Safer and Convenient Synthesis of 3,4-Dicyanofuroxan

Johnson, E.; Bukowski, Eric J.; Sausa, Rosario C.; Sabatini, Jesse J.

doi:10.1021/acs.oprd.9b00186

Cited by 18 publications

(21 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The synthesis of 2 (Scheme 1) commenced by treating cyanoacetic acid with mixed acid in an improved process to yield dicyanofuroxan (DCFO, 3) in 72 % yield and 84 % purity, as we published previously. [11] The impurity was inconsequential, as DCFO was converted uneventfully to diamidoxime 4 in 68 % yield. [12] 4 was isolated in very high purity via Büchner filtration, while the aforementioned impurity remained in the mother liquor.…”

Section: Resultsmentioning

confidence: 99%

“…[12] 4 was isolated in very high purity via Büchner filtration, while the aforementioned impurity remained in the mother liquor. Double diazotization of 4 gave dihydroximoyl chloride 5, [11,12] which was then converted to biisoxazole 6 in reasonable yield. Employing an excess of propargyl alcohol, coupled with slow addition of 5, were critical in obtaining good yields.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Bis(Nitroxymethylisoxazolyl) Furoxan: A Promising Standalone Melt‐Castable Explosive

et al. 2020

Self Cite

View full text Add to dashboard Cite

The synthesis and crystal structure of the heterocyclic explosive bis(nitroxymethylisoxazolyl) furoxan, C 10 H 6 N 6 O 10 , are described. In addition, we report its physical properties and theoretical performance. This material was found to exhibit standalone melt-castable explosive properties, with a melting point of 89.8°C and an onset decomposition temperature of 193.8°C. Bis (nitroxymethylisoxazolyl) furoxan features an insensitive behavior to impact, friction, and electrostatic discharge, with a calculated detonation pressure about 25 % higher than the state-of-the-art melt-castable explosive TNT. 4 5 6 7 8

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Bis(Nitroxymethylisoxazolyl) Furoxan: A Promising Standalone Melt‐Castable Explosive

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…Dicyanofuroxan 14 was synthesized according to a previously published procedure [ 45 ]. 3-Methylfuroxan 15 was prepared via nucleophilic substitution of the nitro group in compound 1 by hydride-anion under the action of NaBH 4 [ 46 ].…”

Section: Resultsmentioning

confidence: 99%

“…The synthesis of 3-cyano-4-nitrofuroxan 12 was accomplished previously by the dehydration of 4nitrofuroxan-3-carboxylic acid amide [44], whereas the oxidation approach provided direct access to the compound 12 through a smaller number of steps starting from the corresponding amine 13. Dicyanofuroxan 14 was synthesized according to a previously published procedure [45]. 3-Methylfuroxan 15 was prepared via nucleophilic substitution of the nitro group in compound 1 by hydride-anion under the action of NaBH4 [46].…”

Section: Synthesis Of Furoxan Derivativesmentioning

confidence: 99%

“…3-Methylfuroxan 15 was prepared via nucleophilic substitution of the nitro group in compound 1 by hydride-anion under the action of NaBH4 [46]. The oxidative N-N coupling of aminofuroxans Dicyanofuroxan 14 was synthesized according to a previously published procedure [45]. 3-Methylfuroxan 15 was prepared via nucleophilic substitution of the nitro group in compound 1 by hydride-anion under the action of NaBH 4 [46].…”

Section: Synthesis Of Furoxan Derivativesmentioning

confidence: 99%

See 1 more Smart Citation

Nitro-, Cyano-, and Methylfuroxans, and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives

et al. 2020

View full text Add to dashboard Cite

In the present work, we studied in detail the thermochemistry, thermal stability, mechanical sensitivity, and detonation performance for 20 nitro-, cyano-, and methyl derivatives of 1,2,5-oxadiazole-2-oxide (furoxan), along with their bis-derivatives. For all species studied, we also determined the reliable values of the gas-phase formation enthalpies using highly accurate multilevel procedures W2-F12 and/or W1-F12 in conjunction with the atomization energy approach and isodesmic reactions with the domain-based local pair natural orbital (DLPNO) modifications of the coupled-cluster techniques. Apart from this, we proposed reliable benchmark values of the formation enthalpies of furoxan and a number of its (azo)bis-derivatives. Additionally, we reported the previously unknown crystal structure of 3-cyano-4-nitrofuroxan. Among the monocyclic compounds, 3-nitro-4-cyclopropyl and dicyano derivatives of furoxan outperformed trinitrotoluene, a benchmark melt-cast explosive, exhibited decent thermal stability (decomposition temperature >200 °C) and insensitivity to mechanical stimuli while having notable volatility and low melting points. In turn, 4,4′-azobis-dicarbamoyl furoxan is proposed as a substitute of pentaerythritol tetranitrate, a benchmark brisant high explosive. Finally, the application prospects of 3,3′-azobis-dinitro furoxan, one of the most powerful energetic materials synthesized up to date, are limited due to the tremendously high mechanical sensitivity of this compound. Overall, the investigated derivatives of furoxan comprise multipurpose green energetic materials, including primary, secondary, melt-cast, low-sensitive explosives, and an energetic liquid.

show abstract

Design and Synthesis of Nitrogen‐Rich Azo‐Bridged Furoxanylazoles as High‐Performance Energetic Materials

Larin

Shaferov

Пивкина

et al. 2021

Chemistry A European J

View full text Add to dashboard Cite

A series of novel energetic materials comprising of azo-bridged furoxanylazoles enriched with energetic functionalities was designed and synthesized. These high-energy materials were thoroughly characterized by IR and multinuclear NMR ( 1 H, 13 C, 14 N) spectroscopy, high-resolution mass spectrometry, elemental analysis, and differential scanning calorimetry (DSC). The molecular structures of representative amino and azo oxadiazole assemblies were additionally confirmed by single-crystal X-ray diffraction and X-ray powder diffraction. A comparison of contributions of explosophoric moieties into the density of energetic materials revealed that furoxan and 1,2,4-oxadiazole rings are the densest motifs while the substitution of the azide and amino fragments on the nitro and azo ones leads to an increase of the density. Azo bridged energetic materials have high nitrogen-oxygen contents (68.8-76.9 %) and high thermal stability. The synthesized compounds exhibit good experimental densities (1.62-1.88 g cm À 3 ), very high enthalpies of formation (846-1720 kJ mol À 1 ), and, as a result, excellent detonation performance (detonation velocities 7.66-9.09 km s À 1 and detonation pressures 25.0-37.7 GPa). From the application perspective, the detonation parameters of azo oxadiazole assemblies exceed those of the benchmark explosive RDX, while a combination of high detonation performance and acceptable friction sensitivity of azo(1,2,4-triazolylfuroxan) make it a promising potential alternative to PETN.

show abstract

Safer and Convenient Synthesis of 3,4-Dicyanofuroxan

Cited by 18 publications

References 18 publications

Bis(Nitroxymethylisoxazolyl) Furoxan: A Promising Standalone Melt‐Castable Explosive

Bis(Nitroxymethylisoxazolyl) Furoxan: A Promising Standalone Melt‐Castable Explosive

Nitro-, Cyano-, and Methylfuroxans, and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives

Design and Synthesis of Nitrogen‐Rich Azo‐Bridged Furoxanylazoles as High‐Performance Energetic Materials

Contact Info

Product

Resources

About