Boron tribromide → Diethyl 2-(2,6-difluoro-4-hydroxyphenyl)malonate

HRID 1786299노트

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HRID 1786299 반응식
[F:1][C:2]1[CH:7]=[C:6]([O:8]C)[CH:5]=[C:4]([F:10])[C:3]=1[CH:11]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:12]([O:14][CH2:15][CH3:16])=[O:13].B(Br)(Br)Br.C(=O)(O)[O-].[Na+]>C(Cl)Cl>[F:1][C:2]1[CH:7]=[C:6]([OH:8])[CH:5]=[C:4]([F:10])[C:3]=1[CH:11]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:12]([O:14][CH2:15][CH3:16])=[O:13]

참가 물질

5

반응물 3

HCID 25134Boron tribromideHCID 516892Sodium BicarbonateHCID 11174138Diethyl 2-(2,6-difluoro-4-methoxyphenyl)malonate

생성물 1

HCID 16103023Diethyl 2-(2,6-difluoro-4-hydroxyphenyl)malonate수율 94.7%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

반응 조건

온도
-78 °C

실험 절차

To a solution of diethyl 2-(2,6-difluoro-4-methoxyphenyl)malonate (2.11 g, 7.0 mmol) in 60 mL of methylene chloride at −78° C. is added boron tribromide (2.65 mL, 28 mmol) dropwise. The mixture is then stirred at −78° C. for 10 minutes, warmed to 0° C., and stirred at 0° C. for 1 h. A 5% aqueous solution of sodium bicarbonate is added slowly to quench the reaction. The product is extracted with ethyl acetate. The combined organic extracts are washed with saturated sodium chloride, dried over magnesium sulfate, and concentrated to a residue. The residue is chromatographed over silica gel, eluting with a gradient of 10% ethyl acetate in hexanes to 30% ethyl acetate in hexanes. Concentration provides diethyl 2-(2,6-difluoro-4-hydroxyphenyl)malonate as a colorless oil (1.91 g). MS: m/z 287.2 (M−H).

후처리

  1. temperaturewarmed to 0° C.
  2. stirringstirred at 0° C. for 1 h
  3. customto quench
  4. customthe reaction
  5. extractionThe product is extracted with ethyl acetate
  6. washThe combined organic extracts are washed with saturated sodium chloride
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated to a residue
  9. customThe residue is chromatographed over silica gel
  10. washeluting with a gradient of 10% ethyl acetate in hexanes to 30% ethyl acetate in hexanes
  11. concentrationConcentration

출처 및 근거

ORD 기록
ord-46c8f9dfedd640ea8424108be2403a20
출처 데이터셋
uspto-grants-2009_03
특허 번호
US07507739B2

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