Sodium Thiosulfate → 3-Bromo-4-fluorophenyl acetate

HRID 1815810Notes

Reaction equation

HRID 1815810 reaction equation
CC([C:4]1[CH:9]=[CH:8][C:7]([F:10])=[C:6]([Br:11])[CH:5]=1)=O.ClC1C=CC=[C:15]([C:19]([O:21]O)=[O:20])C=1.S([O-])([O-])(=O)=S.[Na+].[Na+]>ClCCl.C(OCC)C>[C:19]([O:21][C:4]1[CH:9]=[CH:8][C:7]([F:10])=[C:6]([Br:11])[CH:5]=1)(=[O:20])[CH3:15]

Participants

6

Reactant 3

HCID 24477Sodium ThiosulfateHCID 70297m-Chloroperbenzoic acid3×HCID 705081-(3-Bromo-4-fluorophenyl)ethan-1-one

Product 1

HCID 207854593-Bromo-4-fluorophenyl acetateYield 68%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 1.09 gm (5 mMol) 3-bromo-4-fluoroacetophenone and 3.45 gm (20 mMol) m-chloroperbenzoic acid (70%) in 15 mL dichloromethane was heated at reflux for 18 hours. An additional 3.45 gm m-chloroperbenzoic acid were added and reflux continued for about 12 hours. At this point an additional 1.4 gm m-chloroperbenzoic acid were added and reflux continued for 18 hours. The reaction mixture was cooled to room temperature and was then diluted with 50 mL diethyl ether. The resulting mixture was cooled to 0° C. and was then treated with 15 mL 20% aqueous sodium thiosulfate. The resulting slurry was stirred for about 1 hour and then the phases separated. The organic phase was washed sequentially with 3×20 mL 20% aqueous sodium thiosulfate followed by 3×20 mL saturated aqueous sodium chloride. The organic phase was then dried over sodium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel chromatography, eluting with 10:1 hexane:diethyl ether. Fractions containing product were combined and concentrated under reduced pressure to provide 68% of the desired compound.

Workup

  1. temperatureat reflux for 18 hours
  2. temperaturereflux
  3. temperaturereflux
  4. waitcontinued for 18 hours
  5. temperatureThe resulting mixture was cooled to 0° C.
  6. customthe phases separated
  7. washThe organic phase was washed sequentially with 3×20 mL 20% aqueous sodium thiosulfate
  8. dry with materialThe organic phase was then dried over sodium sulfate
  9. concentrationconcentrated under reduced pressure
  10. washeluting with 10:1 hexane
  11. additionFractions containing product
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-78b32b484ac246e4aa37cc1e6d669230
Source dataset
uspto-grants-2005_04
Patent number
US06881733B1

Reaction notes

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