4-Bromophenol → HCID 62702733, compound

HRID 1970232Notes

Reaction equation

HRID 1970232 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][CH:3]=1.C([O-])([O-])=O.[Cs+].[Cs+].C(OCC)(=O)C.Br[C:22]1[CH:30]=[C:29]([CH3:31])[CH:28]=[CH:27][C:23]=1[C:24]([OH:26])=[O:25]>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][C:22]2[CH:30]=[C:29]([CH3:31])[CH:28]=[CH:27][C:23]=2[C:24]([OH:26])=[O:25])=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 78084-BromophenolHCID 8857Ethyl AcetateHCID 10796Cesium carbonateHCID 2262922-Bromo-4-methylbenzoic acid

Product 1

HCID 62702733HCID 62702733, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

4-Bromophenol (0.87 g, 5 mmol), Cs2CO3 (1.6 g, 5 mmol), CuOTf toluene complex (2:1) (0.0625 mmol, 5 mol % Cu, 33 mg), ethyl acetate (0.013 ml, 0.125 mmol) were added to a solution of 2-bromo-4-methylbenzoic acid (0.86 g, 5 mmol) in toluene (2 mL) in a sealed tube. The reaction mixture was purged with N2, and was heated to 110° C. until the aryl halide was consumed as determined by LC-MS (48 h). After cooling to rt, the mixture was filtered through a Celite plug. The Celite plug was washed with EtOAc. The mixture was acidified by 1N HCl, and extracted w/EtOAc. The combined organic phases were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated. This residue was purified via column chromatography on silica gel (gradient elution with 0-10% MeOH/DCM) to afford 2-(4-bromophenoxy)-4-methylbenzoic acid, MS m/z=309.1 [M+H]+. Calc'd for C14H11BrO3: 307.1.

Workup

  1. customThe reaction mixture was purged with N2
  2. customwas consumed
  3. customas determined by LC-MS (48 h)
  4. temperatureAfter cooling to rt
  5. filtrationthe mixture was filtered through a Celite plug
  6. washThe Celite plug was washed with EtOAc
  7. extractionextracted w/EtOAc
  8. washThe combined organic phases were washed with brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThis residue was purified via column chromatography on silica gel (gradient elution with 0-10% MeOH/DCM)

Sources & evidence

ORD record
ord-0aedde642d7f4adfa2284cfd4e38920e
Source dataset
uspto-grants-2013_04
Patent number
US08426447B2

Reaction notes

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