Sulfuric Acid → Diethyl (2,4-dichloro-5-fluoro-3-nitrobenzoyl)propanedioate

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Reaction Steps

2.1 g of tetrachloromethane are added to 10.1 g of magnesium turnings in 21 ml of ethanol, and mixture of 66.6 g of diethyl malonate, 40 ml of ethanol and 150 ml of toluene are added dropwise at 50°-60° C. after the commencement of hydrogen evolution. The mixture is stirred for 1 hour at this temperature, cooled to -5°--10° C., and a solution of 109.2 g of 2,4-dichloro-5-fluoro-3-nitro-benzoyl chloride in 50 ml of toluene is slowly added dropwise. The mixture is then stirred for 1 hour at 0° C., brought to room temperature overnight, and warmed at 40°-50° C. for a further 2 hours. A mixture of 160 ml of water and 10.4 ml of concentrated sulphuric acid are added to the reaction mixture with ice cooling, and the organic phase is separated off. The aqueous phase is extracted with toluene, and the combined organic extract is washed with saturated sodium chloride solution and dried with sodium sulphate, and the solvent is stripped off. 144.5 g of diethyl (2,4 -dichloro-5-fluoro-3-nitro-benzoyl)malonate are obtained as a crude product. After addition of 200 ml of water and 0.6 g of 4-toluenesulphonic acid, this is refluxed for 3 hours, the mixture is extracted with methylene chloride, the extract is dried using sodium sulphate, and the solvent is removed by distillation in vacuo. 118 g of substituted benzoylacetate are obtained as a crude product. It has adequate purity for the further reactions.

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