1-(3-Bromo-4-fluorophenyl)ethan-1-one → HCID 57825222, compound

HRID 1668722Notes

Reaction equation

HRID 1668722 reaction equation
[Mg].Br[C:3]1[CH:16]=[CH:15][C:6]([O:7][Si:8]([C:11]([CH3:14])([CH3:13])[CH3:12])([CH3:10])[CH3:9])=[C:5](C)[CH:4]=1.[CH3:18][C:19]([C:21]1[CH:26]=[CH:25][C:24]([F:27])=[C:23]([Br:28])[CH:22]=1)=O>O1CCCC1.BrCCBr>[Br:28][C:23]1[CH:22]=[C:21]([C:19]([C:3]2[CH:4]=[CH:5][C:6]([O:7][Si:8]([C:11]([CH3:12])([CH3:13])[CH3:14])([CH3:9])[CH3:10])=[CH:15][CH:16]=2)=[CH2:18])[CH:26]=[CH:25][C:24]=1[F:27]

Participants

6

Reactant 3

HCID 705081-(3-Bromo-4-fluorophenyl)ethan-1-oneHCID 5462224MagnesiumHCID 46183083HCID 46183083, compound

Product 1

HCID 57825222HCID 57825222, compoundYield 90.8%

Reagents, catalysts & solvents 2

HCID 78391,2-DibromoethaneSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

To a mixture of magnesium turnings (1.5 g, 0.06 mol, 1.2 eq) in dry tetrahydrofuran (10 mL), was added a portion (⅕) of (4-bromo-2-methyl-phenoxy)-tert-butyl-dimethyl-silane (16.0 g. 0.05 mol, 1.1 eq) in dry tetrahydrofuran (50 mL) and 1,2-dibromoethane (0.5 mL). The resulting solution was refluxed and the other (⅘) portion of the above solution was added and the resulting solution was refluxed for 2 h. After cooled at 0° C. a solution of 3-bromo-4-fluoroacetophenone (11.5 g, 0.05 mol, 1 eq) in dry tetrahydrofuran (40 mL) was added dropwise and the reaction was stirred for 3 h at room temperature. The mixture was quenched with saturated ammonium chloride solution (20 mL). The aqueous phase was extracted with dichloromethane (3×20 mL), dried (sodium sulfate) and the solvent removed in vacuo. The crude latter was dissolved in toluene (200 mL) and a catalytic amount (30 mg) of p-toluenesulfonic acid was added and refluxed for 3 h. The solvent was removed and the residue was purified by column chromatography (cyclohexane) to afford the title compound as a colourless oil (18.5 g, 39%).

Workup

  1. temperatureThe resulting solution was refluxed
  2. additionthe other (⅘) portion of the above solution was added
  3. temperaturethe resulting solution was refluxed for 2 h
  4. additionwas added dropwise
  5. customThe mixture was quenched with saturated ammonium chloride solution (20 mL)
  6. extractionThe aqueous phase was extracted with dichloromethane (3×20 mL)
  7. dry with materialdried (sodium sulfate)
  8. customthe solvent removed in vacuo
  9. dissolutionThe crude latter was dissolved in toluene (200 mL)
  10. additiona catalytic amount (30 mg) of p-toluenesulfonic acid was added
  11. temperaturerefluxed for 3 h
  12. customThe solvent was removed
  13. customthe residue was purified by column chromatography (cyclohexane)

Sources & evidence

ORD record
ord-14e0e7edd6854363b7672344fec701e1
Source dataset
uspto-grants-2011_08
Patent number
US07989449B2

Reaction notes

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