Water → 4'-Hydroxy-2',6'-dimethyl-[1,1'-biphenyl]-3-carbaldehyde

HRID 1691517Notes

Reaction equation

HRID 1691517 reaction equation
Br[C:2]1[C:7]([CH3:8])=[CH:6][C:5]([OH:9])=[CH:4][C:3]=1[CH3:10].[CH:11]([C:13]1[CH:14]=[C:15](B(O)O)[CH:16]=[CH:17][CH:18]=1)=[O:12].O.C(OCC)(=O)C>C(=O)([O-])[O-].[Na+].[Na+].C(O)C.C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[OH:9][C:5]1[CH:6]=[C:7]([CH3:8])[C:2]([C:17]2[CH:16]=[CH:15][CH:14]=[C:13]([CH:11]=[O:12])[CH:18]=2)=[C:3]([CH3:10])[CH:4]=1

Participants

9

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 819704-Bromo-3,5-dimethylphenolHCID 27343563-Formylphenylboronic acid

Product 1

HCID 231116914'-Hydroxy-2',6'-dimethyl-[1,1'-biphenyl]-3-carbaldehydeYield 75.4%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 1140TolueneSolventHCID 10340Sodium CarbonateSolvent

Conditions

Temperature
80 °C

Procedure

4-Bromo-3,5-dimethylphenol (10.1 g, 50.0 mmol) and (3-formylphenyl)boronic acid (8.25 g, 55.0 mmol) were dissolved in a mixed solution of 1 M aqueous sodium carbonate solution (150 mL), ethanol (50 mL) and toluene (150 mL), and after argon substitution, tetrakis(triphenylphosphine)palladium(0) (2.89 g, 2.50 mmol) was added. The reaction mixture was stirred at 80° C. for 27 hr under argon atmosphere. After cooling the reaction mixture, water and ethyl acetate were added, and the insoluble material was filtered off through celite. The filtrate was separated into an aqueous layer and an organic layer, and the organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane=10:90-40:60), and recrystallized from ethyl acetate-hexane to give the title compound (8.53 g, yield 74%) as colorless prisms.

Workup

  1. additionwere added
  2. filtrationthe insoluble material was filtered off through celite
  3. customThe filtrate was separated into an aqueous layer
  4. washan organic layer, and the organic layer was washed with saturated brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by silica gel column chromatography (ethyl acetate:hexane=10:90-40:60)
  8. customrecrystallized from ethyl acetate-hexane

Sources & evidence

ORD record
ord-d1a8c9fea6d4463e9474be190fead19b
Source dataset
uspto-grants-2012_04
Patent number
US08153694B2

Reaction notes

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