4-Fluorophenol → 2-(4-Fluorophenoxy)-terephthalic acid dimethyl ester

HRID 733399Notes

Reaction equation

HRID 733399 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[CH3:15][O:16][C:17](=[O:29])[C:18]1[CH:27]=[CH:26][C:21]([C:22]([O:24][CH3:25])=[O:23])=[CH:20][C:19]=1I.F[P-](F)(F)(F)(F)F>C1(C)C=CC=CC=1>[CH3:25][O:24][C:22](=[O:23])[C:21]1[CH:26]=[CH:27][C:18]([C:17]([O:16][CH3:15])=[O:29])=[CH:19][C:20]=1[O:8][C:5]1[CH:6]=[CH:7][C:2]([F:1])=[CH:3][CH:4]=1

Participants

6

Reactant 4

HCID 97324-FluorophenolHCID 9886HexafluorophosphateHCID 10796Cesium carbonateHCID 637114Dimethyl iodoterephthalate

Product 1

HCID 578392532-(4-Fluorophenoxy)-terephthalic acid dimethyl esterYield 43.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 4-fluorophenol (1.25 g, 11.15 mmol) in toluene (50 mL) was added cesium carbonate (6.10 g, 18.7 mmol) and the mixture was stirred for 15 min at rt. 2-Iodoterephthalic acid dimethyl ester (3.0 g, 9.37 mmol) and tetrakisacetonitrilecopper hexafluorophosphate (435 mg) were added, and the mixture was heated to reflux for 18 h. The mixture was allowed to cool to rt and poured into an ice-cold saturated ammonium chloride solution. The organic layer was separated, washed with a saturated potassium carbonate solution and brine, dried over magnesium sulfate, filtered, and evaporated. The residue was purified via flash column chromatography (elent gradient 1% to 20% EtOAc in heptane) to yield 1.25 g (43.8%) of title compound 2-(4-fluorophenoxy)-terephthalic acid dimethyl ester, 1e. MS m/z (MH+) 305.0.

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 18 h
  3. temperatureto cool to rt
  4. customThe organic layer was separated
  5. washwashed with a saturated potassium carbonate solution and brine
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. customThe residue was purified via flash column chromatography (elent gradient 1% to 20% EtOAc in heptane)

Sources & evidence

ORD record
ord-f4abc21115c4453a837545cd81dc1c1b
Source dataset
uspto-grants-2009_09
Patent number
US07589104B2

Reaction notes

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