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

HRID 2108828노트

반응식

HRID 2108828 반응식
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]

참가 물질

5

반응물 2

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

생성물 1

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

시약·촉매·용매 2

HCID 9856075Zirconium chloride (ZrCl4), (T-4)-촉매HCID 6344Dichloromethane용매2회

반응 조건

온도
0 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-085dd2254c4043569fd29bb17517d02a
출처 데이터셋
uspto-grants-2009_04
특허 번호
US07514457B2

반응 노트

불러오는 중…