Potassium Carbonate → 3-Chloro-biphenyl-4-carboxaldehyde

HRID 631022Notes

Reaction equation

HRID 631022 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[C:4]([Cl:10])[CH:3]=1.[C:11]1(B(O)O)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.C(=O)([O-])[O-].[K+].[K+].CCCCCCC.C(Cl)(Cl)Cl>O1CCCC1.O.[Cl-].[Na+].O.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Cl:10][C:4]1[CH:3]=[C:2]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH:9]=[CH:8][C:5]=1[CH:6]=[O:7]

Participants

9

Reactant 4

HCID 11430Potassium CarbonateHCID 66827Phenylboronic AcidHCID 141091094-Bromo-2-chlorobenzaldehydeHCID 21875152Heptane chloroforme

Product 1

HCID 214412843-Chloro-biphenyl-4-carboxaldehydeYield 66.7%

Reagents, catalysts & solvents 4

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 5 g (22.78 mmol) of 4-bromo-2-chlorobenzaldehyde in 30 ml of tetrahydrofurane are successively added 3.47 g (28.47 mmol) of phenylboronic acid, 4.72 g (34.17 mmol) of potassium carbonate dissolved in 15 ml of water and 263 mg (0.01 equivalent) of tetrakis(triphenylphosphine) palladium. The reaction mixture is heated at 80° C. for 3 hrs. The reaction mixture is then cooled to ambient temperature and poured on 150 ml of brine. The watery layer is extracted three times with dichloromethane and the combined organic layers are successively washed by a 1M solution of sodium hydroxide, brine and filtered over a ChemElut cartridge to yield after concentration 4.6 g of a brown solid. Column chromatography (gradient heptane/chloroforme) yielded 3.29 g (65% yield) of 3-chlorobiphenyl-4-carbaldehyde as a white solid; mp=90-91° C.

Workup

  1. temperatureThe reaction mixture is then cooled to ambient temperature
  2. extractionThe watery layer is extracted three times with dichloromethane
  3. washthe combined organic layers are successively washed by a 1M solution of sodium hydroxide, brine
  4. filtrationfiltered over a ChemElut cartridge
  5. customto yield after concentration 4.6 g of a brown solid

Sources & evidence

ORD record
ord-14c618b243394265b0c2ce4dd9eb748c
Source dataset
uspto-grants-2016_04
Patent number
US09320277B2

Reaction notes

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