The Facile Synthesis and Energetic Properties of an Energetic Furoxan Lacking Traditional “Explosophore” Moieties: (E,E)‐3,4‐bis(oximomethyl)furoxan (DPX1)

Klapötke, Thomas M.; Piercey, Davin G.; Stierstorfer, Jörg

doi:10.1002/prep.201000057

Cited by 31 publications

(14 citation statements)

References 33 publications

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“…Therefore the heats of formation of the metalfree compounds 1, 5, and 7 were determined by quantum chemical calculations. For energetic nitrogen-rich compounds, it has been shown appropriate in recent studies [39][40] to use the atomization method [according to Eq. (2)] based on CBS-4M enthalpies:…”

Section: à3mentioning

confidence: 99%

The Taming of CN₇⁻: The Azidotetrazolate 2‐Oxide Anion

Klapötke

Piercey

Stierstorfer

2011

Chemistry A European J

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115

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The highly sensitive 5-azidotetrazolate anion was oxidized to its corresponding N-oxide by aqueous oxidation in a buffered oxone solution to the azidotetrazolate 2-oxide anion. After acidic extraction and neutralization with ammonia, the ammonium salt was isolated. Several energetic salts of this novel anion were prepared from the ammonium salt, and in all cases were found to be of lower sensitivity than the corresponding 5-azidotetrazolate salt while still being highly sensitive towards mechanical stimuli. Explosive performances (detonation velocity, detonation pressure) of applicable salts were also found to be higher than the non-N-oxide variants. Preparation of the free acid 2-hydroxy-5-azidotetrazole was achieved by protonation of the anion and identified by NMR spectroscopy, whereas the majority of the azidotetrazolate 2-oxide salts have unequivocal crystallographic proof.

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Section: à3mentioning

confidence: 99%

The Taming of CN₇⁻: The Azidotetrazolate 2‐Oxide Anion

Klapötke

Piercey

Stierstorfer

2011

Chemistry A European J

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115

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“…(E,E)-3,4-bis(oximomethyl)furoxan (DPX-1) [13] and benzotrifuroxan (BTF) [14], are two examples of powerful furoxan-based explosives having a high crystal density and good detonation properties, while lacking traditional "explosophoric" nitro, nitrato, and nitarmine groups.…”

Section: Introductionmentioning

confidence: 99%

Theoretical studies on energetic properties of s-triazine substituted aminofurazan and aminofuroxan derivatives—high performance energetic material systems

Frem¹

2014

Combust Explos Shock Waves

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A series of s-triazine substituted aminofurazan and aminofuroxan derivatives are investigated theoretically as potential high energy density materials (HEDMs). The crystal density, condensed heat of formation (HOF), detonation performance, acceleration ability, and critical pressure of initiation are estimated using empirical relationships. It is shown that the title compounds are characterized by high HOFs (817-4067 kJ/kg) and crystal density values (1.76-1.95 g/cm 3 ). The calculated detonation performance shows that derivatives substituted with N 3 and C(NO 2 ) 3 are potential candidates for future HEDMs. Moreover, the values of the critical pressure of initiation indicate that furoxan derivatives are more sensitive to shock and impact compared to their furazan counterparts and that, for the substitutes NH 2 or nitrogen-containing heterocycles, a similar or lower impact sensitivity than that of TNT (2,4,6-trinitrotoluene) can be obtained.

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“…tion. [21][22][23] However,t he reactionm echanism in Scheme 2, in particular oxime dehydrocyclization, has remainedu nclear.R ecently,t he transition states and intermediates involved in some oxime cyclizations have been qualitativelya nalyzed through experimentsa nd theoretical calculations. [21,24] However,s tudies have yet to explore the geometric configurations of variousp ossible transition states and intermediates on the basis of quantum chemistry;f urthermore, ar easonable reaction pathway has yet to be determined.…”

Section: Introductionmentioning

confidence: 99%

Reaction Mechanism of 3,4‐Dinitrofuroxan Formation from Glyoxime: Dehydrogenation and Cyclization of Oxime

et al. 2016

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The reaction pathway of the formation of 3,4-dinitrofuroxan from glyoxime is theoretically investigated under experimental conditions with 25 % nitric acid and dinitrogentetroxide reagents to clarify the mechanism of formation of a furoxan ring by glyoxime. The geometric configurations of minima and transition-state species are optimized at the (U)B3LYP/6-311++G** level. The CCSD(T) and CASSCF(10e,8o)/CASSCF(9e,8o) single-point energy corrections at the same level are performed on top of the optimized geometries. A subsequent dynamic correlation by using NEVPT2/6-311++G**-level single-point energy calculations based on the CASSCF results is also performed to obtain accurate energy values. The formation reaction is analyzed from two processes: glyoxime nitration and 3,4-dinitroglyoxime (nitration product) oxidative cyclization. Calculation results indicate that the electrophilic substitution of nitronium ions from the protonated HNO3 and the abstraction of hydrogen ions by HNO3 molecules are requisites of glyoxime nitration. The formation of a furoxan ring from 3,4-dinitroglyoxime involves two possible mechanisms: 1) oxydehydrogenation by NO2 molecules and the subsequent torsion of NO radical groups to form a ring and 2) the alternation of dehydrogenation and cyclization. The intermediates and transition states in both routes exhibit monoradical and diradical characteristics. Singlet and triplet reactions are considered for the diradical species. Results show that the singlet reaction mechanism is more favorable for cyclization than the triplet reaction. The formation of a furoxan ring from oxime is in accordance with the stepwise intermolecular dehydrogenation and intramolecular torsion to the ring.

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The Facile Synthesis and Energetic Properties of an Energetic Furoxan Lacking Traditional “Explosophore” Moieties: (E,E)‐3,4‐bis(oximomethyl)furoxan (DPX1)

Cited by 31 publications

References 33 publications

The Taming of CN₇⁻: The Azidotetrazolate 2‐Oxide Anion

The Taming of CN₇⁻: The Azidotetrazolate 2‐Oxide Anion

Theoretical studies on energetic properties of s-triazine substituted aminofurazan and aminofuroxan derivatives—high performance energetic material systems

Reaction Mechanism of 3,4‐Dinitrofuroxan Formation from Glyoxime: Dehydrogenation and Cyclization of Oxime

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The Facile Synthesis and Energetic Properties of an Energetic Furoxan Lacking Traditional “Explosophore” Moieties: (E,E)‐3,4‐bis(oximomethyl)furoxan (DPX1)

Cited by 31 publications

References 33 publications

The Taming of CN7−: The Azidotetrazolate 2‐Oxide Anion

The Taming of CN7−: The Azidotetrazolate 2‐Oxide Anion

Theoretical studies on energetic properties of s-triazine substituted aminofurazan and aminofuroxan derivatives—high performance energetic material systems

Reaction Mechanism of 3,4‐Dinitrofuroxan Formation from Glyoxime: Dehydrogenation and Cyclization of Oxime

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The Taming of CN₇⁻: The Azidotetrazolate 2‐Oxide Anion

The Taming of CN₇⁻: The Azidotetrazolate 2‐Oxide Anion