Argüello-Velasco Rubén Oswaldo, Dziuk Błażej, Zarychta Bartosz, Ordóñez Mario, Kafarski Paweł
Centro de Investigaciones Químicas-IICBA, Universidad Autónoma del Estado de Morelos, 62209 Cuernavaca, Morelos, Mexico.
Department of Crystallography, Faculty of Chemistry, University of Opole, 45-040 Opole, Poland.
ACS Omega. 2019 May 22;4(5):9056-9064. doi: 10.1021/acsomega.9b01137. eCollection 2019 May 31.
The reaction of the title lactams with triethyl phosphite prompted by phosphoryl chloride provided six-membered ring heterocyclic phosphonates or bisphosphonates. These novel scaffolds might be of interest as building blocks in medicinal chemistry. The course of the reaction was dependent on the structure of the used substrate. Thus, morpholin-3-one and thiomorpholin-3-one readily provided the corresponding 1,1-bisphosphonates (compounds , , , and ), whereas the protection of their nitrogen atom resulted in the formation of dehydrophosphonates (compounds , , and ). Piperazin-2-one reacted differently yielding mixture of - and - piperazine-2,3-diyl-bisphosphonates (compounds and ). Since cytosine could be considered as an analogue of piperin-2-one, its ditosyl derivative was used as a substrate affording compound being a product of phosphite addition to double bond. In dependence of their structures, hydrolysis of the obtained diethyl phosphonates resulted either in corresponding cyclic phosphonic acids or in the degradation of carbon-to-phosphorus bond.
由磷酰氯引发的标题内酰胺与亚磷酸三乙酯的反应生成了六元环杂环膦酸酯或双膦酸酯。这些新型骨架作为药物化学中的构建单元可能会引起人们的兴趣。反应过程取决于所用底物的结构。因此，吗啉 - 3 - 酮和硫代吗啉 - 3 - 酮很容易生成相应的1,1 - 双膦酸酯（化合物、、、和），而它们氮原子的保护导致脱氢膦酸酯的形成（化合物、和）。哌嗪 - 2 - 酮的反应不同，生成了 - 和 - 哌嗪 - 2,3 - 二基 - 双膦酸酯的混合物（化合物和）。由于胞嘧啶可被视为哌啶 - 2 - 酮的类似物，其双对甲苯磺酸酯衍生物被用作底物，得到化合物，它是亚磷酸酯加成到双键上的产物。根据其结构，所得二乙基膦酸酯的水解要么产生相应的环状膦酸，要么导致碳 - 磷键的降解。
