Some Cubane Derivatives as Potential Components of Solid Gas Generator Propellants

Лемперт, Д. Б.; Zyuzin, I. N.; Averkov, I. S.; Raznoschikov, V. V.; Yanovskii, L. S.

doi:10.1134/s1070427221020063

Cited by 4 publications

(2 citation statements)

References 19 publications

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“…Frustratingly, attempts at nitration of 2h and 3h using the relatively mild nitrating agent acetyl nitrate led only to unproductive decomposition to complex mixtures, which presented as low-energy gums, suggesting inadvertent destruction of the cuneane skeleton (Figure , eqs 2–3). However, cubane 1h was successfully nitrated using acetyl nitrate to give previously reported nitrate ester 5f (Figure , eq 4). − The isolation process required modification to provide a sufficiently pure material for analysis. We found that trituration of the gummy, impure concentrate of the dichloromethane extract using ethyl acetate gave pure 5f as a white, crystalline solid.…”

Section: Resultsmentioning

confidence: 99%

Exploring Cuneanes as Potential Benzene Isosteres and Energetic Materials: Scope and Mechanistic Investigations into Regioselective Rearrangements from Cubanes

et al. 2023

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Cuneane is a strained hydrocarbon that can be accessed via metal-catalyzed isomerization of cubane. The carbon atoms of cuneane define a polyhedron of the C 2v point group with six faces�two triangular, two quadrilateral, and two pentagonal. The rigidity, strain, and unique exit vectors of the cuneane skeleton make it a potential scaffold of interest for the synthesis of functional small molecules and materials. However, the limited previous synthetic efforts toward cuneanes have focused on monosubstituted or redundantly substituted systems such as permethylated, perfluorinated, and bis(hydroxymethylated) cuneanes. Such compounds, particularly rotationally symmetric redundantly substituted cuneanes, have limited potential as building blocks for the synthesis of complex molecules. Reliable, predictable, and selective syntheses of polysubstituted cuneanes bearing more complex substitution patterns would facilitate the study of this ring system in myriad applications. Herein, we report the regioselective, Ag I -catalyzed isomerization of asymmetrically 1,4-disubstituted cubanes to cuneanes. In-depth DFT calculations provide a charge-controlled regioselectivity model, and direct dynamics simulations indicate that the nonclassical carbocation invoked is short-lived and dynamic effects augment the charge model.

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Section: Resultsmentioning

confidence: 99%

Exploring Cuneanes as Potential Benzene Isosteres and Energetic Materials: Scope and Mechanistic Investigations into Regioselective Rearrangements from Cubanes

et al. 2023

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“…4). [14][15][16][17][18] The isolation process required modification to provide sufficiently pure material for analysis. We found that trituration of the gummy, impure concentrate of the dichloromethane extract using ethyl acetate gave pure 5f as a white, crystalline solid.…”

Section: Table 1 Reaction Optimizationmentioning

confidence: 99%

Exploring Cuneanes as Benzene Isosteres and Energetic Materials: Scope and Mechanistic Investigations into Regioselective Rear-rangements from Cubanes

Son

Aikonen

Morgan

et al. 2023

Preprint

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Cuneane is a strained hydrocarbon accessible via metal-catalyzed isomerization of cubane. The carbon atoms of cuneane define a polyhedron of the C2v point group with six faces- two triangular, two quadrilateral, and two pentagonal. The rigidity, strain, and unique exit vectors of the cuneane skeleton make it a potential scaffold of interest for the synthesis of functional small molecules and materials. However, the limited previous synthetic efforts towards cuneanes have focused on mono-substituted or redundantly substituted systems such as permethylated, perfluorinated, and bis(hydroxymethylated) cu-neanes. Such compounds, particularly rotationally symmetric redundantly substituted cuneanes, have limited potential as building blocks for the synthesis of complex molecules. Reliable, predictable, and selective syntheses of poly-substituted cuneanes bearing more complex substitution patterns would facilitate the study of this ring system in myriad applications. Herein, we report the regioselective, AgI-catalyzed isomerization of asymmetrically 1,4-disubstituted cubanes to cuneanes. In-depth DFT calculations provide a charge-controlled regioselectivity model and direct dynamics simulations indicate that the non-classical carbocation is short-lived and dynamic effects augment the charge model.

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Approaches to 1,4‐Disubstituted Cubane Derivatives as Energetic Materials: Design, Theoretical Studies and Synthesis

Namboothiri

Lal

Bhattacharjee

et al. 2022

Chemistry An Asian Journal

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Novel 1,4‐disubstituted cubane derivatives have been designed and selected ones have been successfully synthesized and characterized by various analytical and spectroscopic techniques, including single‐crystal X‐ray analysis. A detailed computational study at B3LYP/6‐311++G(d,p) level of theory revealed that all newly designed 1,4‐disubstituted cubane derivatives possess higher densities, higher density‐specific impulse and superior ballistic properties when compared to conventional fuels, for example, RP‐1. These compounds also exhibit acceptable kinetic and thermodynamic stabilities which were evaluated in terms of their HOMO‐LUMO energy gap and bond dissociation energies, respectively, and are superior to TEX and many other compounds containing explosophoric groups. These results provide novel insights into the possible application of cubane‐based energetic materials.

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Some Cubane Derivatives as Potential Components of Solid Gas Generator Propellants

Cited by 4 publications

References 19 publications

Exploring Cuneanes as Potential Benzene Isosteres and Energetic Materials: Scope and Mechanistic Investigations into Regioselective Rearrangements from Cubanes

Exploring Cuneanes as Potential Benzene Isosteres and Energetic Materials: Scope and Mechanistic Investigations into Regioselective Rearrangements from Cubanes

Exploring Cuneanes as Benzene Isosteres and Energetic Materials: Scope and Mechanistic Investigations into Regioselective Rear-rangements from Cubanes

Approaches to 1,4‐Disubstituted Cubane Derivatives as Energetic Materials: Design, Theoretical Studies and Synthesis

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