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

HRID 1199751

반응식

HRID 1199751 반응식
[Mg].[H][H].[C:4]([O:12][CH2:13][CH3:14])(=[O:11])[CH2:5][C:6]([O:8][CH2:9][CH3:10])=[O:7].[Cl:15][C:16]1[C:24]([N+:25]([O-:27])=[O:26])=[C:23]([Cl:28])[C:22]([F:29])=[CH:21][C:17]=1[C:18](Cl)=[O:19].S(=O)(=O)(O)O>C(O)C.C1(C)C=CC=CC=1.C(Cl)(Cl)(Cl)Cl.O>[Cl:15][C:16]1[C:24]([N+:25]([O-:27])=[O:26])=[C:23]([Cl:28])[C:22]([F:29])=[CH:21][C:17]=1[C:18]([CH:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])[C:4]([O:12][CH2:13][CH3:14])=[O:11])=[O:19]

참가 물질

10

반응물 5

HCID 1118Sulfuric AcidHCID 7761Diethyl MalonateHCID 5462224MagnesiumHCID 11818130Benzoyl chloride, 2,4-dichloro-5-fluoro-3-nitro-HCID 178418361HCID 178418361, 화합물

생성물 1

HCID 13733139Diethyl (2,4-dichloro-5-fluoro-3-nitrobenzoyl)propanedioate수율 91%

시약·촉매·용매 4

HCID 5943Carbon Tetrachloride촉매HCID 702Ethanol용매2회HCID 962Water용매HCID 1140Toluene용매2회

실험 절차

2.1 g of carbon tetrachloride are added to 10.1 g of magnesium filings in 21 ml of ethanol and, when the 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 subsequently stirred at this temperature for 1 hour and is cooled to -5° to -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. Thereafter, the mixture is stirred at 0° C. for 1 hour, 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 is added to the reaction mixture, while cooling with ice, and the organic phase is separated off. The aqueous phase is extracted with toluene, 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. This is heated under reflux for 3 hours, after addition of 200 ml of water and 0.6 g of 4-toluenesulphonic acid, and the mixture is extracted with methylene chloride and dried with sodium sulphate and the solvent distilled off in vacuo. 118 g of substituted benzoylacetic acid ester are obtained as a crude product. The product is of sufficient purity for the subsequent reactions.

후처리

  1. additionis added dropwise at 50°-60° C
  2. temperatureis cooled to -5° to -10° C.
  3. stirringThereafter, the mixture is stirred at 0° C. for 1 hour
  4. waitbrought to room temperature overnight
  5. temperaturewarmed at 40°-50° C. for a further 2 hours
  6. additionis added to the reaction mixture
  7. temperaturewhile cooling with ice
  8. customthe organic phase is separated off
  9. extractionThe aqueous phase is extracted with toluene
  10. extractionthe combined organic extract
  11. washis washed with saturated sodium chloride solution
  12. dry with materialdried with sodium sulphate

출처 및 근거

ORD 기록
ord-27e17f762a9c423aa7be148cb5e6eafe
출처 데이터셋
uspto-grants-1990_02
특허 번호
US04902795

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