Chlorotrimethylsilane → Trimethyl{3-methyl-4-[(trimethylsilyl)oxy]phenyl}silane

HRID 2217098노트

반응식

HRID 2217098 반응식
Br[C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[C:4]([CH3:9])[CH:3]=1.C([Li])CCC.[CH3:15][Si:16](Cl)([CH3:18])[CH3:17].[Cl-].[NH4+]>C1COCC1>[CH3:9][C:4]1[CH:3]=[C:2]([Si:16]([CH3:18])([CH3:17])[CH3:15])[CH:7]=[CH:6][C:5]=1[O:8][Si:16]([CH3:18])([CH3:17])[CH3:15]

참가 물질

6

반응물 4

HCID 6397ChlorotrimethylsilaneHCID 168964-Bromo-2-methylphenolHCID 25517Ammonium ChlorideHCID 178418339Butyllithium

생성물 1

HCID 59824832Trimethyl{3-methyl-4-[(trimethylsilyl)oxy]phenyl}silane수율 79%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

To a solution of 4-bromo-2-methylphenol (1.5 g, 8.02 mmol) in THF (16 mL) at −78° C. was added n-butyl lithium (12.5 mL, 1.6 M solution in hexanes, 20.05 mmol) and the reaction was stirred at this temperature for 30 minutes. Trimethylsilyl chloride (2.5 mL, 20.05 mmol) was then added and the resulting mixture was stirred at −78° C. for a further 1.5 hours. The reaction was allowed to warm to room temperature and saturated ammonium chloride solution (10 mL) was added. The mixture was extracted with diethyl ether (2×20 mL) and the combined organic extracts were dried (magnesium sulphate) and concentrated under reduced pressure to give the intermediate 2-methyl-4-(trimethylsilyl)phenoxytrimethylsilane as a pale yellow oil (1.6 g). This intermediate was then diluted with THF (3 mL) and treated with TBAF (6.3 mL, 1.0 M solution in THF, 6.33 mmol) at room temperature. The reaction was stirred at this temperature for 5 minutes and poured into water (10 mL). The aqueous portion was then extracted with ether (3×5 mL) and the combined organic extracts were washed (saturated brine), dried (magnesium sulphate) and concentrated under reduced pressure. The resulting oily residue was pre-adsorbed onto silica and the 2-methyl-4-(trimethylsilyl)phenol isolated by column chromatography (SiO2; light petroleum to 7:3 light petroleum-diethyl ether) as a pale yellow oil (0.78 g, 68%). Rf=0.65 (7:3 light petroleum-diethyl ether, silica). 1H NMR (DMSO-d6): δH 0.17 (9 H, s), 2.1 (3 H, s), 6.77 (1 H, d, J=7.8 Hz), 7.12 (1 H, d, J=7.8 Hz), 7.17 (1 H, s), 9.36 (1 H, s).

후처리

  1. stirringthe resulting mixture was stirred at −78° C. for a further 1.5 hours
  2. extractionThe mixture was extracted with diethyl ether (2×20 mL)
  3. dry with materialthe combined organic extracts were dried (magnesium sulphate)
  4. concentrationconcentrated under reduced pressure

출처 및 근거

ORD 기록
ord-a43e8b811bdd4811b6dd28f3dd3c88c3
출처 데이터셋
uspto-grants-2008_08
특허 번호
US07407649B2

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