Synthesis of 2,4,6,8,9,11-hexaaza[3.3.3]propellanes as a new molecular skeleton for explosives

Lee, Byeongil; Shin, Minjung; Seo, Yutaek; Kim, Myeong Hak; Lee, Hye Ryoung; Kim, Jin Seok; Chung, Kyu-Hyun; Yoo, Dongwon; Kim, Young Gyu

doi:10.1016/j.tet.2017.11.046

Cited by 12 publications

(5 citation statements)

References 18 publications

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“…2). Пентанитрозамещенное 9 не было получено [9]. Группой корейских ученых разработан способ получения [3.3.3]гексаазапропелланового каркаса с шестью NH-группами [10] (рис.4).…”

Section: рис 2 получение пентааза[333]пропелланаunclassified

Пропелланы – Перспективные Каркасные Соединения В Создании Высокоэнергетических Веществ

Минакова¹,

Ильясов²

2021

Южно-Сибирский Научный Вестник

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Важной задачей современной органической химии является открытие новых, ранее не известных науке веществ, которые могли бы расширить область наших знаний и пополнить номенклатуру высокоэнергетических или биологически активных продуктов. 3,7,10-Триоксо-2,4,6,8,9,11-гексааза[3.3.3|пропеллан и его нитропроизводные являются новейшими продуктами класса гетероциклов, их азотсодержащая полициклическая структура предполагает наличие интересных и полезных свойств, что обусловливает проявленный интерес к данной работе. Химия 3,7,10-триоксо-2,4,6,8,9,11-гексааза[3.3.3|пропеллана малоизучена и представлена лишь двумя алкилпроизводными и теоретическими расчетами энергетических характеристик нитропроизводных. В статье преставлены результаты исследования нитрования 3,7,10-триоксо-2,4,6,8,9,11-гексааза[3.3.3]пропеллана (THAP) концентрированнойазотной кислотой. Установлено, что в процессе нитрования наблюдается протекание двух конкурирующих реакций – лактам-лактимной перегруппировки и нитрования. Было показано, что продукты реакции сильно зависят от температуры реакционной массы. Установлено, что температуре -40 ºС протекает образование лактимной формы ТНАР, тогда как при постепенном увеличении температуры сначала образуется мононитропроизводное пропеллана, а при температуре 40 ºС идёт селективное образование 3,7,10-триоксо-2,6-динитро-2,4,6,8,9,11-гексааза[3.3.3]пропеллана с выходом 30%. An important task of modern organic chemistry is the discovery of new substances previously unknown to science, which could expand the area of our knowledge and replenish the range of high-energy or biologically active products. 3,7,10-Trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane and its nitro derivatives are the newest products of the class of heterocycles; interest in this work. The chemistry of 3,7,10-trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane is poorly understood and is represented by only two alkyl derivatives and theoretical calculations of the energy characteristics of nitro derivatives. The article presents the results of a study of the nitration of 3,7,10-trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane (THAP) with concentrated nitric acid. It was found that in the process of nitration, there are two competing reactions - lactam-lactam rearrangement and nitration. It was shown that the reaction products strongly depend on the temperature of the reaction mixture. It was found that at a temperature of -40 ºС the formation of the lactimic form of THAP proceeds, whereas with a gradual increase in temperature, a mononitro derivative of propellane is first formed, and at a temperature of 40 ºС, the selective formation of 3,7,10-trioxo-2,6-dinitro-2,4,6,8,9,11-hexaaza[3.3.3]propellane in 30% yield.

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Section: рис 2 получение пентааза[333]пропелланаunclassified

Пропелланы – Перспективные Каркасные Соединения В Создании Высокоэнергетических Веществ

Минакова¹,

Ильясов²

2021

Южно-Сибирский Научный Вестник

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“…It should be noted that, for many decades, alkyl aluminum compounds have been widely used in carbonyls reduction [ 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 ] and alkenes and alkynes hydroalumination reactions [ 35 , 36 , 37 ]. i -Bu 2 AlH is commonly used in selective reduction reactions, such as the reduction of trioxohexaaza[3.3.3]propelane to saturated hexaazapropelane derivatives, regioselective transformation of the CN group to the amine or the direct reduction of carboxylic acid esters to aldehydes [ 38 , 39 , 40 ].…”

