tert-Butyl methyl ether → 4-(tert-Butyl)-3,5-difluorophenol

HRID 2108828ノート

反応式

HRID 2108828 の反応式
CO[C:3]([CH3:6])([CH3:5])[CH3:4].[F:7][C:8]1[CH:9]=[C:10]([OH:15])[CH:11]=[C:12]([F:14])[CH:13]=1>C(Cl)Cl.[Cl-].[Cl-].[Cl-].[Cl-].[Zr+4]>[C:3]([C:13]1[C:8]([F:7])=[CH:9][C:10]([OH:15])=[CH:11][C:12]=1[F:14])([CH3:6])([CH3:5])[CH3:4]

参加物

5

反応物 2

HCID 15413tert-Butyl methyl etherHCID 759283,5-Difluorophenol

生成物 1

HCID 670464324-(tert-Butyl)-3,5-difluorophenol収率 31.5%

試薬・触媒・溶媒 2

HCID 9856075Zirconium chloride (ZrCl4), (T-4)-触媒HCID 6344Dichloromethane溶媒2 回

反応条件

温度
0 °C

実験手順

To a suspension of zirconium tetrachloride (1.17 g, 5 mmol) in DCM (10 ml) was added tert-butyl methyl ether (0.44 g, 5 mmol) at 0° C. After stirring for 30 minutes at 0° C., 3,5-difluorophenol (0.65 g, 5 mmol) in DCM was placed there and the mixture was stirred for 8 hours at 60° C. The reaction was quenched with saturated sodiumbicarbonate aqueous solution followed by addition of DCM. Then, organic layer was separated, dried over magnesium sulfate, evaporated in vacuo to give the residue which was purified through silica gel column chromatography eluting with hexane/EtOAc (20:1 to 4:1) to furnish 4-tert-butyl-3,5-difluorophenol as colorless oil (293 mg, 31%). 1H NMR (300 MHz, CDCl3): δ 1.42 (9H, t, J=2.2 Hz), 5.22 (1H, bs), 6.32 (2H, d, J=11.9 Hz).

後処理

  1. stirringthe mixture was stirred for 8 hours at 60° C
  2. customThe reaction was quenched with saturated sodiumbicarbonate aqueous solution
  3. additionfollowed by addition of DCM
  4. customThen, organic layer was separated
  5. dry with materialdried over magnesium sulfate
  6. customevaporated in vacuo
  7. customto give the residue which
  8. customwas purified through silica gel column chromatography
  9. washeluting with hexane/EtOAc (20:1 to 4:1)

出典と根拠

ORDレコード
ord-085dd2254c4043569fd29bb17517d02a
出典データセット
uspto-grants-2009_04
特許番号
US07514457B2

反応ノート

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