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

HRID 1877656ノート

反応式

HRID 1877656 の反応式
[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

参加物

6

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 3007855Zincchloride触媒HCID 1140Toluene溶媒

反応条件

温度
70 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-1bef9b217ff74435a9f92020a7bc0e50
出典データセット
uspto-grants-2012_11
特許番号
US08309558B2

反応ノート

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