Dimethylformamide → 1,1'-{Sulfonylbis[(4,1-phenylene)oxy]}bis[3-(trifluoromethyl)benzene]

HRID 973892Notes

Reaction equation

HRID 973892 reaction equation
[F:1][C:2]([F:11])([F:10])[C:3]1[CH:4]=[C:5]([OH:9])[CH:6]=[CH:7][CH:8]=1.[CH:12]1[C:17]([S:18]([C:21]2[CH:26]=[CH:25][C:24](Cl)=[CH:23][CH:22]=2)(=[O:20])=[O:19])=[CH:16][CH:15]=[C:14](Cl)[CH:13]=1.[C:29]([O-:32])([O-])=O.[K+].[K+].CN(C=O)C>O.CCOCC>[F:1][C:2]([F:10])([F:11])[C:3]1[CH:4]=[C:5]([CH:6]=[CH:7][CH:8]=1)[O:9][C:14]1[CH:15]=[CH:16][C:17]([S:18]([C:21]2[CH:26]=[CH:25][C:24]([O:32][C:29]3[CH:6]=[CH:7][CH:8]=[C:3]([C:2]([F:11])([F:10])[F:1])[CH:4]=3)=[CH:23][CH:22]=2)(=[O:20])=[O:19])=[CH:12][CH:13]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 66254,4'-Dichlorodiphenyl sulfoneHCID 73763-(Trifluoromethyl)phenolHCID 11430Potassium Carbonate

Product 1

HCID 199870431,1'-{Sulfonylbis[(4,1-phenylene)oxy]}bis[3-(trifluoromethyl)benzene]

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Procedure

All apparatus is rigorously dried and flushed with nitrogen before use. The reaction is performed in a 250 mL 3-necked flask equipped with a mechanical stirrer, a reflux condenser topped with a nitrogen inlet tube, and a stopper. The flask is charged with 3-trifluoromethyl-phenol (11.29 g, 69.7 mmol), 4,4'-dichlorodiphenyl sulfone (10.00 g, 34.8 mmol), K2CO3 (15.00 g, 109 mmol) and DMF (125 mL). The reacting mixture is stirred and heated at reflux for 12 hours. The mixture is analyzed by gas chromatography, which showed that almost no starting materials remained. The reaction mixture is diluted with water, and the aqueous layer is removed to leave an oil. This oil is diluted with ether and washed with 5% NaOH to remove any acidic species. It is then washed with brine, dried with MgSO4, and the solvent removed on the rotary evaporator to leave a white crystalline solid. This solid is purified by column chromatography on flash grade silica gel using a 1:1 mixture of CH 2 Cl2 /Hexane as eluent. Further purification is accomplished by recrystallization of the white solid from ethanol to give white, diamond-shaped crystals (11.08 g, 59%), m.p. 96.5-97.5° C.

Workup

  1. customAll apparatus is rigorously dried
  2. customflushed with nitrogen before use
  3. customThe reaction is performed in a 250 mL 3-necked flask
  4. customequipped with a mechanical stirrer, a reflux condenser
  5. customtopped with a nitrogen inlet tube
  6. temperatureheated
  7. temperatureat reflux for 12 hours
  8. customthe aqueous layer is removed
  9. customto leave an oil
  10. washwashed with 5% NaOH
  11. customto remove any acidic species
  12. washIt is then washed with brine
  13. dry with materialdried with MgSO4
  14. customthe solvent removed on the rotary evaporator
  15. customto leave a white crystalline solid
  16. customThis solid is purified by column chromatography on flash grade silica gel using
  17. additiona 1:1 mixture of CH 2 Cl2 /Hexane as eluent
  18. customFurther purification
  19. customis accomplished by recrystallization of the white solid from ethanol
  20. customto give white

Sources & evidence

ORD record
ord-a99319ada2724f38a5ca644c045463dd
Source dataset
uspto-grants-1991_11
Patent number
US05066409

Reaction notes

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