- Preparation, crystal structure and properties of a new crystal form of diammonium 5,5′-bistetrazole-1,1′-diolate
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A new crystal form of diammonium 5,5′-bistetrazole-1,1′-diolate (1) was prepared by two novel methods and fully characterized by using IR, NMR spectroscopy, elementary analysis, single crystal X-ray crystallography and thermal gravity/differential thermal analysis (TG/DTA). Crystalline 1 was found as monoclinic and space group of P21/c (14). The TG/DTA analysis showed that the decomposition temperature of 1 was 287.8°C with a mass loss of 91.2% in the range of 220-300°C at a heating rate of 5°C/min. The sensitivities test towards impact, friction of 1 indicated that 1 has much lower sensitivities than those of RDX/HMX and is comparable to those of TNT, which suggested that 1 could be used as a good candidate of new insensitive energetic compound. A new crystal form of diammonium 5,5′-bistetrazole-1,1′-diolate (1) was prepared by two different novel methods and found as monoclinic and space group of P21/c (14). The thermal decomposition analysis and sensitivities test towards impact, friction of 1 indicated that 1 has much lower sensitivities than those of RDX/HMX and comparable to those of TNT, which suggested that 1 could be used as a good candidate of new insensitive energetic compound.
- Wang, Xiaojun,Jin, Shaohua,Zhang, Chunyuan,Li, Lijie,Chen, Shusen,Shu, Qinghai
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Read Online
- Method for preparation of insensitive high explosive
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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.
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Page/Page column 7
(2021/11/03)
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- High-Throughput Screening of Earth-Abundant Water Reduction Catalysts toward Photocatalytic Hydrogen Evolution
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Noble-metal photosensitizers and water reduction co-catalysts (WRCs) still present the highest activity in homogeneous photocatalytic hydrogen production. The search for earth-abundant alternatives is usually limited by the time required to screen new catalyst combinations; however, here, we utilize newly designed and developed high-throughput photoreactors for the parallel synthesis of novel WRCs and colorimetric screening of hydrogen evolution. This unique approach allowed rapid optimization of photocatalytic water reduction using the organic photosensitizer Eosin Y and the archetypal cobaloxime WRC [Co(GL1)2pyCl], where GL1 is dimethylglyoxime and py is pyridine. Subsequent combinatorial synthesis generated 646 unique cobalt complexes of the type [Co(LL)2pyCl], where LL is a bidentate ligand, that identified promising new WRC candidates for hydrogen production. Density functional theory (DFT) calculations performed on such cobaloxime derivative complexes demonstrated that reactivity depends on hydride affinity. Alkyl-substituted glyoximes were necessary for hydrogen production and showed increased activity when paired with ligands containing strong hydrogen-bond donors.
- Motz, Rachel N.,Lopato, Eric M.,Connell, Timothy U.,Bernhard, Stefan
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supporting information
p. 774 - 781
(2021/02/05)
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- METHOD FOR SYNTHESIS OF TKX-50 USING INSENSITIVE INTERMEDIATE
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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.
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Paragraph 0065
(2021/06/04)
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- Synthesis method of 2-pyrazine carboxylic ester compound
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The invention provides a synthetic method of a 2-pyrazine carboxylic ester compound. The synthesis method comprises the following steps: S1, carrying out addition reaction on a compound 1 and glyoxal dioxime under the action of a Lewis acid catalyst to obtain an intermediate 1; and step S2, carrying out first dehydration reaction on the intermediate 1 to obtain the 2-pyrazine carboxylic ester compound, wherein the structural general formulas of the compound 1, the intermediate 1 and the 2-pyrazine carboxylic ester compound are sequentially shown in the specification, R1 being a C1-C15 substituted or unsubstituted alkyl group, and R2 being a C1-C10 alkyl group. The preparation cost (or commercially available price) of the initial raw material compound 1 adopted by the invention is generally far lower than that of a trifluoropyruvate methyl ester compound. Compared with the traditional preparation method of 3-trifluoromethyl-2-methyl pyrazinecarboxylate, the method has the advantages of mild reaction conditions, simple operation and wide raw material sources, avoids the use of an expensive coupling catalyst, and greatly reduces the cost.
