2580-79-2Relevant articles and documents
A Convenient and Safer Synthesis of Diaminoglyoxime
Johnson, Eric C.,Sabatini, Jesse J.,Zuckerman, Nathaniel B.
, p. 2073 - 2075 (2017)
A new procedure for the synthesis and isolation of diaminoglyoxime (DAG) is described. A previous procedure involved treating glyoxal with 2 equiv each of hydroxylammonium chloride and sodium hydroxide to form glyoxime, followed by further treatment of this intermediate with two additional equivalents of hydroxylammonium chloride and sodium hydroxide at 95 °C to form DAG. Two recrystallizations were needed to obtain the desired product in pure form. Another previous procedure employed glyoxal in the presence of 4 equiv each of hydroxylammonium chloride and sodium hydroxide at 95 °C to form DAG. Though this latter procedure gives product after a few hours, yields do not exceed 40%, and the reaction is prone to thermal runaway. Furthermore, the use of decolorizing carbon and recrystallization of the crude solid are necessary to obtain a pure product. The new disclosed procedure involves treating a preheated aqueous hydroxylamine solution (50 wt %, 10 equiv) with aqueous glyoxal (40 wt %), followed by heating at 95 °C for 72-96 h. The reaction is cooled to room temperature and then to 0-5 °C to obtain DAG in pure form, without recrystallization or decolorizing carbon in 77-80% yield. The exothermic nature of the reaction is also minimized by this updated process.
Bis(1,2,4-oxadiazole)bis(methylene) Dinitrate: A High-Energy Melt-Castable Explosive and Energetic Propellant Plasticizing Ingredient
Johnson, Eric C.,Sabatini, Jesse J.,Chavez, David E.,Sausa, Rosario C.,Byrd, Edward F. C.,Wingard, Leah A.,Guzmàn, Pablo E.
, p. 736 - 740 (2018)
Discussed herein is the synthesis of bis(1,2,4-oxadiazole)bis(methylene) dinitrate, determination of its crystal structure by X-ray diffractometry, calculations of its explosive performance, and sensitivity measurements. Steps taken to optimize the synthesis process and to improve yields of the dinitrate are also discussed. Bis(1,2,4-oxadiazole)bis(methylene) dinitrate has a calculated detonation pressure 50% higher than that of TNT. The dinitrate compound exhibits a relatively high decomposition temperature that is rarely observed for nitrate-based compounds. The dinitrate was found to have lower sensitivities to impact and friction compared with RDX. It is believed that intramolecular hydrogen bonding observed in the crystal lattice assists in the relatively high thermal stability and relatively low sensitivity of the material.
Synthesis and Characterization of the Potential Melt-Castable Explosive 3-(1,2,4-Oxadiazolyl)-5-Nitratomethyl Isoxazole
Byrd, Edward F. C.,Johnson, Eric C.,Miller, Christopher W.,Orlicki, Joshua A.,Reid, Tristen A.,Sabatini, Jesse J.,Sausa, Rosario C.
, p. 875 - 878 (2021/07/22)
The synthesis of 3-(1,2,4-oxadiazolyl)-5-nitratomethyl isoxazole (C6H4N4O5), its physical properties, and its theoretical performances are described. This energetic material was found to have a melting point range of 76.6–79.2 °C, and a thermal onset decomposition temperature of 184.5 °C. These thermal features put this material into the standalone melt-castable explosive class. The material was found to have TNT performance, and was found to be insensitive to impact, friction, and electrostatic discharge, despite having a nitric ester functionality. A critical reaction in making this molecule was the desymmetrization of diaminoglyoxime. The optimization of this transformation is described. Previous reports of this desymmetrization were found to be inaccurate, as the desymmetrization reaction produces a co-crystal of mono- and bi-1,2,4-oxadiazole products.
A new Ni-diaminoglyoxime-g-C3N4complex towards efficient photocatalytic ethanol splitting: Via a ligand-to-metal charge transfer (LMCT) mechanism
Du, Cui,Xu, Yanqi,Yang, Shengyang,Zhou, Chen
supporting information, p. 7171 - 7174 (2020/07/14)
We report a novel Ni-diaminoglyoxime-g-C3N4 (Ni-DAG-CN) complex for H2 evolution through photocatalytic ethanol splitting. Compared to that of pristine g-C3N4, Ni-DAG-CN exhibits a 21-fold enhancement of photocatalytic activity (296.1 μmol h-1 g-1) under irradiation with excellent stability. The enhanced photocatalytic activity can be attributed to a proposed ligand-to-metal charge transfer (LMCT) mechanism, which is illustrated both experimentally and theoretically. This work provides great potential in the future design of low-cost, high-performance photocatalysts for H2 evolution from alcohol splitting.
