Ethyl Acetate → HCID 66735956, compound

HRID 1641522Notes

Reaction equation

HRID 1641522 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([C:15](=[O:17])[CH3:16])=[C:11]([CH3:18])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Na+].[Br-:20].S([O-])([O-])=O.[Na+].[Na+].C(OCC)(=O)C>CC(C)=O.O.OOS([O-])=O.[K+]>[CH2:1]([O:8][C:9]1[C:14]([Br:20])=[CH:13][C:12]([C:15](=[O:17])[CH3:16])=[C:11]([CH3:18])[CH:10]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 24437Sodium SulfiteHCID 253881Sodium BromideHCID 890054HCID 890054, compound

Product 1

HCID 66735956HCID 66735956, compoundYield 97.8%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolvent4×HCID 23707502Potassium hydroxy sulfiteSolvent

Procedure

To a solution of 1-[4-(benzyloxy)-2-methylphenyl]ethanone (20.9 g, 87.1 mmol) in acetone (300 mL), a solution of NaBr (9.86 g, 95.9 mmol) in water (100 mL), water (200 mL) and Oxone® (oxone monopersulfate compound, Aldrich) (59.0 g, 95.9 mmol) were added and stirred at room temperature for 2.5 hours. The reaction mixture was mixed with a solution of sodium sulfite (20 g) in water (50 mL) under ice cooling, followed by addition of water and ethyl acetate to separate the organic layer. The organic layer was washed with 20 wt. % aqueous sodium sulfite and saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate. After filtering off the desiccant, the solvent was distilled off under reduced pressure to give a mixture (27.2 g) of 1-[4-(benzyloxy)-5-bromo-2-methylphenyl]ethanone and 1-[4-(benzyloxy)-3-bromo-2-methylphenyl]ethanone. To this mixture, a 5% solution of sodium hypochlorite (300 mL, 255 mmol) and a solution of potassium hydroxide (4.80 g, 85.3 mmol) in water (10 mL) were added and stirred at 120° C. for 1 hour. The reaction mixture was cooled to room temperature and filtered to collect the precipitated insoluble product, to which 2N hydrochloric acid was then added. After extraction with ethyl acetate, the organic layer was washed with 2N hydrochloric acid and saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate. After filtering off the desiccant, the solvent was distilled off under reduced pressure and the resulting residue was washed with methanol to give the titled compound (16.6 g, 59%, 2 steps) as a colorless powder.

Workup

  1. customto separate the organic layer
  2. washThe organic layer was washed with 20 wt. % aqueous sodium sulfite and saturated aqueous sodium chloride
  3. dry with materialdried over anhydrous magnesium sulfate
  4. filtrationAfter filtering off the desiccant
  5. distillationthe solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-d8c1e943364749848e769df016346704
Source dataset
uspto-grants-2012_02
Patent number
US08115017B2

Reaction notes

Loading…