Resorcinol → 1,3-bis(3-fluorophenoxy)benzene

HRID 586099Notes

Reaction equation

HRID 586099 reaction equation
[C:1]1([CH:8]=[CH:7][CH:6]=[C:4]([OH:5])[CH:3]=1)O.F[C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([F:16])[CH:11]=1.[C:17](=[O:20])([O-])[O-].[K+].[K+]>CN1CCN(C)C1=O>[F:16][C:12]1[CH:11]=[C:10]([CH:15]=[CH:14][CH:13]=1)[O:5][C:4]1[CH:6]=[CH:7][CH:8]=[C:1]([O:20][C:17]2[CH:15]=[CH:10][CH:11]=[C:12]([F:16])[CH:13]=2)[CH:3]=1

Participants

5

Reactant 3

HCID 5054ResorcinolHCID 97411,3-DifluorobenzeneHCID 11430Potassium Carbonate

Product 1

HCID 121356931,3-bis(3-fluorophenoxy)benzeneYield 53%

Reagents, catalysts & solvents 1

HCID 66611,3-Dimethyl-2-imidazolidinoneSolvent

Conditions

Temperature
220 °C

Procedure

In a nitrogen atmosphere, 76.4 g (0.693 mole) of resorcinol, 382 g (3.34 mole) of m-difluorobenzene, 500 g (3.62 mole) of potassium carbonate and 1 liter of 1,3-dimethyl-2-imidazolidinone (abbreviated to DMI hereinafter) were placed in a 3-liter SUS autoclave, and the autoclave was closed. Then, the reaction vessel was purged with nitrogen, and the internal temperature was raised up to 220° C. with stirring. The contents in the reaction vessel were stirred for 20 hours under heating at 220° C. During the stirring, the internal pressure was not more than 0.7 MPa. The progress of the reaction was confirmed by high performance liquid chromatography (HPLC). The intermediate product, 3-(3fluorophenoxy)phenol almost disappeared at this time. After cooling to room temperature, the reaction mixture was filtered to separate a salt. To the resulting filtrate, 1 liter of toluene and 2 liters of water were added. Then, liquid separation was carried out to obtain an organic phase. The organic phase was washed with 1 liter of a 5% sodium hydroxide aqueous solution and then washed with 1 liter of water. The solvent and the starting difluorobenzene were distilled off under reduced pressure, and then quantitative determination was made by HPLC. As a result, the reaction yield of 1,3-bis(3-fluorophenoxy)benzene was 63%. The resulting crude compound was purified by vacuum distillation (bp 190° C./6.5 hPa) to obtain 109 g (0.365 mole, purity (HPLC): 99%, yield: 53%) of 1,3-bis(3-fluorophenoxy)benzene as a colorless oily product. The structure and the properties of the compound are as follows.

Workup

  1. customthe autoclave was closed
  2. customThen, the reaction vessel was purged with nitrogen
  3. stirringThe contents in the reaction vessel were stirred for 20 hours
  4. temperatureunder heating at 220° C
  5. temperatureAfter cooling to room temperature
  6. filtrationthe reaction mixture was filtered
  7. customto separate a salt
  8. additionTo the resulting filtrate, 1 liter of toluene and 2 liters of water were added
  9. customThen, liquid separation
  10. customto obtain an organic phase
  11. washThe organic phase was washed with 1 liter of a 5% sodium hydroxide aqueous solution
  12. washwashed with 1 liter of water
  13. distillationThe solvent and the starting difluorobenzene were distilled off under reduced pressure
  14. distillationThe resulting crude compound was purified by vacuum distillation (bp 190° C./6.5 hPa)

Sources & evidence

ORD record
ord-f4413bee1d3e4ed49d9ab006ac70b4fe
Source dataset
uspto-grants-2005_08
Patent number
US06933411B2

Reaction notes

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