Cesium carbonate → Methyl 3-(hydroxymethyl)-5-methylbenzoate

HRID 14122

반응식

HRID 14122 반응식
Br[C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([CH2:12][OH:13])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].[C:14](=O)([O-])[O-].[Cs+].[Cs+].C(=O)([O-])[O-].[K+].[K+].CB1OB(C)OB(C)O1>O1CCOCC1>[OH:13][CH2:12][C:10]1[CH:9]=[C:4]([CH:3]=[C:2]([CH3:14])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6]

참가 물질

6

반응물 4

HCID 10796Cesium carbonateHCID 11430Potassium CarbonateHCID 574072TrimethylboroxineHCID 11356988Methyl 3-bromo-5-(hydroxymethyl)benzoate

생성물 1

HCID 21086184Methyl 3-(hydroxymethyl)-5-methylbenzoate

시약·촉매·용매 1

HCID 312751,4-Dioxane용매

실험 절차

To a stirred solution of methyl 3-bromo-5-(hydroxymethyl)benzoate (4.53 g, 18.5 mmol) in dioxane (74 mL) is added cesium carbonate (6.0 g, 18.5 mmol), potassium carbonate (5.1 g, 37 mmol), and palladium(0)tetrakis(triphenylphosphine) (2.1 g, 1.85 mmol), followed by trimethyl boroxine (5.1 mL, 37 mmol). The reaction mixture is refluxed for 12 h, cooled to room temperature, and then partitioned between water and ethyl acetate. The organic layer is washed with water and brine, dried (magnesium sulfate), filtered, and concentrated under reduced pressure. The black oil is adsorbed onto silica gel followed by purification by flash column chromatography (silica, 25% ethyl acetate/hexanes) to provide the title compound. 1H NMR (300 MHz, CDCl3) δ 7.75 (s, 1H), 7.65 (s, 1H), 7.39 (s, 1H), 5.31 (br s, 1H), 4.53 (s, 1H), 3.84 (s, 3H), 2.36 (s, 3H).

후처리

  1. temperatureThe reaction mixture is refluxed for 12 h
  2. custompartitioned between water and ethyl acetate
  3. washThe organic layer is washed with water and brine
  4. dry with materialdried (magnesium sulfate)
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customfollowed by purification by flash column chromatography (silica, 25% ethyl acetate/hexanes)

출처 및 근거

ORD 기록
ord-24bd8b96751c4203a4cbb24cfac9f02d
출처 데이터셋
uspto-grants-2010_06
특허 번호
US07727997B2

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