Systèmes aromatiques à 10 électrons π derivés de l'aza‐3a pentalène. XVII. Tautomérie azido/tétrazole dans la série du pyrazole

Alcalde, Ermitas; Mendoza, Javier de; Elguero, José

doi:10.1002/jhet.5570110613

Cited by 35 publications

(3 citation statements)

References 26 publications

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“…The second bicyclic system presented here featuring catena -5 nitrogen systems involves the edge fusion of a tetrazole and pyrazole in the pyrazolo[1,5- d ]tetrazole bicycle. − Analogous to the azoindole systems discussed above, these may be formed by the cyclization of azidopyrazole or by the addition of a nitrene (primary amine followed by dehydrogenation) to diazopyrzole (Scheme ).…”

Section: Catenated Nitrogen Compoundsmentioning

confidence: 99%

Properties and Promise of Catenated Nitrogen Systems As High-Energy-Density Materials

2020

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The properties of catenated nitrogen molecules, molecules containing internal chains of bonded nitrogen atoms, is of fundamental scientific interest in chemical structure and bonding, as nitrogen is uniquely situated in the periodic table to form kinetically stable compounds often with chemically stable N–N bonds but which are thermodynamically unstable in that the formation of stable multiply bonded N2 is usually thermodynamically preferable. This unique placement in the periodic table makes catenated nitrogen compounds of interest for development of high-energy-density materials, including explosives for defense and construction purposes, as well as propellants for missile propulsion and for space exploration. This review, designed for a chemical audience, describes foundational subjects, methods, and metrics relevant to the energetic materials community and provides an overview of important classes of catenated nitrogen compounds ranging from theoretical investigation of hypothetical molecules to the practical application of real-world energetic materials. The review is intended to provide detailed chemical insight into the synthesis and decomposition of such materials as well as foundational knowledge of energetic science new to most chemists.

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Section: Catenated Nitrogen Compoundsmentioning

confidence: 99%

Properties and Promise of Catenated Nitrogen Systems As High-Energy-Density Materials

2020

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“…We therefore looked to characterize the equilibrium shown in eq 1 via spectroscopic techniques in the polar solvent dimethyl sulfoxide. Using the 13 C chemical shift of the quaternary carbon of tert-butylamine as a spectroscopic handle for the protonation state of tertbutylamine, 47 we were able to measure an equilibrium constant of K = 1.1 × 10 −2 according to eq 2 using 1 H NMR spectroscopy. This value corresponds to an unfavorable freeenergy change of ΔG rxn = +2.6 kcal/mol.…”

mentioning

confidence: 99%

“…Cyclization represents a convenient method to form new linkages between synthons. (Hetero)cyclic compounds are also central to the biological activity of molecules. − To inorganic and physical organic chemists, cyclic functional groups are important for tuning the stability − and electronic properties of molecules. − Nitrogen-rich heterocycles have been a focus for novel explosives and propellants. − Heterocycles, especially aromatic azoles, constitute nitrogen-rich energetics with surprising kinetic stability and promising physical properties. − ,− …”

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confidence: 99%

Metal-Free Reversible Double Cyclization of Cyanuric Diazide to an Asymmetric Bitetrazolate via Cleavage of the Six-Membered Aromatic Ring

Vaddypally,

Byrne,

Goldsmith

et al. 2024

Inorg. Chem.

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Crystallization of the reaction mixture of 2-amino-4,6-diazido-1,3,5-triazine and excess tert-butylamine results in the isolation of tert-butylammonium N,N-[1′H-(1,5′-bitetrazol)-5-yl]cyanamidate, suggesting a complex decyclization/cyclization rearrangement involving breakage of the six-membered aromatic ring and the formation of two new five-membered azole rings mediated by deprotonation of the precursor by the amine. The addition of tert-butylamine to 2-amino-4,6-diazido-1,3,5-triazine gives spectroscopic indication of thermodynamically unfavorable reactivity in low-dielectric solvents, and high-level quantum chemical computations also suggest its formation to be unfavorable. A computed interconversion pathway describes the likely reaction mechanism and supports the general thermodynamic unfavorability of the reaction and the requirement for a high-dielectric environment to template formation of the ionic product and its trapping by crystallization.

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5,5‐System With a Bridgehead Nitrogen Atom

Paolini¹

1977

Chemistry of Heterocyclic Compounds: A Series of Monographs

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Systèmes aromatiques à 10 électrons π derivés de l'aza‐3a pentalène. XVII. Tautomérie azido/tétrazole dans la série du pyrazole

Cited by 35 publications

References 26 publications

Properties and Promise of Catenated Nitrogen Systems As High-Energy-Density Materials

Properties and Promise of Catenated Nitrogen Systems As High-Energy-Density Materials

Metal-Free Reversible Double Cyclization of Cyanuric Diazide to an Asymmetric Bitetrazolate via Cleavage of the Six-Membered Aromatic Ring

5,5‐System With a Bridgehead Nitrogen Atom

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