Chromophoric macrocycles from the oxidation of bis(aminofurazanylic) ethers of 1,2‐diols

Sheremetev, Aleksei B.; Shatunova, E. V.; Аверкиев, Борис Б.; Дмитриев, Д. Е.; Petukhov, V. A.; Antipin, M. Yu.

doi:10.1002/hc.10226

Cited by 24 publications

(7 citation statements)

References 38 publications

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“…No characterizable product could be obtained when the amine 1d was exposed to oxidation with KMnO 4 under acidic reaction conditions [1]. In sharp contrast to this result, the amine 1d reacted with the dibromoisocyanurate (DBI) [14] in an organic solvent to give the desired azofurazan 9 (Scheme 3).…”

Section: Synthesismentioning

confidence: 62%

The first general synthesis of 3‐iodo‐4‐R‐furazans

Sheremetev

Shamshina

Дмитриев

et al. 2004

Heteroatom Chemistry

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Section: Synthesismentioning

confidence: 62%

The first general synthesis of 3‐iodo‐4‐R‐furazans

Sheremetev

Shamshina

Дмитриев

et al. 2004

Heteroatom Chemistry

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“…A series of furoxan-based energetic compounds can be derived throughe lectron transfer in the two carbon atoms to add substituents. [7] So far,m uch research hasf ocused on polyfuroxans on ac hain or ar ing [8][9][10] and in macrocycles [11,12] in experiment and theoryf or good prospect of applications. However,s ingle furoxan systems have rarely been studied, [13][14][15][16][17] especially in theoreticalr esearch.…”

Section: Introductionmentioning

confidence: 99%

“…So far, much research has focused on polyfuroxans on a chain or a ring and in macrocycles in experiment and theory for good prospect of applications. However, single furoxan systems have rarely been studied, especially in theoretical research.…”

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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“…Many experimental and computational studies were centered on benzofuroxans [10][11][12], poly-furoxans on a chain or a circle [13][14][15][16][17][18][19][20], and macrocycles [6,[21][22][23][24][25], but single furoxan systems have been studied less extensively [4,[26][27][28][29][30]. Khmelnitskii and coworkers [30] reported the synthesis of 3,4-dinitrofuroxan (DNFX), a highly oxidized and fully nitrated heterocycle.…”

Section: Introductionmentioning

confidence: 99%

Theoretical studies of furoxan-based energetic nitrogen-rich compounds

et al. 2010

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Density functional theory calculations were performed to study the effects of different substituents and nitrogen-containing heterocyclic rings on the heats of formation (HOFs), energetic properties, and thermal stability for a series of furoxan derivatives. The isodesmic reaction method was employed to calculate the HOFs of the derivatives using total energies obtained from electronic structure calculations. The detonation velocities and pressures were evaluated by using the semiempirical KamletJacobs equations, based on the theoretical densities and HOFs. The bond dissociation energies and bond orders for the weakest bonds were analyzed to investigate the thermal stability of the furoxan derivatives. These results provide basic information for the molecular design of novel high energy density materials.

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Chromophoric macrocycles from the oxidation of bis(aminofurazanylic) ethers of 1,2‐diols

Cited by 24 publications

References 38 publications

The first general synthesis of 3‐iodo‐4‐R‐furazans

The first general synthesis of 3‐iodo‐4‐R‐furazans

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

Theoretical studies of furoxan-based energetic nitrogen-rich compounds

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