<i>N</i>-(2-Fluoro-2,2-dinitroethyl)azoles: a novel assembly of diverse explosophoric building blocks for energetic compound design

Палысаева, Надежда В.; Гладышкин, Алексей Г.; Вацадзе, И. А.; Suponitsky, Kyrill Yu.; Дмитриев, Д. Е.; Sheremetev, Aleksei B.

doi:10.1039/c8qo01173g

Cited by 38 publications

(13 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…On the one hand, according to combined geometrical and energetic analysis (see the Supporting Information, Tables 3S and 4 S), compound 24 has 18 closest neighbors versus 15 for compound 25 . At that, higher number of the closest neighbors might be an indication of a tighter crystal packing . In addition, molecules of compound 25 form more stacking interactions which, to some extent, decrease an ability for close packing .…”

Section: Resultsmentioning

confidence: 99%

“…At that, higher number of the closest neighbors might be an indication of a tighter crystal packing. [30] In addition, molecules of compound 25 form more stacking interactions which, to some extent, decrease an ability for close packing. [11a] On the other hand, more and somewhat stronger CÀ H…O and O…π contacts as well as NO 2 …NO 2 interactions are formed in crystals of compound 25 which usually favor tight crystal packing.…”

Section: Resultsmentioning

confidence: 99%

“…3‐Phenyl‐1,2,3,4‐oxatriazolium‐5‐phenylaminide (22) : Yield 83 %, mp 110–112 °C (CH 2 Cl 2 ) (lit. mp 110–111 °C).…”

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Nitration of Azasydnones and Azasydnonimines: A Method for the Functionalization of Aryl Derivatives

et al. 2019

Self Cite

View full text Add to dashboard Cite

The first example of functionalization of mesoionic 3‐R‐1,2,3,4‐oxatriazol‐5‐ones and 3‐substituted‐1,2,3,4‐oxatriazol‐5‐imines (azasydnones and azasydnonimines, respectively) by the electrophilic reaction without destruction of the oxatriazole ring is reported. Nitration of a range of aryl derivatives bearing various electron donating and withdrawing substituents at the ortho‐, meta‐ and para‐positions using HNO3/H2SO4 mixtures has been assessed in order to develop an approach for the synthesis of corresponding nitroaryl derivatives. Whereas nitration occurs meta to the azasydnone ring, the regioselectivity of the electrophilic substitution can be affected by the nature of the substituent attached to the aryl ring, and a variety of polyfunctionalized derivatives can be readily accessed by using this methodology, which may have applications in the target‐oriented synthesis. The reactivity, synthesis, and structure of the mesoionic 3‐substituted‐1,2,3,4‐oxatriazole derivatives described here provide interesting new information on this known but poorly understood heterocycle.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Nitration of Azasydnones and Azasydnonimines: A Method for the Functionalization of Aryl Derivatives

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…Another approach is based on the simultaneous analysis of the density of the isolated molecule (d mol ) and a change in this density in going from the free molecule to the crystal (Δ OED ). [51][52][53][54] It is assumed that the molecules interact with each other by overlapping their electron densities. Therefore, the volume of the isolated molecule is larger than that in the crystal.…”

Section: Experimental and Calculationsmentioning

confidence: 99%

Crystal structure features of nitro derivatives of methylcytizine and their relationship with second-order nonlinear optical susceptibility

et al. 2020

View full text Add to dashboard Cite

The crystal packings of mono-(1) and dinitro derivatives (3) of methylcytizine are analyzed in terms of combined geometric and energy approaches and based on the evaluation of the degree of molecular deformation (a decrease in the molecular volume) in going from the free molecule to the crystal. An increase in the crystal density in going from the mono-to dinitro derivative (1.440 g cm-3 for 1 and 1.528 g cm-3 for 3 at 120 K) is associated with an increase in the density of the isolated molecule rather than with an increase in the packing density, which is almost equal in the crystals of compounds 1 and 3. The second-order nonlinear optical susceptibility of crystals was estimated in terms of a charge model, the prediction error of which is within 10%, being comparable with experimental accuracy. The similarity of the packing densities of compounds 1 and 3 enabled a detailed comparative analysis of the eff ect of the crystal fi eld on the nonlinear optical properties. Both compounds are characterized by relatively high nonlinear optical susceptibility, which is higher than that of urea, a commonly accepted standard, by a factor of 10 and 6.5 for compounds 1 and 3, respectively.

show abstract

“…Various designs of HEDM have been based on the introduction of explosophoric groups (nitro, azido and azo) and active moieties such as C(NO 2 ) 2 F and C(NO 2 ) 3 to a nitrogen-containing framework [11,15,16]. These are the oxygen-rich groups that provide balance for intermolecular combustion leading to facilitated detonation reaction and enhanced energetic performance [9,17,18].…”

Section: Introductionmentioning

confidence: 99%

High energy density materials based on fluorinated bridged trinitromethyl azo triazole derivatives: a quantum chemical study of thermodynamic and energetic properties

2020

View full text Add to dashboard Cite

High energy density materials (HEDM) have gained extensive attention due to their energetic properties and safety issues. Nitro and fluoro groups, among others, have become viable substituents on the triazole framework because of their particular contribution to detonation properties and moderate sensitivity. In this study, Density Function Theory (DFT) approach was employed to design fluorinated bis(trinitromethyl) azo triazoles. The molecular structures, thermodynamic properties of gaseous species (e.g., enthalpies of detonation and enthalpies of formation) and energetic properties of solid materials (detonation heat Q, pressure PD and velocity VD) have been investigated. The best characteristics attained for the designed azo fluorinated solid compounds are as follows: Q 1650-1690 cal g −1 , PD 44-46 GPa and VD 9.8 km s −1 . These characteristics are superior to those of conventional explosives, indicating that fluorinated bis(trinitromethyl) azo triazoles are promising HEDM.

show abstract

N-(2-Fluoro-2,2-dinitroethyl)azoles: a novel assembly of diverse explosophoric building blocks for energetic compound design

Abstract: The first protocol for N-(dinitrofluoroethyl)ation of azoles has been created.

Cited by 38 publications

References 54 publications

Nitration of Azasydnones and Azasydnonimines: A Method for the Functionalization of Aryl Derivatives

Nitration of Azasydnones and Azasydnonimines: A Method for the Functionalization of Aryl Derivatives

Crystal structure features of nitro derivatives of methylcytizine and their relationship with second-order nonlinear optical susceptibility

High energy density materials based on fluorinated bridged trinitromethyl azo triazole derivatives: a quantum chemical study of thermodynamic and energetic properties

Contact Info

Product

Resources

About