METHOD FOR PREPARING DIHYDROXYLAMMONIUM 5,5'-BISTETRAZOLE-1,1'-DIOLATE
-
Paragraph 0061; 0062-0064, (2019/05/15)
The present invention relates to a method for manufacturing dihydroxylammonium 5,5andprime;-bistetrazole-1,1andprime;-diolate. More specifically, the present invention relates to the method for manufacturing dihydroxylammonium 5,5andprime;-bistetrazole-1,1andprime;-diolate using a diaminoglyoxime intermediate. The present invention can provide a safe and convenient method for manufacturing TKX-50.(AA) ^(13)C-NMR spectrum of TKX-50COPYRIGHT KIPO 2019
Exploiting the energetic potential of 1,2,4-oxadiazole derivatives: Combining the benefits of a 1,2,4-oxadiazole framework with various energetic functionalities
Yan, Chao,Wang, Kangcai,Liu, Tianlin,Yang, Hongwei,Cheng, Guangbin,Zhang, Qinghua
, p. 14210 - 14218 (2017/11/06)
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).
Energetic materials containing fluorine. Design, synthesis and testing of furazan-containing energetic materials bearing a pentafluorosulfanyl group
Martinez, Henry,Zheng, Zhaoyun,Dolbier Jr., William R.
, p. 112 - 122,11 (2020/08/20)
The advantageous impact of a pentafluorosulfanyl substituent on the properties of furazan-containing energetic materials was demonstrated by the synthesis and study of the energetic properties of ten new compounds. The thermal stability of these compounds was evaluated by DSC and TGA, whereas densities, heats of formation, pressures of detonation and speeds of detonation were obtained computationally. On the basis of these data, it was concluded that the combination of the SF5 substituent with the furazan ring led to materials of higher density and predicted detonation properties than other known furazans or SF5-containing materials. In addition, the synthetic studies provided insight regarding the electron-withdrawing nature of the furazan ring, in particular its effect on the basicity and nucleophilic reactivity of amino furazans.
Microwave mediated fast synthesis of diaminoglyoxime and 3,4-diaminofurazan: Key synthons for the synthesis of high energy density materials
Kusurkar, Radhika S.,Goswami, Shailesh K.,Talawar, Mahadev B.,Gore, Girish M.,Asthana, Shri N.
, p. 245 - 247 (2007/10/03)
This paper reports the first microwave-assisted synthesis of diaminoglyoxime (DAG) and diaminofurazan (DAF). The synthesis involved the vicarious nucleophilic substitution of H of glyoxime using hydroxylamine hydrochloride under microwave irradiation for 2 to 3 min to obtain DAG, which on further irradiation in alkali solution for 20 min yielded DAF. Conversion of glyoxime into DAF was also achieved in a one pot sequence in good overall yield using microwave irradiation.
Solid-phase versus solution synthesis of asymmetrically disubstituted furazano[3,4-b]pyrazines
Fernández,García-Ochoa,Huss,Mallo,Bueno,Micheli,Paio,Piga,Zarantonello
, p. 4741 - 4745 (2007/10/03)
Herein we describe a straightforward solid-phase synthesis directed towards the preparation of families of asymmetrically disubstituted furazano[3,4-b]pyrazines by stepwise displacement of the two chlorine atoms in 5,6-dichlorofurazano[3,4-b]pyrazine by nucleophiles. This synthesis has avoided selectivity problems found in solution chemistry.
A Two-Step Synthesis of Diaminofurazan and Synthesis of N-Monoarylmethyl and N,N'-Diarylmethyl Derivatives
Zelenin, Alexander K.,Trudell, Mark L.
, p. 1057 - 1060 (2007/10/03)
Diaminofurazan (1) was synthesized from glyoxal (2) by an improved two-step procedure. The N-monoarylmethyl derivatives 4a-e and N,N'-diarylmethyl derivatives 5a-e of 1 were prepared in good yields by reductive alkylation with the corresponding aryl aldehydes.
