Sodium Carbonate → 2',4'-Dichloro-4-ethylbiphenyl-3-carbaldehyde

HRID 1193242Notes

Reaction equation

HRID 1193242 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([CH2:10][CH3:11])=[C:6]([CH:9]=1)[CH:7]=[O:8].[Cl:12][C:13]1[CH:18]=[C:17]([Cl:19])[CH:16]=[CH:15][C:14]=1B(O)O.C(=O)([O-])[O-].[Na+].[Na+]>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].COCCOC>[Cl:12][C:13]1[CH:18]=[C:17]([Cl:19])[CH:16]=[CH:15][C:14]=1[C:2]1[CH:3]=[CH:4][C:5]([CH2:10][CH3:11])=[C:6]([CH:7]=[O:8])[CH:9]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 2734659(2,4-Dichlorophenyl)boronic acidHCID 547723895-Bromo-2-ethylbenzaldehyde

Product 1

HCID 866636742',4'-Dichloro-4-ethylbiphenyl-3-carbaldehyde

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

A suspension of 5-bromo-2-ethylbenzaldehyde (1.0 g, 4.7 mmol), 2,4-dichlorophenyl boronic acid (1.34 g, 7.0 mmol) and sodium carbonate (0.99 g, 7.98 mmol) in a mixed solvent system of 1,2-dimethoxyethane (12 ml) and distilled water (4 ml) is stirred under a nitrogen atmosphere, then flushed with nitrogen (×2). [1,1′-Bis(diphenylphosphino)ferrocene]palladium(II)chloride (1.15 g, 1.41 mmol) is then added in one portion and the suspension is again flushed with nitrogen, then heated at reflux overnight. After cooling to room temperature the reaction mixture is diluted with distilled water (10 ml) and extracted with dichloromethane (10 ml). The aqueous phase is extracted again with dichloromethane (×2), and the combined organic fractions are finally washed with brine then dried over magnesium sulfate. The crude product is purified by flash column chromatography (isohexane to 75:25 isohexane/ethyl acetate ratio eluant) to afford 2′,4′-dichloro-4-ethylbiphenyl-3-carbaldehyde as a yellow oil.

Workup

  1. distillationdistilled water (4 ml)
  2. customflushed with nitrogen (×2)
  3. customthe suspension is again flushed with nitrogen
  4. temperatureheated
  5. temperatureat reflux overnight
  6. additionis diluted with distilled water (10 ml)
  7. extractionextracted with dichloromethane (10 ml)
  8. extractionThe aqueous phase is extracted again with dichloromethane (×2)
  9. washthe combined organic fractions are finally washed with brine
  10. dry with materialthen dried over magnesium sulfate
  11. customThe crude product is purified by flash column chromatography (isohexane to 75:25 isohexane/ethyl acetate ratio eluant)

Sources & evidence

ORD record
ord-f5870c26ab274a429f7609d55f893510
Source dataset
uspto-grants-2014_03
Patent number
US08680299B2

Reaction notes

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