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Paragraph 0038; 0045-0047
(2021/04/14)
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- Bis(Substituted Phenylamino)Glyoxime derivatives: Synthesis, characterization, and antimicrobial evaluation
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In present work, a set of bis(substituted phenylamino) glyoxime derivatives are presented by the dropwise addition of corresponding primary aryl amines to the dichloroglyoxime (1). Reactions of corresponding primary aryl amines containing various substituents in different positions with dichloroglyoxime (1) gave thirteen compounds. The structural characterization of a set of bis(substituted phenylamino) glyoxime derivatives have been performed on the basis of FTIR, mass, proton, and carbon NMR methods. The crystal structure of compound 3a has been determined by X-ray diffraction on a single crystal. The NMR spectrum and X-ray data of 3a show that two hydroxyl groups of dioxime situated at anti position. Furthermore, all of the synthesized compounds (3a-m) were tested for in vitro both antimicrobial activity. The minimal inhibitory concentrations (MICs) against 7 bacteria and 3 yeasts were also determined. Among them, compound 3f was the most potent compound against S. aureus with the value of MIC = 9.76 μg/mL for the antibacterial activity, in addition to this, compound 3i has a good potency against S. aureus and C. tropicalis (MIC = 78.12 μg/mL) for both antibacterial and antifungal activities, respectively.
- Bayrak, Nilüfer,Matarac?-Kara, Emel,Ozbek-Celik, Berna,Tuyun, Ama? Fatih,Y?ld?r?m, Hatice,Y?ld?z, Mahmut
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- Synthesis and Synthetic Application of Chloro- And Bromofuroxans
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Furoxans are potentially useful heteroaromatic units in pharmaceuticals and agrichemicals. However, the applications for furoxan-based compounds have been hampered due to the underdevelopment of their synthetic methods. Herein, we report a new synthetic approach for the synthesis of chloro- and bromofuroxans. The starting materials were dichloro- and dibromofuroxans, and the substituents were directly introduced to the furoxan ring in a modular fashion. The synthesized monohalofuroxans served as substrates for the installation of a second substituent to prepare further functionalized furoxans.
- Ando, Akihiro,Hasebe, Hayu,Hayashi, Masahiko,Kim, Hojin,Matsubara, Ryosuke,Tsuneda, Takao
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p. 5959 - 5972
(2020/05/26)
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- SYNTHESIS OF TKX-50 USING INSENSITIVE INTERMEDIATE
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The present invention relates to a method for synthesizing TKX-50 using an insensitive intermediate. More specifically, the present invention relates to a method for manufacturing TKX-50 comprising the following steps: preparing DCG as a starting material; forming a THP-DAG intermediate from the DCG; and synthesizing TKX-50 through the THP-DAG intermediate. The present invention allows an operator to synthesize TKX-50 more safely.(AA) Glyoxal(BB) GlyoximeCOPYRIGHT KIPO 2020
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Paragraph 0059; 0060
(2020/05/01)
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- SYNTHESIS OF TKX-50 USING INSENSITIVE INTERMEDIATE
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TKX-50 Is a method for synthesizing, using an obtuse intermediate, in which DCG is prepared from the starting material; and DCG is formed from THP-DAG, and; is synthesized through the THP-DAG intermediate. TKX-50. The method of; comprising the steps, TKX-50 and. (by machine translation)
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Paragraph 0024; 0059-0060
(2020/06/06)
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- FUNCTIONALITY PROTECTED DIAZIDOGLYOXIME AND SYNTHESIS METHOD OF THE SAME