Section: Introductionmentioning

confidence: 99%

Hydrogenation of β-Keto Sulfones to β-Hydroxy Sulfones with Alkyl Aluminum Compounds: Structure of Intermediate Hydroalumination Products

et al. 2022

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β-Hydroxy sulfones are important in organic synthesis. The simplest method of β-hydroxy sulfones synthesis is the hydrogenation of β-keto sulfones. Herein, we report the reducing properties of alkyl aluminum compounds R3Al (R = Et, i-Bu, n-Bu, t-Bu and n-Hex); i-Bu2AlH; Et2AlCl and EtAlCl2 in the hydrogenation of β-keto sulfones. The compounds i-Bu2AlH, i-Bu3Al and Et3Al are the at best reducing agents of β-keto sulfones to β-hydroxy sulfones. In reactions of β-keto sulfones with aluminum trialkyls, hydroalumination products with β-hydroxy sulfone ligands [R2AlOC(C6H5)CH2S(O)2(p-R1C6H4]n [where n = 1,2; 2aa: R = i-Bu, R1 = CH3; 2ab: R = i-Bu, R1 = Cl; 2ba: R = Et, R1 = CH3; 2bb: R = Et, R1 = Cl] and {[Et2AlOC(C6H5)CH2S(O)2(p-ClC6H4]∙Et3Al}n3bb were obtained. These complexes in the solid state have a dimeric structure, while in solutions, they appear as equilibrium monomer–dimer mixtures. The hydrolysis of both the isolated 2aa, 2ab, 2ba, 2bb and 3bb and the postreaction mixtures quantitatively leads to pure racemic β-hydroxy sulfones. Hydroalumination reaction of β-keto sulfones with alkyl aluminum compounds and subsequent hydrolysis of the complexes is a simple and very efficient method of β-hydroxy sulfones synthesis.

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“…In another study, Lee et al [ 5 ] reported a synthetic method for the [3.3.3]hexaazapropellane cage bearing six NH groups, 3,7,10-trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane ( 19 , THAP) ( Scheme 2 ).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Nitro- and Acetyl Derivatives of 3,7,10-Trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane

et al. 2022

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Here, we report the study results of the nitration of 3,7,10-trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane (THAP) by different nitrating agents such as nitric acid, mixed nitric/sulfuric acids, nitric anhydride, and mixed concentrated nitric acid/acetic anhydride to furnish 3,7,10-trioxo-2-nitro-2,4,6,8,9,11-hexaaza[3.3.3]propellane and 3,7,10-trioxo-2,8-dinitro-2,4,6,8,9,11-hexaaza[3.3.3]propellane, whereas a lactam–lactim rearrangement was found to take place upon vigorous cooling to give 10-hydroxy-2,4,6,8,9,11-hexaazatricyclo[3.3.3.01,5]undec-9-ene-3,7-dione. The two competing reactions, lactam–lactim rearrangement, and nitration were found to take place. The acylation of 3,7,10-trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane was examined and the formation conditions of 2,6-di- and 2,6,9-triacetyl-substituted and 3,7,10-trioxo-2,4,6,8,9,11-hexaacetyl-2,4,6,8,9,11-hexaaza[3.3.3]propellane were established. The acetyl derivatives were found to be instable in an acidic medium and to undergo deacylation. The obtained findings correlate well with the quantum-chemical calculations.

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Synthesis of 2,4,6,8,9,11-hexaaza[3.3.3]propellanes as a new molecular skeleton for explosives

Cited by 12 publications

References 18 publications

Пропелланы – Перспективные Каркасные Соединения В Создании Высокоэнергетических Веществ

Пропелланы – Перспективные Каркасные Соединения В Создании Высокоэнергетических Веществ

Hydrogenation of β-Keto Sulfones to β-Hydroxy Sulfones with Alkyl Aluminum Compounds: Structure of Intermediate Hydroalumination Products

Synthesis of Nitro- and Acetyl Derivatives of 3,7,10-Trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane

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