tert-Butyldimethylsilyl chloride → 2-(T-Butyldimethylsilyloxy)-4-bromoanisole

HRID 970957노트

반응식

HRID 970957 반응식
C(N(C(C)C)C(C)C)C.[Br:10][C:11]1[CH:12]=[CH:13][C:14]([O:18][CH3:19])=[C:15]([OH:17])[CH:16]=1.[C:20]([Si:24](Cl)([CH3:26])[CH3:25])([CH3:23])([CH3:22])[CH3:21].C([O-])(O)=O.[Na+]>CN(C=O)C.CCOCC.O>[Br:10][C:11]1[CH:12]=[CH:13][C:14]([O:18][CH3:19])=[C:15]([CH:16]=1)[O:17][Si:24]([C:20]([CH3:23])([CH3:22])[CH3:21])([CH3:26])[CH3:25]

참가 물질

8

반응물 4

HCID 28928tert-Butyldimethylsilyl chlorideHCID 81531DiisopropylethylamineHCID 1422285-Bromo-2-methoxyphenolHCID 516892Sodium Bicarbonate

생성물 1

HCID 109800492-(T-Butyldimethylsilyloxy)-4-bromoanisole수율 99%

시약·촉매·용매 3

HCID 962Water용매HCID 3283Diethyl Ether용매HCID 6228Dimethylformamide용매

실험 절차

Ethyldiisopropylamine (1.72 ml, 9.85 mmol) was added to a solution of 5-bromo-2-methoxy-phenol (0.80 g, 3.94 mmol) in DMF (10 ml) at rt. The clear, colorless solution was stirred for 5 min. followed by addition of tert-butylchlorodimethylsilane (0.71 g, 4.73 mmol). The reaction was complete in about two hours. Distilled water (˜6 ml) was added to the clear solution, stirred for 10 min., added ether (50 ml) and sat. NaHCO3 (10 ml), stirred for 30 min. The ether portion was separated and the aqueous phase was extracted with ether (2×50 ml). The combined ether phases were washed with water (100 ml), brine (60 ml), dried over MgSO4, filtered and concentrated to an oil, which was further purified by flash column chromatography [100% hexane with 0.5% triethylamine gradient to 30% EtOAc in hexane with 0.5% Et3N] to give (5-bromo-2-methoxy-phenoxy)-tert-butyl-dimethyl-silane as an oil (0.59 g, 99%), HPLC purity 99.5% at 1.43 min. (90/10 ACN/0.1% H3PO4): 1H NMR (DMSO-d6) δ 7.04-6.97(m, 2H, Ar), 6.71 (d, J=8 Hz, Ar), 3.78 (s, 3H, single OCH3), 0.99 (s, 9H, 30CH3), 0.16 (s, 6H, 2OCH3). The product was carried over to the next step.

후처리

  1. waitThe reaction was complete in about two hours
  2. stirringstirred for 10 min.
  3. stirringstirred for 30 min
  4. customThe ether portion was separated
  5. extractionthe aqueous phase was extracted with ether (2×50 ml)
  6. washThe combined ether phases were washed with water (100 ml), brine (60 ml)
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated to an oil, which
  10. customwas further purified by flash column chromatography [100% hexane with 0.5% triethylamine gradient to 30% EtOAc in hexane with 0.5% Et3N]

출처 및 근거

ORD 기록
ord-9e120d6d8fb343bc90e0777752dc36bd
출처 데이터셋
uspto-grants-2007_12
특허 번호
US07312241B2

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