Synthesis of new N-polysubstituted oxaazaisowurtzitanes by acid-catalyzed condensation of sulfonamides with glyoxal

Paromov, Artyom E.; Sysolyatin, S. V.

doi:10.1134/s1070428017110197

Cited by 11 publications

(6 citation statements)

References 16 publications

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“…We have previously explored the condensation between substituted sulfonamides (methanesulfonamide, benzenesulfonamide, 4-dimethylaminobenzenesulfonamide or isopropylsulfonamide) and glyoxal, whereby a series of new oxaazaisowurtzitane derivatives were obtained, some polyheterocyclic caged systems were discovered and new condensation regularities were established [ 62 , 63 , 64 ]. More specifically, the increased basicity of the amido group in the sulfonamide molecule was found to facilitate the incorporation of aza groups into the oxaazaisowurtzitane cage.…”

Section: Resultsmentioning

confidence: 99%

“…Extensive research focused on upgrading the existing synthetic technologies for CL-20 and on finding alternative methods for obtaining the same has been pursued, dating back decades. The most promising direction is to develop a synthetic method for hexaazaisowurtzitane derivatives by direct condensation, which are nitratable to CL-20 [ 16 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 ].…”

Section: Introductionmentioning

confidence: 99%

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Acid-Catalyzed Condensation of Benzamide with Glyoxal, and Reaction Features

et al. 2022

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Scholars from around the world have been attempting to simplify and cheapen the synthetic method for the promising high-energy compound CL-20 for decades. The lack of understanding of the formation mechanisms of hexaazaisowurtzitane derivatives―CL-20 precursors―is a barrier to solving the said problems. Here, we report the results from an in-depth study into the acid-catalyzed condensation between benzamide and glyoxal in a molar ratio of 2:1 in polar protic and aprotic solvents. Sixteen compounds were isolated and identified, of which eight were synthesized for the first time. A geminal diol, N,N’-(2,2-dihydroxyethane-1,1-diyl)dibenzamide, was synthesized. Two isomers of 1,2-bis(benzoylamino)-1,2-ethanediol were isolated and identified. N,N’-(1-oxoethane-1,2-diyl)dibenzamide and 2-oxo-2-[(phenylcarbonyl)amino]ethyl benzoate were produced that were likely formed due to the 1,2-hydride shift. N-polysubstituted 1,4-dioxane-2,3,5,6-tetramine was synthesized for the first time, whose structure may be of interest as a scaffold for new explosives. DMSO, THF and HCOOH were found to be able to engage in a reaction with benzamide, or condensation products thereof, and glyoxal under acid-catalyzed conditions.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Acid-Catalyzed Condensation of Benzamide with Glyoxal, and Reaction Features

et al. 2022

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“…While selecting amides, we took into account the basicity of the reagents and the ease of N-nitration of the condensation products, except for mesyl amide that is highly resistant to acidic medium and capable of generating polyheterocyclic cage compounds. − The basicity of amides and the tendency of their condensation products toward N-nitration depends on the value of the partially negative charge on the amide nitrogen atom. This charge is due to the inductive effect of the substituent and increases in the row: CH 3 SO 2 NH 2 < HCONH 2 < CH 3 CONH 2 < (CH 3 ) 2 CHCONH 2 < CH 3 CH 2 CONH 2 < (CH 3 ) 3 CCONH 2 .…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Diaminoacetic Acid Derivatives as a Promising Scaffold for the Synthesis of Polyheterocyclic Cage Compounds

Paromov

Sysolyatin

2021

ACS Omega

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Here, we explored in detail an acid-catalyzed condensation of glyoxylic acid or its ethyl ester with several carboxamides of different basicity, or with mesyl amide, to furnish diaminoacetic acid derivatives. The most suitable synthesis conditions and the reaction catalysts were identified. Properties such as structure and basicity of the starting amides were demonstrated to influence the condensation process. Elemental iodine was used for the first time herein as an acid catalyst for the condensation of glyoxylic acid or its ester, which gave access to diaminoacetic acid derivatives in higher yields in most cases, as opposed to p-toluenesulfonic acid (PTSA). An abnormally high activity of mesyl amide when condensed with ethyl glyoxylate was noticed, which may evidence a special impact of the sulfonyl moiety in the amide molecule on the condensation.

