Methyl vinyl ketone → 4,4-Bis(3-fluorophenyl)cyclohexenone

HRID 1029935Notes

Reaction equation

HRID 1029935 reaction equation
[CH3:1][C:2](=[O:5])[CH:3]=[CH2:4].[F:6][C:7]1[CH:8]=[C:9]([CH:13]([C:16]2[CH:21]=[CH:20][CH:19]=[C:18]([F:22])[CH:17]=2)[CH:14]=O)[CH:10]=[CH:11][CH:12]=1.[OH-].[K+]>C(OCC)C.C(O)C.C(OCC)(=O)C.O>[F:6][C:7]1[CH:8]=[C:9]([C:13]2([C:16]3[CH:21]=[CH:20][CH:19]=[C:18]([F:22])[CH:17]=3)[CH2:14][CH2:1][C:2](=[O:5])[CH:3]=[CH:4]2)[CH:10]=[CH:11][CH:12]=1

Participants

8

Reactant 3

HCID 6570Methyl vinyl ketoneHCID 14797Potassium HydroxideHCID 54068354HCID 54068354, compound

Product 1

HCID 543073284,4-Bis(3-fluorophenyl)cyclohexenone

Reagents, catalysts & solvents 4

HCID 702EthanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Butenone (50.4 cc) is added to a solution of bis-(3-fluorophenyl)acetaldehyde (144.5 g) in ethyl ether (500 cc) and then, after cooling to 0° C., a solution of potassium hydroxide (13.9 g) in ethanol (89 cc) is added dropwise. The reaction mixture is stirred for 2 h at 0° C. and then for 16 hours at 25° C. and diluted with ethyl acetate (300 cc) and water (500 cc). The aqueous phase is washed with ethyl acetate (300 cc). The combined organic phases are washed with saturated sodium chloride solution (500 cc), dried over magnesium sulphate and concentrated under reduced pressure (2.7 kPa). The residue is chromatographed (in two passes) on silica gel (particle size 0.04-0.063 mm, columns 8.5 cm in diameter and 34 cm high), eluting under a nitrogen pressure of 0.5 bar with a mixture of cyclohexane and ethyl acetate (90/10). 4,4-bis-(3-Fluorophenyl)-cyclohexenone (90.3 g) is obtained in the form of white crystals. m.p.=95° C.

Workup

  1. waitfor 16 hours at 25° C.
  2. washThe aqueous phase is washed with ethyl acetate (300 cc)
  3. washThe combined organic phases are washed with saturated sodium chloride solution (500 cc)
  4. dry with materialdried over magnesium sulphate
  5. concentrationconcentrated under reduced pressure (2.7 kPa)
  6. customThe residue is chromatographed (in two passes) on silica gel (particle size 0.04-0.063 mm, columns 8.5 cm in diameter and 34 cm high)
  7. washeluting under a nitrogen pressure of 0.5 bar
  8. additionwith a mixture of cyclohexane and ethyl acetate (90/10)

Sources & evidence

ORD record
ord-c72e6252e77d42bda61bdea4f6c0e687
Source dataset
uspto-grants-1992_04
Patent number
US05102667

Reaction notes

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