Dichlorination of β-Keto Esters and 1,3-Diketones Mediated by Oxone/Aluminum Trichloride Mixture in Aqueous Medium
Vasileios Giannopoulos, Nikolaos Katsoulakis, Ioulia Smonou*
*Department of Chemistry, University of Crete, 71003 Voutes,
Heraklion, Greece, Email: smonou
uoc.gr
V. Giannopoulos, N. Katsoulakis, I. Smonou, Synthesis, 2022, 54, 2457-2463.
DOI: 10.1055/s-0041-1737412
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Abstract
The use of Oxone/aluminum trichloride mixture enables an α,α-dichlorination of β-keto esters and 1,3-diketones in aqueous medium. The dichlorinated compounds have been produced in one step, high yields, and short reaction times.
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Details
The document details a new method for the α,α-dichlorination of β-keto esters and 1,3-diketones using an Oxone/aluminum trichloride (AlCl3) mixture in an aqueous medium. This method is efficient, yielding high amounts of dichlorinated compounds in short reaction times. The process is advantageous due to its use of inexpensive, non-toxic reagents and water as the solvent, contrasting with previous methods that required organic solvents and toxic reagents. The reaction mechanism involves Oxone oxidizing chloride ions from AlCl3 to chlorine cations, which then react with the enol form of the dicarbonyl compounds to produce the dichlorinated products. The method was tested on various β-keto esters and 1,3-diketones, achieving yields between 50-85%. The study also explored the reaction conditions, optimizing the ratios of Oxone and AlCl3 to maximize yields and minimize side products. This new method offers a practical and environmentally friendly approach to synthesizing α,α-dichloro dicarbonyl compounds, which are valuable in medicinal chemistry and organic synthesis. The research was supported by the University of Crete and the State Scholarships Foundation, with no conflicts of interest declared.
Key Words
Oxone, aluminum trichloride, dichlorination, chlorination of ketones, chlorination of esters, β-dicarbonyl compounds
ID: J66-Y2022
