Water → 4-[Cyclohexylidene(4-hydroxyphenyl)methyl]-2-fluorobenzaldehyde

HRID 2100094ノート

反応式

HRID 2100094 の反応式
C([Li])CCC.Br[C:7]1[CH:12]=[CH:11][C:10]([CH:13]2[O:17]CCO2)=[C:9]([F:18])[CH:8]=1.[CH:19]1([C:25]([C:27]2[CH:32]=[CH:31][C:30]([O:33]COC)=[CH:29][CH:28]=2)=O)[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]1.O>C1COCC1>[C:19]1(=[C:25]([C:27]2[CH:28]=[CH:29][C:30]([OH:33])=[CH:31][CH:32]=2)[C:7]2[CH:12]=[CH:11][C:10]([CH:13]=[O:17])=[C:9]([F:18])[CH:8]=2)[CH2:20][CH2:21][CH2:22][CH2:23][CH2:24]1

参加物

6

反応物 4

HCID 962WaterHCID 219386012-(4-Bromo-2-Fluorophenyl)-1,3-DioxolaneHCID 68654452Cyclohexyl[4-(methoxymethoxy)phenyl]methanoneHCID 178418339Butyllithium

生成物 1

HCID 860299754-[Cyclohexylidene(4-hydroxyphenyl)methyl]-2-fluorobenzaldehyde収率 35%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

n-Butyllithium (1.6 M in hexanes, 1.33 mL, 2.13 mmol) was added dropwise to 88 (503 mg, 2.04 mmol) dissolved in anhydrous THF (25 mL) at −78° C. The reaction mixture was stirred for 20 min and 87 (460 mg, 1.85 mmol), dissolved in THF (25 mL), was added dropwise. The mixture was warmed slowly to RT and stirred overnight. Water (150 mL) was added and the mixture was extracted with ether (3×100 mL). The combined ethereal extracts were washed with water (200 mL), brine (200 mL), dried (MgSO4), and concentrated under reduced pressure. The resulting crude oil was taken up in a mixture of EtOH (10 mL) and 12 M HCl (2 mL) and refluxed for 2 h. Removal of solvent and flash chromatography (20:1 to 5:1 hexanes:EtOAc) afforded 200 mg (35%) of 89 as a white solid. 1H NMR (400 MHz, CDCl3): δ 1.60 (br s, 6H), 2.23 (m, 4H), 6.00 (s, 1H), 6.79 (d, J=8.2 Hz, 2H), 6.89-6.95 (m, 3H), 7.02 (d, J=7.9 Hz, 1H), 7.76 (t, J=7.6 Hz, 1H), 10.28 (s, 1H).

後処理

  1. additionwas added dropwise
  2. stirringstirred overnight
  3. extractionthe mixture was extracted with ether (3×100 mL)
  4. washThe combined ethereal extracts were washed with water (200 mL), brine (200 mL)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated under reduced pressure
  7. additionThe resulting crude oil was taken up in a mixture of EtOH (10 mL) and 12 M HCl (2 mL)
  8. temperaturerefluxed for 2 h
  9. customRemoval of solvent and flash chromatography (20:1 to 5:1 hexanes:EtOAc)

出典と根拠

ORDレコード
ord-9f40432e8968496fafbbcf1dbb34e98b
出典データセット
uspto-grants-2009_08
特許番号
US07569601B2

反応ノート

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