Tetrahydrofuran → 4-Ethoxy-2,2',3,3'-tetrafluorobiphenyl-4-carboaldehyde

HRID 1941720Notes

Reaction equation

HRID 1941720 reaction equation
C1C[O:4][CH2:3]C1.[CH2:6]([O:8][C:9]1[CH:14]=[CH:13][C:12]([C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([F:21])[C:16]=2[F:22])=[C:11]([F:23])[C:10]=1[F:24])[CH3:7].C([Li])(CC)C>CN(C=O)C>[CH2:6]([O:8][C:9]1([CH:3]=[O:4])[CH:14]=[CH:13][C:12]([C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([F:21])[C:16]=2[F:22])=[C:11]([F:23])[CH:10]1[F:24])[CH3:7]

Participants

5

Reactant 3

HCID 8028TetrahydrofuranHCID 58453709HCID 58453709, compoundHCID 178418400CID 53628100

Product 1

HCID 866599304-Ethoxy-2,2',3,3'-tetrafluorobiphenyl-4-carboaldehydeYield 70%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
-65 °C

Procedure

THF (400 ml) was added to 4-ethoxy-2,2′,3,3′-tetrafluorobiphenyl (6) (39.25 g) prepared by means of a conventional coupling reaction in a reaction vessel under an atmosphere of nitrogen. The solution was cooled to −65° C. or lower, and sec-butyllithium (1.08 M in cyclohexane and n-hexane; 141.3 ml) was added dropwise. After the reaction mixture had been stirred at −65° C. for another 1 hour, N,N,-dimethylformamide (21.2 g) was added dropwise, and the reaction mixture was warmed slowly to room temperature. The reaction mixture was quenched with a saturated aqueous solution of ammonium chloride, and water (500 ml) was added to give two layers. The water layer was extracted with toluene (200 ml) twice, and the combined organic layer was washed with water and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was treated with silica gel chromatography (silica gel: 30 g, eluent: toluene) to give 4-ethoxy-2,2′,3,3′-tetrafluorobiphenyl-4-carboaldehyde (7) (30 g) in 70% yield.

Workup

  1. customprepared by means of a conventional coupling reaction in a reaction vessel under an atmosphere of nitrogen
  2. temperaturethe reaction mixture was warmed slowly to room temperature
  3. customThe reaction mixture was quenched with a saturated aqueous solution of ammonium chloride, and water (500 ml)
  4. additionwas added
  5. customto give two layers
  6. extractionThe water layer was extracted with toluene (200 ml) twice
  7. washthe combined organic layer was washed with water
  8. dry with materialdried over anhydrous magnesium sulfate
  9. distillationThe solvent was distilled off under reduced pressure
  10. additionThe residue was treated with silica gel chromatography (silica gel: 30 g, eluent: toluene)

Sources & evidence

ORD record
ord-ff00ac905d7943bcaa639a49024ff2da
Source dataset
uspto-grants-2013_03
Patent number
US08389073B2

Reaction notes

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