Pyridine → 3,5-Difluoro-4-formylphenyl octan-2-yl carbonate

HRID 68247

반응식

HRID 68247 반응식
[CH3:1][CH:2]([OH:9])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].ClC(Cl)(O[C:14](=[O:20])[O:15][C:16](Cl)(Cl)Cl)Cl.N1C=CC=CC=1.[F:28][C:29]1[CH:36]=C(O)[CH:34]=[C:33]([F:38])[C:30]=1[CH:31]=[O:32]>C(Cl)Cl.O.C1COCC1>[C:14](=[O:20])([O:9][CH:2]([CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8])[CH3:1])[O:15][C:16]1[CH:36]=[C:29]([F:28])[C:30]([CH:31]=[O:32])=[C:33]([F:38])[CH:34]=1

참가 물질

8

반응물 4

HCID 1049Pyridine2회HCID 200832-OctanolHCID 94429TriphosgeneHCID 249035482,6-Difluoro-4-hydroxybenzaldehyde

생성물 1

HCID 582347323,5-Difluoro-4-formylphenyl octan-2-yl carbonate수율 137.1%

시약·촉매·용매 3

HCID 962Water용매HCID 6344Dichloromethane용매HCID 8028Tetrahydrofuran용매

실험 절차

To a 250 mL dry round bottom flask were added 2-octanol (4.51 g, 34.6 mmol), triphosgene (3.44 g, 11.6 mmol) and anhydrous THF (100 mL). The mixture was stirred in an ice-water bath, then pyridine (5.6 mL, 69.2 mmol) was injected slowly. After stirring at room temperature for 30 minutes, the mixture was filtered, and the filtrate was concentrated. The residue was dissolved in 15 mL of CH2Cl2 and cooled in an ice-water bath. To this stirring solution, a solution of 2,6-difluoro-4-hydroxybenzaldehyde (4.2 g, 26.6 mmol) and pyridine (2.80 mL, 34.6 mmol) in 20 mL of anhydrous CH2Cl2 was added slowly. After stirring at room temperature for 2 hours, water (80 mL) was added to the reaction mixture. The CH2Cl2 layer was separated, and the aqueous layer was extracted continually with CH2Cl2 (100 mL×3). The combined CH2Cl2 solution was dried over Na2SO4. After removal of the solvent, the residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting) to give 3,5-difluoro-4-formylphenyl octan-2-yl carbonate (5.0 g) as a colorless oil. Yield: 46%. 13C NMR (CDCl3, 75.5 MHz): δ=183.2, 163.4 (dd, J=263.0, 8.53 Hz), 156.3 (t, J=15.2 Hz), 151.2, 111.8 (t, J=11.0 Hz), 105.9 (dd, J=25.7, 3.62 Hz), 78.0, 35.6, 31.6, 28.9, 25.1, 22.4, 19.6, 13.9.

후처리

  1. customTo a 250 mL dry round bottom flask
  2. stirringAfter stirring at room temperature for 30 minutes
  3. filtrationthe mixture was filtered
  4. concentrationthe filtrate was concentrated
  5. dissolutionThe residue was dissolved in 15 mL of CH2Cl2
  6. temperaturecooled in an ice-water bath
  7. stirringAfter stirring at room temperature for 2 hours
  8. customThe CH2Cl2 layer was separated
  9. extractionthe aqueous layer was extracted continually with CH2Cl2 (100 mL×3)
  10. dry with materialThe combined CH2Cl2 solution was dried over Na2SO4
  11. customAfter removal of the solvent
  12. customthe residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting)

출처 및 근거

ORD 기록
ord-683052c4758f420bbee8b8c281e7c86d
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08822435B2

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