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Is a,sectional view of a diazidoglycol protected with a functional group according to an embodiment of the present invention 1, which is represented by the following Formula : [Formula 1] (Wherein, R denotes tetrahydropyranyl (Tetrahydropyranyl; THP), methyl (Methyl; Me), methoxymethyl (Methoxymethyl; MOM),methoxymethyl (Methoxythiomethyl; MTM),methoxymethyl (Benzyloxymethyl; BOM), 2- methoxymethyl-(2-Methoxymethyl; MEM), 2-(-methoxymethyl)-methoxybenzyl ((2-(Trimethylsilyl)ethoxymethyl); SEM), trimethylsilyl-(Tetrahydrofuranyl; THF), t-methoxyethyl-(t-Butyl),methoxyethyl-(Allyl),trimethoxyacetate (Benzyl), p- dimethoxymethyl (p-Methoxybenzyl), 3,4-methylsilyl (3,4-Dimethoxybenzyl), o-trimethoxyethyl] (o-Nitrobenzyl), p-trimethoxyethyl -t- triethylsilyl (p-Nitrobenzyl),trimethoxyethyl] (Chloroacetate),butyl (Triphenylmethyl), (Triphenylmethoxyacetate),methylsilyl-(Benzoate) hexyl p- (Di-t-butylmethylsilyl; DTBMS), (Trimethylsilyl; TMS),(Acetate; Ac), methoxybenzyl (Triethylsilyl; TES),(Methoxyacetate), trimethoxyethyl] (Pivaloate), (Triisopropylsilyl; TIPS), t-trimethoxyethyl (p-Toluenesulfonate; Ts). (t-Butyldimethylsilyl; TBDMS), t-trimethoxyethyl]-butyl-(t-Butyldiphenylsilyl; TBDPS),).methylsilyl-triethylsilyl-trimethoxyethyl]-benzenesulfonate (Diphenylmethylsilyl; DPMS). (by machine translation)
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Paragraph 0087-0090
(2020/06/09)
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- Method for preparing important intermediate 1H-1,2,3-triazole of Tazobactam
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The invention discloses a method for preparing an important intermediate 1H-1,2,3-triazole of Tazobactam. The method comprises the steps: firstly, subjecting glyoxal to a reaction with hydroxylamine hydrochloride, so as to obtain an intermediate I; subjecting the intermediate I and an ammonium salt to cyclization in the presence of a catalyst, so as to obtain an intermediate II; and subjecting the intermediate II to a reaction with nitrite under acidic conditions to deaminate so as to obtain crude triazole, and carrying out further refining, thereby obtaining finished triazole. According to the method, the operation is simple, the production cycle is short, the aftertreatment is simple, few waste gases, waste water and waste residues are produced, and the obtained product is high in yield, good in purity and low in cost, so that the method is more applicable to industrial large-scale production.
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Paragraph 0047; 0048; 0053; 0054
(2019/10/01)
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- Preparation and characterization of nitrogen-rich bis-1-methylimidazole1H,1′H-5,5′-bistetrazole-1,1′-diolate energetic salt
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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.
- Luo, Liqiong,Jin, Bo,Peng, Rufang,Shang, Yu,Xiao, Lipengcheng,Chu, Shijin
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- Novel insensitive energetic-cocrystal-based BTO with good comprehensive properties
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Combining a layer construction strategy with cocrystallization techniques, we designed and prepared a structurally unusual 1H,1′H-5,5′-bistetrazole-1,1′-diolate (BTO) based energetic cocrystal, which we also confirmed by single-crystal X-ray diffraction and powder-crystal X-ray diffraction. The obtained cocrystal crystallizes in a triclinic system, P-1 space group, with a density of 1.72 g cm-3. The properties including the thermal stability, sensitivity and detonation performance of the cocrystal were analyzed in detail. In addition, the thermal decomposition behavior of the cocrystal was studied by differential calorimetry and thermogravimetry tandem infrared spectroscopy. The results indicated that the cocrystal exhibits strong resistance to thermal decomposition up to 535.6 K. The cocrystal also demonstrates a sensitivity of >50 J. Moreover, its formation enthalpy was estimated to be 2312.0 kJ mol-1, whereas its detonation velocity and detonation pressure were predicted to be 8.213 km s-1 and 29.1 GPa, respectively, by applying K-J equations. Therefore, as expected, the obtained cocrystal shows a good comprehensive performance, which proves that a high degree of layer-by-layer stacking is essential for the structural density, thermal stability and sensitivity.
