A Study on Nitration of 4,10‐Dibenzyl‐2,6,8,12‐Tetraacetyl‐2,4,6,8,10,12‐Hexaazaisowurtzitane

Surmachev, V. N.; Kubasova, Valentina A.; Zimin, D. E.

doi:10.1002/prep.202000174

Propellants Explo Pyrotec

2020

DOI: 10.1002/prep.202000174

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A Study on Nitration of 4,10‐Dibenzyl‐2,6,8,12‐Tetraacetyl‐2,4,6,8,10,12‐Hexaazaisowurtzitane

V. N. Surmachev

Valentina A. Kubasova

D. E. Zimin

Abstract: Here we explored the nitration of 4,10-dibenzyl-2,6,8,12-tetraacetylhexaazaisowurtzitane (TADB) and isolated and identified all the nitration intermediates. The substitution of the first acetyl group was found to be a key stage in this process. It is this stage where side destructive reactions of the hexaazaisowurtzitane cage take place actively, reducing the yield of CL-20.

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2024

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Cited by 3 publications

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Synthesis of Oxaazaisowurtzitane Derivatives Via Condensation of p‐Toluenesulfonamide With Glyoxal

Paromov,

Kubasova,

Sysolyatin

2024

Journal of Heterocyclic Chem

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This work presents the study results on the acid‐catalyzed cascade condensation of p‐toluenesulfonamide with glyoxal in H2SO4 in order to synthesize aza‐ and oxaazaisowurtzitanes—a platform for promising high‐energy‐density compounds—and explore their formation processes. The effects of the ratio of starting reactants, acidity, reaction medium concentration, and temperature on this process were studied in detail. Five novel compounds were derived, including four oxaazaisowurtzitanes comprising one to three aza groups, and one condensation intermediate. The most favorable conditions for the formation of the resultant caged compounds were established and some new regularities of the process were revealed. For instance, the reaction medium concentration was discovered for the first time to influence the generation process of oxaazaisowurtzitanes via direct condensation. The limiting stage of the cage formation process of oxaazaisowurtzitanes was identified. The formation rate of the oxaazaisowurtzitanes was shown to be dependent on their structure. The factor dramatically reducing the yield of the oxaazaisowurtzitanes at elevated synthesis temperature was also revealed.

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Synthesis of Oxaazaisowurtzitane Derivatives Via Condensation of p‐Toluenesulfonamide With Glyoxal

Paromov,

Kubasova,

Sysolyatin

2024

Journal of Heterocyclic Chem

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Nitration of 2,6,8,12-Tetraacetyl-2,4,6,8,10,12-Hexaazaisowurtzitane Derivatives

2022

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Condensation of Benzyl Carbamate with Glyoxal in Polar Protic and Aprotic Solvents

Paromov

2023

Molecules

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The synthesis of substituted 2,4,6,8,10,12-hexaazaisowurtzitane via direct condensation is challenging. The selection of starting ammonia derivatives is very limited. The important step in developing alternative synthetic routes to these compounds is to investigate their formation process in detail. Here, we examined an acid-catalyzed condensation between benzyl carbamate and glyoxal in a ratio of 2:1 in a range of polar protic and aprotic solvents, and discovered a new process occurring during the cascade condensation of glyoxal with ammonia derivatives as well as discovered several processes hindering the formation of caged compounds. More specifically, a cyclic compound, N,N′-bis(carbobenzoxy)-3,6-diamino-1,4-dioxane-2,5-diol, was found to form at the early stage of condensation under low acidity conditions. The formation of this compound is governed by an easier condensation of alcohol groups compared to the amide ones. The condensation intermediates, N,N′-bis(carbobenzoxy)ethan-1,2-diol, N,N′,N″-tris(carbobenzoxy)ethanol, and N,N′,N″,N‴-tetrakis(carbobenzoxy)ethan, were obtained at a higher acidity. A range of solvents were identified: those that react with benzyl carbamate, those that promote the progress of side processes, and those that promote precipitation of condensation intermediates. A few byproducts were isolated and identified. It was found that DMSO exhibits a strong deactivating ability, while CH3CN exhibits a strong activating ability towards the acid-catalyzed condensation process of benzyl carbamate with glyoxal.

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A Study on Nitration of 4,10‐Dibenzyl‐2,6,8,12‐Tetraacetyl‐2,4,6,8,10,12‐Hexaazaisowurtzitane

Cited by 3 publications

References 9 publications

Synthesis of Oxaazaisowurtzitane Derivatives Via Condensation of p‐Toluenesulfonamide With Glyoxal

Synthesis of Oxaazaisowurtzitane Derivatives Via Condensation of p‐Toluenesulfonamide With Glyoxal

Nitration of 2,6,8,12-Tetraacetyl-2,4,6,8,10,12-Hexaazaisowurtzitane Derivatives

Condensation of Benzyl Carbamate with Glyoxal in Polar Protic and Aprotic Solvents

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