Methyl vinyl ketone → HCID 54467890, compound

HRID 1029941Notes

Reaction equation

HRID 1029941 reaction equation
C(=O)([O-])[O-].[K+].[K+].[F:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[CH:14]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[F:23])[CH:15]=[O:16].[CH3:24][C:25](=[O:28])[CH:26]=[CH2:27]>COCCOC.C(OCC)(=O)C.O>[F:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[C:14]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[F:23])([CH2:27][CH2:26][C:25](=[O:28])[CH3:24])[CH:15]=[O:16]

Participants

7

Reactant 3

HCID 6570Methyl vinyl ketoneHCID 11430Potassium CarbonateHCID 54241887HCID 54241887, compound

Product 1

HCID 54467890HCID 54467890, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-50 °C

Procedure

Potassium carbonate (26.9 g) is added to a solution of bis-(2-fluorophenyl)acetaldehyde (30.8 g) in 1,2-dimethoxyethane (135 cc) and, after cooling to -50° C., butenone (19.9 cc) is then added dropwise. The reaction mixture is stirred for 12 h at -50° C. and then for 6 hours at 25° C. and diluted with ethyl acetate (250 cc) and water (200 cc). The organic phase is washed with water (3×200 cc) and then with saturated sodium chloride solution (200 cc), dried over magnesium sulphate and concentrated under reduced pressure (2.7 kPa). The residue is chromatographed on a silica gel column (particle size 0.04-0.063 mm, diameter 5.5 cm, height 50 cm), eluting under a nitrogen pressure of 0.5 bar with a mixture of cyclohexane and ethyl acetate (90/10). 2,2-bis-(2-Fluorophenyl)-5-oxohexanal (9 g) is obtained in the form of a yellow oil. A solution of this compound (6.65 g) in toluene (100 cc) containing paratoluenesulphonic acid (1.5 g) is refluxed for 3 hours, washed with water (2×100 cc) and then with saturated sodium chloride solution (100 cc), dried over magnesium sulphate and concentrated under reduced pressure (2.7 kPa). The residue is chromatographed on a silica gel column (particle size 0.04-0.063 mm, diameter 4 cm, height 30 cm), eluting under a nitrogen pressure of 0.5 bar with a mixture of cyclohexane and ethyl acetate (90/10) and collecting 15 cc fractions. Fractions 21 to 26 are combined and concentrated to dryness under reduced pressure (2.7 kPa) to give 4,4-bis-(2-fluorophenyl)-cyclohexenone (2.83 g) in the form of yellow oil.

Workup

  1. waitfor 6 hours at 25° C.
  2. washThe organic phase is washed with water (3×200 cc)
  3. dry with materialwith saturated sodium chloride solution (200 cc), dried over magnesium sulphate
  4. concentrationconcentrated under reduced pressure (2.7 kPa)
  5. customThe residue is chromatographed on a silica gel column (particle size 0.04-0.063 mm, diameter 5.5 cm, height 50 cm)
  6. washeluting under a nitrogen pressure of 0.5 bar
  7. additionwith a mixture of cyclohexane and ethyl acetate (90/10)

Sources & evidence

ORD record
ord-de5626a069144ed2815eb5a7691cfdff
Source dataset
uspto-grants-1992_04
Patent number
US05102667

Reaction notes

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