Quinone → Ethyl 2-(4-fluorophenyl)-5-hydroxybenzofuran-3-carboxylate

HRID 1025184노트

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HRID 1025184 반응식
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:15])[CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:4][CH:3]=1.[C:16]1(=O)[CH:21]=[CH:20][C:19](=[O:22])[CH:18]=[CH:17]1.CCOC(C)=O>C1(C)C=CC=CC=1.[Cl-].[Zn+2].[Cl-]>[F:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[O:15][C:16]3[CH:21]=[CH:20][C:19]([OH:22])=[CH:18][C:17]=3[C:9]=2[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:6][CH:7]=1

참가 물질

6

반응물 3

HCID 4650QuinoneHCID 8857Ethyl AcetateHCID 2758844Ethyl 3-(4-Fluorophenyl)-3-Oxopropanoate

생성물 1

HCID 56604952Ethyl 2-(4-fluorophenyl)-5-hydroxybenzofuran-3-carboxylate

시약·촉매·용매 2

HCID 3007855Zincchloride촉매HCID 1140Toluene용매

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온도
70 °C

실험 절차

To a stirred solution of zinc chloride (8.39 g, 1.14 mmol, 1 eq) in toluene at ambient temperature, ethyl 3-(4-fluorophenyl)-3-oxopropanoate (13 g, 2.74 mmol, 1 eq) was added and stirred at 70° C. for 15 min. Benzoquinone (6.66 g, 0.72 mmol, 1 eq) was added portion wise into the reaction mixture and stirred at the same temperature for 15-20 min. Dean-stark apparatus was assembled and the reaction mixture was heated at 140° C. for 12 h and cooled to ambient temperature. Reaction completion was judged by TLC. EtOAc was added to the reaction mass and filtered through the filter paper, to remove the inorganic material. Brine was added to the reaction mixture (filtrate) and extracted, dried over sodium sulphate and concentrated to get the crude material. Further it was purified by column chromatography using 10% EtOAc/Hexane system. Yield: 8.0 g (43%). 1H NMR (400 MHz, CDCl3): δ 1.38-1.42 (t, 3H, J=7.14 Hz), 4.37-4.42 (q, 2H, J=7.13 Hz), 5.2 (br s, 1H), 6.87-6.9 (q, 1H, J=3.81 Hz), 7.14-7.18 (q, 2H, J=5.82 Hz), 7.36-7.39 (d, 1H, J=8.80 Hz), 7.50-7.51 (d, 1H, J=2.56 Hz), 8.00-8.03 (m, 2H). LCMS: (ES+) m/z=301 (M+H).

후처리

  1. stirringstirred at the same temperature for 15-20 min
  2. temperaturethe reaction mixture was heated at 140° C. for 12 h
  3. temperaturecooled to ambient temperature
  4. customReaction completion
  5. filtrationfiltered through the filter paper
  6. customto remove the inorganic material
  7. additionBrine was added to the reaction mixture (filtrate)
  8. extractionextracted
  9. dry with materialdried over sodium sulphate
  10. concentrationconcentrated

출처 및 근거

ORD 기록
ord-103afc93d1a14d95b36a99e7d95a742b
출처 데이터셋
uspto-grants-2014_05
특허 번호
US08722688B2

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