- Tao, Jingjing,Jin, Bo,Chu, Shijin,Peng, Rufang,Shang, Yu,Tan, Bisheng
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p. 1784 - 1790
(2018/02/06)
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- Optimization Studies on Synthesis of TKX-50
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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.
- Golenko, Yulia D.,Topchiy, Maxim A.,Asachenko, Andrey F.,Nechaev, Mikhail S.,Pleshakov, Dmitriy V.
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supporting information
p. 98 - 102
(2017/02/05)
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- Hydroheteroarylation of Unactivated Alkenes Using N-Methoxyheteroarenium Salts
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We report the first reductive coupling of unactivated alkenes with N-methoxy pyridazinium, imidazolium, quinolinium, and isoquinolinium salts under hydrogen atom transfer (HAT) conditions, and an expanded scope for the coupling of alkenes with N-methoxy pyridinium salts. N-Methoxy pyridazinium, imidazolium, quinolinium, and isoquinolinium salts are accessible in 1-2 steps from the commercial arenes or arene N-oxides (25-99%). N-Methoxy imidazolium salts are accessible in three steps from commercial amines (50-85%). In total 36 discrete methoxyheteroarenium salts bearing electron-donating, electron-withdrawing, alkyl, aryl, halogen, and haloalkyl substituents were prepared (several in multigram quantities) and coupled with 38 different alkenes. The transformations proceed under neutral conditions at ambient temperature, provide monoalkylation products exclusively, and form a single alkene addition regioisomer. Preparatively useful and complementary site selectivities in the addition of secondary and tertiary radicals to pyidinium salts are documented: harder secondary radicals favor C-2 addition (2->10:1), while softer tertiary radicals favor bond formation to C-4 (4.7->29:1). A diene possessing a 1,2-disubstituted and 2,2-disubstituted alkene undergoes hydropyridylation at the latter exclusively (61%) suggesting useful site selectivities can be obtained in polyene substrates. The methoxypyridinium salts can also be employed in dehydrogenative arylation, borono-Minisci, and tandem arylation processes. Mechanistic studies support the involvement of a radical process.
- Ma, Xiaoshen,Dang, Hester,Rose, John A.,Rablen, Paul,Herzon, Seth B.
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supporting information
p. 5998 - 6007
(2017/05/04)
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- Synthesis, thermal behavior, and energetic properties of diuronium 1H,1′H-5,5′-bistetrazole-1,1′-diolate salt
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A new nitrogen-rich energetic salt called diuronium 1H,1′H-5,5′-bistetrazole-1,1′-diolate (DUBTO) was first synthesized by reacting urea with 1H,1′H-5,5′-bistetrazole-1,1′-diolate dihydrate (H2BTO 2H2O). The structure of this new energetic salt was fully characterized through single-crystal X-ray diffraction, FT-IR, 1H NMR, 13C NMR, and elemental analysis. DUBTO was crystallized in the monoclinic space group P21/n. The thermal stability was investigated through differential scanning calorimetry (DSC) and thermogravimetric tandem infrared spectrometry. Results showed that DUBTO contained one endothermic process and two exothermic processes. The second exothermic process is mainly intense exothermic decomposition with a mass loss of approximately 69.3% in the temperature range of 523.8–594.6?K. The non-isothermal kinetic parameters of the main exothermic process were calculated based on methods proposed by Kissinger and Ozawa-Doyle. Based on the Kamlet-Jacobs formula, the detonation velocity and detonation pressure of DUBTO were calculated as 8267?m?s?1 and 29.15?GPa, respectively.