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“…Данная работа является продолжением нашего исследования процессов формирования аза-и оксаазаизовюрцитанов. Ранее мы уже изучали конденсацию ряда замещённых сульфонамидов с глиоксалем [17][18][19][20].…”

Section: основная частьunclassified

synthesis of oxaazaisowurtzitane derivatives by condensation of p-toluenesulfonamide with glyoxal

Паромов,

Кубасова,

Сысолятин

2023

Южно-Сибирский Научный Вестник

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Синтез легконитруемых производных 2,4,6,8,10,12-гексаазатетрацикло[5.5.0.03,11.05,9]додекана (2,4,6,8,10,12-гексаазаизовюрцитана) – прекурсоры перспективного высокоэнергетического соединения 2,4,6,8,10,12-гексанитро-2,4,6,8,10,12-гексаазаизовюрцитана (CL-20, HNIW, ГАВ), методом прямой конденсации является сложной задачей. С момента открытия данных соединений в середине 90-х годов и до настоящего времени не останавливаются попытки разработать доступный способ синтеза данных веществ. На данный момент синтез ГАВ все еще остается слишком дорогим. Выбор исходных производных аммиака для получения производных 2,4,6,8,10,12-гексаазаизовюрцитана весьма ограничен. Важным шагом в разработке альтернативного двустадийного способа синтеза легконитруемых производных 2,4,6,8,10,12-гексаазаизовюрцитана, который радикально может снизить стоимость ГАВ, является детальное исследование процесса формирования каркаса 2,4,6,8,10,12-гексаазаизовюрцитана. В данной работе представлены данные исследования реакции конденсации п-толуолсульфонамида с глиоксалем в мольном соотношении 2 : 1 в среде водной H2SO4 с целью исследования процессов образования и синтеза новых производных аза- и оксаазаизовюрцитанов. В работе получено три новых оксаазаизовюрцитана различной структуры включающие одну и две азагруппы. Показано влияние кислотности реакционной среды на процесс. В частности, отмечена низкая устойчивость некоторых соединений. А также разработан способ разделения двух полученных изомерных оксаазаизовюрцитанов: 2,6,8,12-тетраокса-4,10-диаизовюрцитана и 6,10,2,4,8,12-тетраокса-6,10-диазаизовюртцитана, с помощью препаративной хроматографии. The synthesis of easily nitratable derivatives of 2,4,6,8,10,12-hexaazatetracyclo[5.5.0.03,11.05,9]dodecane (2,4,6,8,10,12-hexazaisowurtzitane), the precursors of the promising high-energy compound 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12- hexazaisowurtzitane (CL-20, HNIW), via the direct condensation is challenging. Since the discovery of these compounds in the mid-1990s and to the present, there has been no stop in the attempts to develop a facile synthetic method for these compounds. At present, the synthesis of HNIW still remains to be very espensive. The selection of starting ammonia derivatives for the synthesis of 2,4,6,8,10,12-hexazaisowurtzitane derivatives is rather limited. The important step in the development of an alternative two-stage synthetic method for easily nitratable 2,4,6,8,10,12-hexazaisowurtzitane derivatives, which can cardinally reduce the cost of HNIW, is a detailed study on the formation process of the 2,4,6,8,10,12-hexazaisowurtzitane cage. This paper reports the study results on the condensation reaction between p-toluenesulfonamide and glyoxal in a molar ratio of 2 : 1 in aqueous H2SO4 in order to examine the formation processes of aza- and oxaazaisowurtzitanes. Three new oxaazaisowurtzitanes differing in structure were synthesized herein that incorporate one or two aza groups. In particular, some compounds were noted to be low-stability. In addition, a method was developed for the separation of the two resultant isomeric oxaazaisowurtzitanes, 2,6,8,12-tetraoxa-4,10-diazaisowurtzitane and 6,10,2,4,8,12-tetraoxa-6,10-diazaisowurtzitane, by preparative chromatography.

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Synthesis of new N-polysubstituted oxaazaisowurtzitanes by acid-catalyzed condensation of sulfonamides with glyoxal

Cited by 11 publications

References 16 publications

Acid-Catalyzed Condensation of Benzamide with Glyoxal, and Reaction Features

Acid-Catalyzed Condensation of Benzamide with Glyoxal, and Reaction Features

Synthesis of Diaminoacetic Acid Derivatives as a Promising Scaffold for the Synthesis of Polyheterocyclic Cage Compounds

synthesis of oxaazaisowurtzitane derivatives by condensation of p-toluenesulfonamide with glyoxal

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