate [PVI-SO3H]NO3was synthesized and fully characterized. Then, [PVI-SO3H]NO3was applied for the preparation of energetic materials such as 1,1-diamino-2,2-dinitroethene (FOX-7), pentaerythritol tetranitrate (PETN), 1,3,5-trinitro-1,3,5-triazinane (RDX) and trinitrotoluene (TNT). The major advantages of the presented methodology are mild, facile workup, high yields and short reaction times. [PVI-SO3H]NO3is a suitable nitrating agent forin situgeneration of NO2and without using any co-catalysts of the described nitrating reagent.
- Sepehrmansourie, Hassan,Zarei, Mahmoud,Zolfigol, Mohammad Ali,Mehrzad, Amin,Hafizi-Atabak, Hamid Reza
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p. 8367 - 8374
(2021/03/03)
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- A 1, 1 - diamino - 2, 2 - dinitro ethylene synthesis method
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The invention discloses a method for synthesizing 1,1-diamino-2,2-dinitroethylene. The method comprises the steps as follows: sulfuric acid is added to a reaction flask firstly, nitric acid is then added dropwise, and mixed nitric-sulfuric acid is prepared; 2-methyl-4,6-pyrimidinedione or 2-methyl-4,6-hydroxypyrimidine is added to the mixed nitric-sulfuric acid in batch, filtering is performed after reaction, a nitrating acid filtrate is collected, a filter cake is added to ice water, filtering and drying are performed, and 1,1-diamino-2,2-dinitroethylene is obtained; fuming sulfuric acid withmass fraction of 50% and nitric acid with mass fraction of 98% are added to the collected nitrating acid filtrate in proportion sequentially, and the prepared mixed nitric-sulfuric acid can be recycled directly. The method is used for synthesizing 1,1-diamino-2,2-dinitroethylene.
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Paragraph 0039-0042
(2019/11/13)
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- METHOD FOR PREPARATION OF 1,1-DIAMINO-2,2-DINITROETHYLENE
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Disclosed is a method for preparation of 1,1-diamino-2,2-dinitroethylene (DADNE) through the hydrolysis of 4,6-dihydroxy-5,5-dinitro-2-(dinitromethylene)-2,5-dihydropyrimidine (DHDNDP) obtained by the nitration of 4,6-dihydroxy-2-methylpyrimidine (DHMP), which can avoid eruption or sudden frothing of a reaction solution on a lab scale and even a large scale preparation as well as reduce the reaction time.
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Page/Page column 2
(2012/07/27)
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- Study on reactions of 2-(dinitromethylene)-4,5-imidazolidinedione
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Some new reactions of 2-(dinitromethylene)-4,5-imidazolidinedione (1) with water, alcohols, carboxylic acids, and alkalis were discovered. By reaction of 1 with carboxylic acids, large particle size 1,1-diamino-2,2-dinitroethylene (2) was prepared. By reaction of 1 with methanol, the methanol adduct (4) was synthesized and characterized. By reaction of 1 with water, the synthetic pathway of 2-methylimidazole to 2 could be achieved in a continuous process. By reaction of 1 with KOH, 2 and potassium dinitromethane (6) could be formed at different temperature, respectively. Compounds 1 and 4 decomposed into parabanic acid (5), losing nitrogen oxides and carbon oxides. Some explosive properties of 1 were studied. The mechanisms of synthesis of 1, 2, and 5 are discussed.
- Cai, Huaqiang,Shu, Yuanjie,Huang, Hui,Cheng, Bibo,Li, Jinshan
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p. 4369 - 4374
(2007/10/03)
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- Nitration of the 6-methyl-1,3,5-triazine derivatives, 6-methyl-1,3,5-triazine-2,4(1H,3H)-dione and 2,4-dimethoxy-6-methyl-1,3,5-triazine
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Nitration of 2-methylpyrimidin-4,6(3H,5H)-dione (II) is known to give, after hydrolysis of the tetranitro intermediate, 1,1-diamino-2,2-dinitroethene (I). However, nitration of analogous 6-methyl-1,3,5-triazine derivatives was found to lead to somewhat different products. Nitration of 6-methyl-1,3,5-triazine-2,4(1H,3H)-dione (III) gave 2,4,6-trihydroxy-1,3,5-triazine (cyanuric acid, V) and tetranitromethane (VI). Nitration of 2,4-dimethoxy-6-methyl-1,3,5-triazine (IV) with mixed acid gave 2,4-dimethoxy-6-trinitromethyl-1,3,5-triazine (VII), whilst with nitric acid alone a furazan N-oxide derivative (IX) was obtained.
- Bellamy, Anthony J.,Latypov, Nikolaj V.,Goede, Patrick
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p. 943 - 958
(2007/10/03)
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- Method of preparing salts of dinitromethane
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A method of preparing dinitromethane salts usable as intermediate products add starting material for production of explosives and propellants. Substituted 1,2-diazoles, 1,2,4 -triazoles or 1,3-diazines, such as barbituric acid, are nitrated to obtain a gem-dinitro group on a carbon atom in the heterocyclic ring. The product is hydrolysed to split off dinitromethane which is neutralised with a neutralising agent to obtain a corresponding salt of dinitromethane.
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- Chemical compound suitable for use as an explosive, intermediate and method for preparing the compound
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A new compound, 1,1-diamino-2,2-dinitroethylene suitable for use as an explosive, as well as an intermediate for preparing the compound consisting of a heterocyclic 5- or 6-ring of the general formula wherein n=at least 1. The compound is prepared by nitrating a heterocyclic 5- or 6-ring containing the structural element wherein Y is an alkoxy group, with a nitrating acid at a low temperature, preferably 0-30° C., and selecting the acidity of the nitrating acid for obtaining a substantial yield of a product containing the structural element and hydrolyzing said product in an aqueous medium for separating 1,1-diamino-2,2--dinitroethylene which is recovered as a precipitate.
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- Synthesis and reactions of 1,1-diamino-2,2-dinitroethylene
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Low temperature nitrations of 2-methylimidazole gave in addition to the known 2-methyl-5(4)-nitroimidazole (1), 2- (dinitromethylene)-5,5-dinitro-4- imidazolidinone (3) and parabanic acid (2). The tetranitro compound 3 was also obtained by nitration of 2-methyl-4,5-dihydro-(1H)-5-imidazolone (8). Thermal decomposition of 3 gave 2-(dinitromethylene)-4,5-imidazolidinedione (4) which also was the product from nitration of the new compound 2-methoxy- 2-methyl-4,5- imidazolidinedione. Treatment of 4 with aqueous ammonia gave the previously unknown 1,1-diamino-2,2-dinitroethylene (5). The physical properties and chemical behaviour of (5) are described.
- Latypov, Nikolai V.,Bergman, Jan,Langtet, Abraham,Wellmar, Ulf,Bemm, Ulf
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p. 11525 - 11536
(2007/10/03)
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