- Shang, Yu,Jin, Bo,Liu, Qiangqiang,Peng, Rufang,Guo, Zhicheng,Zhang, Qingchun
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p. 519 - 525
(2016/12/30)
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- Exploiting the energetic potential of 1,2,4-oxadiazole derivatives: Combining the benefits of a 1,2,4-oxadiazole framework with various energetic functionalities
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A series of 1,2,4-oxadiazole-derived energetic compounds were successfully synthesized using 1,2,4-oxadiazole-3-chloroxime as a versatile starting material. These energetic compounds were fully characterized by NMR spectroscopy, IR spectroscopy, and elemental analysis. The structures of compounds 5, 6a, 6c, 8 and 8a were determined by single crystal X-ray diffraction. The physicochemical and energetic properties of all the synthesized energetic compounds, including density, thermal stability and energetic performance (e.g., detonation velocities and detonation pressures) were investigated. Among these energetic compounds, hydrazinium salts 6b and 8b and hydroxylammonium salts 6c and 8c exhibit satisfactory calculated detonation performances, which outperform the commonly used high explosive RDX. Potassium salt 5 shows good detonation performance, high density as well as high sensitivity, making it a potential primary explosive. Compound 9 is a potential candidate for melt-cast explosives due to its remarkable liquid range between melting point (Tm = 98 °C) and decomposition temperature (Td = 208 °C).
- Yan, Chao,Wang, Kangcai,Liu, Tianlin,Yang, Hongwei,Cheng, Guangbin,Zhang, Qinghua
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p. 14210 - 14218
(2017/11/06)
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- Production of dichloroglyoxime
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The present invention addresses the problem of providing a dichloroglyoxime production method by which dichloroglyoxime, which can be used as an industrial anti-bacterial agent, a preservative, a slime control agent or the like, can be obtained with greater safety and efficiency. In order to solve this problem, the present invention provides a method for producing dichloroglyoxime by reacting glyoxal with hydroxylamine and then chlorinating, the method additionally including: a step of incorporating a water-immiscible low boiling point organic solvent; a step of incorporating 20-90% of water following completion of the chlorination so as to cause separation into two layers, and then separating the organic layer; and a step of removing a water-miscible low boiling point organic solvent from the organic layer.
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Paragraph 0034-0041
(2017/12/27)
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- Nitrogen-rich energetic salts of 1: H,1′ H -5,5′-bistetrazole-1,1′-diolate: Synthesis, characterization, and thermal behaviors
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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.
- Shang, Yu,Jin, Bo,Peng, Rufang,Guo, Zhicheng,Liu, Qiangqiang,Zhao, Jun,Zhang, Qingchun
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p. 48590 - 48598
(2016/06/09)
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- N -Oxides light up energetic performances: Synthesis and characterization of dinitraminobisfuroxans and their salts
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4,4′-Diamino-[3,3′-bi(1,2,5-oxadiazole)]-5,5′-dioxide and 4,4′-diamino-[3,3′-bi(1,2,5-oxadiazole)]-2,2′-dioxide were nitrated in 100% HNO3 at -10 °C to give 4,4′-dinitramino-[3,3′-bi(1,2,5-oxadiazole)]-5,5′-dioxide (3) and 4,4′-diamino-[3,3′-bi(1,2,5-oxadiazole)]-2,2′-dioxide (4). Nine nitrogen-rich salts were prepared and were characterized by infrared and multinuclear NMR spectroscopy, elemental analysis, differential scanning calorimetry (DSC) and X-ray single crystal diffraction in some cases. Their detonation properties were evaluated by EXPLO 5 code using the measured density and calculated heat of formation. The sensitivities were determined by standard BAM methods. Several of the new molecules exhibit detonation and other properties which compete with or exceed those of HMX.
- He, Chunlin,Tang, Yongxing,Mitchell, Lauren A.,Parrish, Damon A.,Shreeve, Jean'Ne M.
