Laboratory 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, Russia.
Department of Chemistry, Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia.
Molecules. 2022 Feb 7;27(3):1094. doi: 10.3390/molecules27031094.
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, ,'-(2,2-dihydroxyethane-1,1-diyl)dibenzamide, was synthesized. Two isomers of 1,2-bis(benzoylamino)-1,2-ethanediol were isolated and identified. ,'-(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. -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.
几十年来，来自世界各地的学者一直在试图简化和降低高能量化合物 CL-20 的合成方法的成本。缺乏对六氮杂异伍兹烷衍生物-CL-20 前体形成机制的理解，是解决这些问题的障碍。在这里，我们报告了在极性质子和非质子溶剂中，苯甲酰胺和乙二醛摩尔比为 2:1 的酸催化缩合的深入研究结果。分离并鉴定了十六种化合物，其中八种是首次合成的。合成了偕二醇，即'-(2,2-二羟乙基)-二苯甲酰胺。分离并鉴定了 1,2-双(苯甲酰胺基)-1,2-乙二醇的两种异构体。由于 1,2-氢迁移，生成了'-(1-氧代乙烷-1,2-二基)二苯甲酰胺和 2-氧代-2-[(苯基羰基)氨基]乙基苯甲酸酯。首次合成了 -多取代的 1,4-二氧杂环己烷-2,3,5,6-四胺，其结构可能作为新型炸药的骨架引起人们的兴趣。发现 DMSO、THF 和 HCOOH 在酸催化条件下能够与苯甲酰胺或其缩合产物以及乙二醛反应。
