Synthesis of Cyclic Phosphinates by Microwave-Assisted Ionic-Liquid-Promoted Alcoholysis
Nikoletta Harsági, Nóra Zsuzsa Kiss, László Drahos, György Keglevich*
*Department of Organic Chemistry and Technology, Budapest,
University of Technology and Economics, 1521 Budapest, Hungary, Email:
keglevich.gyorgy
vbk.bme.hu
N. Harsági, N. Z. Kiss, L. Drahos, G. Keglevich, Synthesis, 2022, 54, 3899-3905.
DOI: 10.1055/a-1504-8924
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Abstract
A series of 1-alkoxy-3-methyl- and 3,4-dimethyl-3-phospholene 1-oxides, as well as 1-alkoxy-3-methylphospholane 1-oxides were prepared in good yields by a microwave-assisted and [bmim][PF6]-catalyzed transesterification of the corresponding methyl or ethyl esters.
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Details
The document details the synthesis of cyclic phosphinates using a microwave-assisted, ionic-liquid-promoted alcoholysis method. The study, conducted by researchers from Budapest University of Technology and Economics and the Research Centre for Natural Sciences, explores the transesterification of methyl or ethyl esters to produce 1-alkoxy-3-methyl- and 3,4-dimethyl-3-phospholene 1-oxides, as well as 1-alkoxy-3-methylphospholane 1-oxides. The process utilizes microwave irradiation and ionic liquids like [bmim][PF6] to achieve high yields (86-94%) and efficient conversions. The method offers an alternative to traditional esterification techniques, demonstrating significant advantages in terms of reaction speed and efficiency due to the microwave's local overheating effects. The study also highlights the sensitivity of the alcoholysis process to steric factors and the beneficial role of ionic liquids in enhancing microwave energy absorption. Additionally, the research includes continuous flow experiments, further showcasing the method's potential for scalable applications. The findings are supported by 31P NMR and HRMS analyses, ensuring the purity and identification of the synthesized compounds. This innovative approach provides a valuable contribution to the field of organophosphorus chemistry, particularly in the synthesis of P-heterocycles.
Key Words
alcoholysis, transesterification, phospholene oxide, phospholane oxide, microwave synthesis, ionic liquids
ID: J66-Y2022