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supporting information
p. 8969 - 8973
(2016/07/06)
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- A click chemistry approach to 5,5′-disubstituted-3,3′- bisisoxazoles from dichloroglyoxime and alkynes: Luminescent organometallic iridium and rhenium bisisoxazole complexes
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5,5′-Disubstituted-3,3′-bisisoxazoles are prepared in one step by the dropwise addition of aqueous potassium hydrogen carbonate to a mixture of dichloroglyoxime and terminal alkynes. The reaction exhibits a striking preference for the 5,5′-disubstituted 3,3′-bisisoxazole over the 4,5′-regioisomer. Organometallic iridium and rhenium bisisoxazole complexes are luminescent with emission wavelengths varying depending upon the identity of the 5,5′-substituent (phenyl, butyl).
- Van Der Peet, Phillip L.,Connell, Timothy U.,Gunawan, Christian,White, Jonathan M.,Donnelly, Paul S.,Williams, Spencer J.
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p. 7298 - 7304
(2013/08/23)
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- Nitrogen-rich salts of 1H,1′H-5,5′-Bitetrazole-1,1′-diol: Energetic materials with high thermal stability
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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
- Fischer, Niko,Klapoetke, Thomas M.,Reymann, Marius,Stierstorfer, Joerg
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p. 2167 - 2180
(2013/06/04)
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- Pushing the limits of energetic materials - The synthesis and characterization of dihydroxylammonium 5,5′-bistetrazole-1,1′- diolate
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The safe preparation and characterization (XRD, NMR and vibrational spectroscopy, DSC, mass spectrometry, sensitivities) of a new explosive dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50) that outperforms all other commonly used explosive materials is detailed. While much publicized high-performing explosives, such as octanitrocubane and CL-20, have been at the forefront of public awareness, this compound differs in that it is simple and cheap to prepare from commonly available chemicals. TKX-50 expands upon the newly exploited field of tetrazole oxide chemistry to produce a material that not only is easily prepared and exceedingly powerful, but also possesses the required thermal insensitivity, low toxicity, and safety of handling to replace the most commonly used military explosive, RDX (1,3,5-trinitro-1,3,5-triazacyclohexane). In addition, the crystal structures of the intermediates 5,5′-bistetrazole-1,1′-diol dihydrate, 5,5′-bistetrazole-1,1′-diol dimethanolate and dimethylammonium 5,5′-bistetrazole-1,1′-diolate were determined and presented.
- Fischer, Niko,Fischer, Dennis,Klapoetke, Thomas M.,Piercey, Davin G.,Stierstorfer, Joerg
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supporting information
p. 20418 - 20422
(2013/02/25)
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- Hydrogen generation catalyzed by fluorinated diglyoxime-iron complexes at low overpotentials
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FeII complexes containing the fluorinated ligand 1,2-bis(perfluorophenyl)ethane-1,2-dionedioxime (dArFgH2; H = dissociable proton) exhibit relatively positive FeII/I reduction potentials. The air-stable difluoroborated species [(dArFgBF 2)2Fe(py)2] (2) electrocatalyzes H2 generation at -0.9 V vs SCE with icat/ip ≈ 4, corresponding to a turnover frequency (TOF) of ～20 s-1 [Faradaic yield (FY) = 82 ± 13%]. The corresponding monofluoroborated, proton-bridged complex [(dArFg2H-BF2)Fe(py) 2] (3) exhibits an improved TOF of ～200 s-1 (i cat/ip ≈ 8; FY = 68 ± 14%) at -0.8 V with an overpotential of 300 mV. Simulations of the electrocatalytic cyclic voltammograms of 2 suggest rate-limiting protonation of an Fe "0" intermediate (kRLS ≈ 200 M-1 s-1) that undergoes hydride protonation to form H2. Complex 3 likely reacts via protonation of an FeI intermediate that subsequently forms H2 via a bimetallic mechanism (kRLS ≈ 2000 M-1 s-1). 3 catalyzes production at relatively positive potentials compared with other iron complexes.
- Rose, Michael J.,Gray, Harry B.,Winkler, Jay R.
