Sodium Carbonate → 2,2',3,4'-Tetrafluoro-[1,1'-biphenyl]-4-carbaldehyde

HRID 531066Notes

Reaction equation

HRID 531066 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1B(O)O.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1.C(=O)([O-])[O-].[Na+].[Na+].Br[C:48]1[CH:55]=[CH:54][C:51]([CH:52]=[O:53])=[C:50]([F:56])[C:49]=1[F:57]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O.C1(C)C=CC=CC=1>[F:57][C:49]1[C:50]([F:56])=[C:51]([CH:52]=[O:53])[CH:54]=[CH:55][C:48]=1[C:3]1[CH:4]=[CH:5][C:6]([F:8])=[CH:7][C:2]=1[F:1]

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 27343342,4-Difluorophenylboronic acidHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 269863904-Bromo-2,3-difluorobenzaldehyde

Product 1

HCID 1179922312,2',3,4'-Tetrafluoro-[1,1'-biphenyl]-4-carbaldehydeYield 94.9%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

(2,4-Difluorophenyl)boronic acid (5.39 g), dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine (1.40 g), a 2 M aqueous sodium carbonate solution (34.1 mL), and tris(dibenzylideneacetone)dipalladium(0) (1.46 g) were added at room temperature to a toluene (150 mL) solution of 4-bromo-2,3-difluorobenzaldehyde (5.03 g), and the mixture was stirred at 100° C. for 16 hours in a nitrogen atmosphere. Water was added to the reaction mixture at room temperature, and the mixture was filtered through celite. Then, the filtrate was subjected to extraction with ethyl acetate. The obtained organic layer was washed with water and saturated saline in this order and dried over anhydrous magnesium sulfate, and then, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain the title compound (5.49 g).

Workup

  1. filtrationthe mixture was filtered through celite
  2. extractionThen, the filtrate was subjected to extraction with ethyl acetate
  3. washThe obtained organic layer was washed with water and saturated saline in this order
  4. dry with materialdried over anhydrous magnesium sulfate
  5. distillationthe solvent was distilled off under reduced pressure
  6. customThe obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate)

Sources & evidence

ORD record
ord-e5019d2c88364d569be373c880c11bdd
Source dataset
uspto-grants-2016_05
Patent number
US09353108B2

Reaction notes

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