Sulfuric Acid → Diethyl 2-(2,4-dichloro-5-fluorobenzoyl)malonate

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Reaction Steps

24.3 g of magnesium chips are suspended in 50 ml of anhydrous ethanol. 5 ml of carbon tetrachloride are added and, when the reaction has started, a mixture of 160 g of diethyl malonate, 100 ml of absolute ethanol and 400 ml of anhydrous ether is added dropwise, whereupon vigorous reflux is to be observed. When the reaction has subsided, the mixture is heated at the boiling point for a further 2 hours and cooled to -5° C. to -10° C. with dry ice/acetone, and a solution of 227.5 g of 2,4-dichloro-5-fluoro-benzoyl chloride in 100 ml of absolute ether is slowly added dropwise at this temperature. The mixture is stirred at 0° C. to -5° C. for 1 hour and allowed to come to room temperature overnight, and a mixture of 400 ml of ice-water and 25 ml of concentrated sulphuric acid is run in, while cooling with ice. The phases are separated and subsequently extracted twice with ether. The combined ether solutions are washed with saturated sodium chloride solution and dried with sodium sulphate and the solvent is stripped off in vacuo. 349.5 g of diethyl 2,4-dichloro-5-fluoro-benzoyl-malonate are obtained as a crude product.

Provenance & Evidence