Acid-Catalyzed Condensation of Benzamide with Glyoxal, and Reaction Features
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 probl...
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| Format: | Article |
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MDPI AG
2022-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/3/1094 |
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| author | Artyom Paromov Irina Shchurova Alla Rogova Irina Bagryanskaya Dmitriy Polovyanenko |
| author_facet | Artyom Paromov Irina Shchurova Alla Rogova Irina Bagryanskaya Dmitriy Polovyanenko |
| author_sort | Artyom Paromov |
| collection | DOAJ |
| description | 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, <i>N</i>,<i>N</i>’-(2,2-dihydroxyethane-1,1-diyl)dibenzamide, was synthesized. Two isomers of 1,2-bis(benzoylamino)-1,2-ethanediol were isolated and identified. <i>N</i>,<i>N</i>’-(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. <i>N</i>-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. |
| first_indexed | 2024-03-09T23:26:16Z |
| format | Article |
| id | doaj.art-4de46a4d313349bbbc05799e5c933c2c |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T23:26:16Z |
| publishDate | 2022-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-4de46a4d313349bbbc05799e5c933c2c2023-11-23T17:17:30ZengMDPI AGMolecules1420-30492022-02-01273109410.3390/molecules27031094Acid-Catalyzed Condensation of Benzamide with Glyoxal, and Reaction FeaturesArtyom Paromov0Irina Shchurova1Alla Rogova2Irina Bagryanskaya3Dmitriy Polovyanenko4Laboratory for Chemistry of Nitrogen Compounds, Institute for Problems of Chemical and Energetic Technologies, Siberian Branch of the Russian Academy of Sciences (IPCET SB RAS), 659322 Biysk, RussiaLaboratory for Chemistry of Nitrogen Compounds, Institute for Problems of Chemical and Energetic Technologies, Siberian Branch of the Russian Academy of Sciences (IPCET SB RAS), 659322 Biysk, RussiaLaboratory for Chemistry of Nitrogen Compounds, Institute for Problems of Chemical and Energetic Technologies, Siberian Branch of the Russian Academy of Sciences (IPCET SB RAS), 659322 Biysk, RussiaDepartment of Chemistry, Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, RussiaDepartment of Chemistry, Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, RussiaScholars 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, <i>N</i>,<i>N</i>’-(2,2-dihydroxyethane-1,1-diyl)dibenzamide, was synthesized. Two isomers of 1,2-bis(benzoylamino)-1,2-ethanediol were isolated and identified. <i>N</i>,<i>N</i>’-(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. <i>N</i>-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.https://www.mdpi.com/1420-3049/27/3/1094condensationdomino reactionsnitrogen heterocyclesoxygen heterocycles2,4,6,8,10,12-Hexaazatetracyclo[5.5.0.0<sup>3,11</sup>.0<sup>5,9</sup>]dodecane |
| spellingShingle | Artyom Paromov Irina Shchurova Alla Rogova Irina Bagryanskaya Dmitriy Polovyanenko Acid-Catalyzed Condensation of Benzamide with Glyoxal, and Reaction Features Molecules condensation domino reactions nitrogen heterocycles oxygen heterocycles 2,4,6,8,10,12-Hexaazatetracyclo[5.5.0.0<sup>3,11</sup>.0<sup>5,9</sup>]dodecane |
| title | Acid-Catalyzed Condensation of Benzamide with Glyoxal, and Reaction Features |
| title_full | Acid-Catalyzed Condensation of Benzamide with Glyoxal, and Reaction Features |
| title_fullStr | Acid-Catalyzed Condensation of Benzamide with Glyoxal, and Reaction Features |
| title_full_unstemmed | Acid-Catalyzed Condensation of Benzamide with Glyoxal, and Reaction Features |
| title_short | Acid-Catalyzed Condensation of Benzamide with Glyoxal, and Reaction Features |
| title_sort | acid catalyzed condensation of benzamide with glyoxal and reaction features |
| topic | condensation domino reactions nitrogen heterocycles oxygen heterocycles 2,4,6,8,10,12-Hexaazatetracyclo[5.5.0.0<sup>3,11</sup>.0<sup>5,9</sup>]dodecane |
| url | https://www.mdpi.com/1420-3049/27/3/1094 |
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