반응 #62802

반응 방정식

diethyl malonate

magnesium

2,4-dichloro-5-fluoro-3-nitrobenzoyl chloride

hydrogen

sulphuric acid

→

diethyl(2,4-dichloro-5-fluoro-3-nitrobenzoyl)malonate

수율 91.0%

용매

toluene

ethanol

ethanol

toluene

water

반응 조건

후처리

1. 1
   workup.ADDITIONis added dropwise at 50°-60° C
2. 2
   온도cooled to -5° to -10° C.
3. 3
   workup.STIRRINGThe mixture is then stirred at 0° C. for 1 hour
4. 4
   workup.WAITbrought to room temperature overnight
5. 5
   온도heated at 40°-50° C. for 2 hours
6. 6
   온도The reaction mixture is cooled in ice
7. 7
   workup.ADDITIONis added
8. 8
   기타the organic phase is separated off
9. 9
   추출The aqueous phase is extracted with toluene
10. 10
    추출the combined organic extract
11. 11
    세척is washed with saturated sodium chloride solution
12. 12
    건조dried with sodium sulphate
13. 13
    기타the solvent is removed in vacuo

실험 절차

2.1 g of tetrachloromethane are added to 10.1 g of magnesium turnings in 21 ml of ethanol and, after evolution of hydrogen has started, a mixture of 66.6 g of diethyl malonate, 40 ml of ethanol and 150 ml of toluene is added dropwise at 50°-60° C. The mixture is stirred at this temperature for 1 hour, then cooled to -5° to -10° C., and a solution of 109.2 g of 2,4-dichloro-5-fluoro-3-nitrobenzoyl chloride in 50 ml of toluene is slowly added dropwise. The mixture is then stirred at 0° C. for 1 hour, brought to room temperature overnight, and then heated at 40°-50° C. for 2 hours. The reaction mixture is cooled in ice, and a mixture of 160 ml of water and 10.4 ml of concentrated sulphuric acid is added, 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, dried with sodium sulphate, and the solvent is removed in vacuo. 144.5 g of diethyl(2,4-dichloro-5-fluoro-3-nitrobenzoyl)malonate are obtained as a crude product. 200 ml of water and 0.6 g of 4-toluenesulphonic acid are added to this, and the mixture is heated under reflux for 3 hours, extracted with methylene chloride, and the extract is dried with Sodium sulphate and the solvent is removed by distillation in vacuo. 118 g of substituted benzoyl acetic ester are obtained as a crude product. It is sufficiently pure for the subsequent reactions.

출처