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scheme or table
p. 8310 - 8313
(2012/06/29)
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- An exceptionally stable Ti superoxide radical ion: A novel heterogeneous catalyst for the direct conversion of aromatic primary amines to nitro compounds
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A matrix-bound superoxide radical anion, generated by treating Ti(OR)4 (R =iPr, nBu) with H2O2, is a selective heterogeneous catalyst for the oxidation of anilines to the corresponding nitroarenes with 50 % aqueous H2O2 [Eq. (1)]. Yields of 82-98 % are obtained, even with anilines bearing electron-withdrawing substituents (R = NO2, COOH).
- Dewkar, Gajanan K.,Nikalje, Milind D.,Ali, Iliyas Sayyed,Paraskar, Abhimanyu S.,Jagtap,Sudalai
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p. 405 - 408
(2007/10/03)
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- Uranyl Compounds with α-Dioximes: Mixed-Ligand Carbonatooxalate Complexes
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The interaction of uranyl complexes with α-dioximes having different structures in a carbonate-oxalate system was studied. It was shown that the pathway of the reaction and the compositions and the structures of the nascent complexes were significantly influenced by the α-dioxime structure. An X-ray diffraction study of (C2N2H10)2[(UO2) 2(CO3)(C2O4)2(C 3H4N2O2)] · H2O single crystals was carried out. The complex has a binuclear structure with bridging carbonate and methylglyoximate groups.
- Beirakhov,Orlova,Gorbunova,Mikhailov,Shchelokov
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p. 1414 - 1419
(2008/10/08)
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- A Convenient synthesis of 1,2,3-triazole with glyoxal
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A new synthetic method of 1,2,3-triazole from glyoxal mono-hydrazone mono-oxime (1a) has been developed. 1a obtained by the thermal disproportionation of glyoxal bis-hydrazone (1b) and glyoxime (1c) was treated with acetic anhydride to give 2-acetyl-1,2,3-triazole, following alcoholysis gave 1,2,3-triazole in high yield.
- Harada, Katsumasa,Oda, Mizuho,Matsushita, Akio,Shirai, Masashi
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p. 431 - 433
(2007/10/03)
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- A Convenient Laboratory Preparation of Cyanogen
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A convenient laboratory scale preparation of cyanogen has been developed.This new method generates cyanogen from the pyrolysis of diacetylglyoxime which can be easily prepared from glyoxime.
- Park, Dennis J.,Stern, Alfred G.,Willer, Rodney L.
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p. 2901 - 2906
(2007/10/02)
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- Products of the Reductions of 2-Nitroimidazoles
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Reductions under neutral conditions of misonidazole (1-(2'-hydroxy-3'-methoxypropyl)-2-nitroimidazole) and 1-methyl-2-nitroimidazole have been studied with radiation chemical, electrochemical, and chemical (zinc/ammonium chloride) techniques.Major products accounting for 70-80percent of the reduction mixture have been identified as the cis:trans isomers of 4 (1-substituted 2-amino-4,5-dihydro-4,5-dihydroxyimidazolium ions).These have been independently synthesized by the reaction of glyoxal and the appropriate guanidinium ion.Their presence after nitroreduction has been established by 1H NMR and by spectroscopic analysis in which 4 is converted into glyoxal bis-oxime.The ability of misonidazole reduction mixtures to form glyoxal derivatives has been noted previously, even in vivo; the presence of the cyclic 4 accounts for this.The four-electron-reduced product, a 2-(hydroxylamino)imidazole, is the precursor of 4.The hydroxylamine is unstable at pH 7, but it can be observed in acid where decomposition also gives 4 but in a much slower reaction.Nitroreduction or hydroxylamine decomposition in pH 7 phosphate gives two additional products which have been identified on the basis of their 1H NMR spectra as cis:trans isomers of monophosphate esters of 4.The reaction leading to these may model the DNA binding which is observed with reduced misonidazole.Azomycin (2-nitroimidazole) has been investigated by the radiation chemical technique.At pH 7 the isomers of 4 are formed, but they are minor products.The major product (70percent) is 2-aminoimidazole.
- Clelland, Robert A. Mc,Panicucci, Rick,Rauth, A. Michael
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p. 4308 - 4314
(2007/10/02)
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