Water → 2',4,6'-Trifluorobiphenyl-3-carbaldehyde

HRID 1529276Notes

Reaction equation

HRID 1529276 reaction equation
Br[C:2]1[C:7]([F:8])=[CH:6][CH:5]=[CH:4][C:3]=1[F:9].[F:10][C:11]1[CH:16]=[CH:15][C:14](B(O)O)=[CH:13][C:12]=1[CH:20]=[O:21].C([O-])([O-])=O.[Na+].[Na+].O>C1(C)C=CC=CC=1.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]>[F:9][C:3]1[CH:4]=[CH:5][CH:6]=[C:7]([F:8])[C:2]=1[C:14]1[CH:15]=[CH:16][C:11]([F:10])=[C:12]([CH:20]=[O:21])[CH:13]=1

Participants

7

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 1235571-Bromo-2,6-difluorobenzeneHCID 2778651(4-Fluoro-3-formylphenyl)boronic acid

Product 1

HCID 640388312',4,6'-Trifluorobiphenyl-3-carbaldehydeYield 49.4%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 2-bromo-1,3-difluorobenzene (100 g, 477.46 mmol) and 4-fluoro-3-formylphenylboronic acid (96.2 g, 572.95 mmol) in toluene (1432 mL) at RT was added Na2CO3 (2M in H2O) (477.46 mL, 954.2 mmol) and PdCl2(dppf) (7.798 g, 9.54 mmol). The reaction mixture was stirred at 100° C. for 8 h and cooled to RT. Water was added to the reaction mixture and extracted with EtOAc (2×500 mL). Organic layer was washed with brine and dried over Na2SO4. The organic layer was concentrated and purified by column using silica (100-200 mesh) and 0-5% EtOAc-hexane to provide 2′,4,6′-trifluorobiphenyl-3-carbaldehyde (54.3 g, 49.4% yield).

Workup

  1. temperaturecooled to RT
  2. extractionextracted with EtOAc (2×500 mL)
  3. washOrganic layer was washed with brine
  4. dry with materialdried over Na2SO4
  5. concentrationThe organic layer was concentrated
  6. custompurified by column

Sources & evidence

ORD record
ord-61e63afbe4194cf69cdf0b326bef5c55
Source dataset
uspto-grants-2015_07
Patent number
US09090593B2

Reaction notes

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