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

HRID 34524

반응식

HRID 34524 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.ClC(Cl)(Cl)Cl.O>[CH2:13]([O:12][C:4](=[O:11])[CH:5]([C:18](=[O:19])[C:17]1[CH:21]=[C:22]([F:29])[C:23]([Cl:28])=[C:24]([N+:25]([O-:27])=[O:26])[C:16]=1[Cl:15])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH3:14]

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 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.

후처리

  1. additionis added dropwise at 50°-60° C
  2. temperaturecooled to -5° to -10° C.
  3. stirringThe mixture is then stirred at 0° C. for 1 hour
  4. waitbrought to room temperature overnight
  5. temperatureheated at 40°-50° C. for 2 hours
  6. temperatureThe reaction mixture is cooled in ice
  7. additionis added
  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
  13. customthe solvent is removed in vacuo

출처 및 근거

ORD 기록
ord-fe3563ef3e0f4a5582cd87e5611697b6
출처 데이터셋
uspto-grants-1988_08
특허 번호
US04762831

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