1,2,4,5-Tetrakis(diazidomethyl)benzene

Wieland, Marcel; Su, Kuan-Jen; Wagner, G.; Brinker, Udo H.; Arion, Vladimir B.

doi:10.1107/s0108270109013894

Cited by 6 publications

(5 citation statements)

References 20 publications

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“…Nitrogen-rich heterocyclic azides have currently attracted significant attention as effective precursors for carbon nitride nanomaterials and potential high-energy density materials (HEDMs) − due to their relative high heats of formation (HOFs) raised by the azido group which adds about 87 kcal/mol to a hydrocarbon compound. Carbon nitrides with the bulk formulas C 3 N 4 and C 3 N 5 have been prepared from cyanuric azide (TAT) as well as 3,6-diazido-1,2,4,5-tetrazine (DiAT) .…”

Section: Introductionmentioning

confidence: 99%

First-Principle Study on High-Pressure Behavior of Crystalline Polyazido-1,3,5-triazine

Wang

Zhang

et al. 2012

J. Phys. Chem. C

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A detailed study on the structural, electronic, and thermodynamic properties of the solid polyazide 4,4′,6,6′-tetra(azido)azo-1,3,5-triazine (TAAT) under the hydrostatic pressure of 0−100 GPa was performed using the plane-wave density function theory method. The predicted crystal structure compares well with the experimental results at the ambient pressure. The results show that a pressure less than 40 GPa does not significantly change the crystal and molecular structures. When the higher pressure is applied, the molecular geometry, band structure, and density of states change regularly except at 48 and 90 GPa where the azide−tetrazole transformation occurs. At 48 GPa, the tetrazole rings are almost coplanar with the triazine rings, whereas it has a big deviation at 90 GPa. The azide cyclization for polyazido-1,3,5-triazine has not been observed in the gas phase or polar solvents. Moreover, the band gap reduction is more pronounced in the low-pressure range than in the high-pressure region. The band gap decreases to nearly zero at 70 GPa. This means the electronic character of the organic crystal has metallic properties. An analysis of density of states shows that the electronic delocalization in TAAT increases generally under the influence of pressure. This shows that an applied pressure may increase the impact sensitivity.

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Section: Introductionmentioning

confidence: 99%

First-Principle Study on High-Pressure Behavior of Crystalline Polyazido-1,3,5-triazine

Wang

Zhang

et al. 2012

J. Phys. Chem. C

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“…[1] They are at the forefront of high‐energy density materials due to the numerous applications, such as effective precursors for carbon nanospheres and nanomaterials, solid fuels in micropropulsion systems, and pyrotechnic ingredients. [2–12] Among them, polyazido‐substituted heteroaromatic compounds have been investigated extensively because they possess even higher heat of formation raised by the azido group which adds about 87 kcal/mol to a hydrocarbon compound. However, heterocylic polyazides such as cyanuric azide[13] and 3,6‐diazido‐1,2,4,5‐tetrazine (DiAT)[14] are usually notorious for high sensitivity to shock and friction and thus makes the handling difficult and hazardous.…”

Section: Introductionmentioning

confidence: 99%

Density functional theory study of high‐pressure effect on crystalline 4,4′,6,6′‐tetra(azido)hydrazo‐1,3,5‐triazine

Wang

Liu

et al. 2012

J Comput Chem

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Periodic density functional theory calculations are performed to study the hydrostatic compression effects on the structure, electronic, and thermodynamic properties of the energetic polyazide 4,4',6,6'-tetra(azido)hydrazo-1,3,5-triazine (TAHT) in the range of 0-100 GPa. At the ambient pressure, the local density approximation/Ceperley-Alder exchange-correlation potential parameterized by Perdew and Zunger relaxed crystal structure compares well with the experimental results. The predicted heat of sublimation is 38.68 kcal/mol, and the evaluated condensed phase of formation (414.04 kcal/mol) approximates to the experimental value. The detonation velocity and detonation pressure for the solid TAHT are calculated to be 7.44 km/s and 23.71 GPa, respectively. When the pressure is exerted less than 35 GPa, the crystal structure and geometric parameters change slightly. However, at 36 GPa, the molecular structure, band structure, and density of states change abnormally because of the azide-tetrazole transformation that has not been observed in gas phase or polar solvents. The azido group cyclizes to form a five-membered tetrazole ring that is coplanar with the riazine ring and contributes to a larger conjunction system. As the pressure augments further to 80 GPa, the hydrogen transfer is found and a new covalent bond H2-N9 is formed. In the studied pressure range, the band gap decreases generally except for some breaks due to the molecular transformation and drops to nearly zero at 100 GPa, which means the electronic character of the crystal changes toward a metallic system. An analysis of the electronic structure shows that an applied pressure increases the impact sensitivity of TAHT.

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“…A brief overview on the synthetic pathways is provided in Scheme 2. 2,3,6,[27][28][29][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50] Scheme 2 Overview of classical methods for diazidation; X = halogen We point out that the traditional diazidation by substitution of dihalides is undoubtedly the oldest of several options for diazidation, albeit probably the most reliable. Since a manifold of functional groups are well tolerated, this method has been successfully applied to many functional substrates, cyclic and acyclic (Scheme 3).…”

Section: Preparation Of Geminal Diazidesmentioning

confidence: 99%

“…A brief overview on the synthetic pathways is provided in Scheme 2 . 2 3 6 , 27 28 29 , 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50…”

Section: Preparation Of Geminal Diazidesmentioning

confidence: 99%

Reactions with Geminal Diazides: Long Known, Full of Surprises, and New Opportunities

Kirsch¹,

Bensberg²

2022

Synthesis

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Geminal diazides are uncommon yet powerful tools in organic synthesis. The chemistry of this class of functional compounds is characterized by quite unusual reactivities, including fragmentations and degradations, along with known reactions of organic azides. This Short Review highlights the major reactivities of various structural units having geminal diazido moieties, and provides an overview on the synthetic opportunities of such compounds.1 Introduction2 Preparation of Geminal Diazides3 Reactivities of Geminal Diazides3.1 α,α-Diazido Carbonyls3.2 1,3-Diketones3.3 Diazidated β-Ketoesters3.4 Diazidated Malonates3.5 Diazidated Malonamides3.6 Miscellaneous Geminal Diazides4 Conclusion

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1,2,4,5-Tetrakis(diazidomethyl)benzene

Cited by 6 publications

References 20 publications

First-Principle Study on High-Pressure Behavior of Crystalline Polyazido-1,3,5-triazine

First-Principle Study on High-Pressure Behavior of Crystalline Polyazido-1,3,5-triazine

Density functional theory study of high‐pressure effect on crystalline 4,4′,6,6′‐tetra(azido)hydrazo‐1,3,5‐triazine

Reactions with Geminal Diazides: Long Known, Full of Surprises, and New Opportunities

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