Dimethyl Sulfoxide → 2',6'-Dimethyl-4'-(3-(methylsulfonyl)propoxy)biphenyl-3-carbaldehyde

HRID 1848789Notes

Reaction equation

HRID 1848789 reaction equation
Br[C:2]1[C:7]([CH3:8])=[CH:6][C:5]([O:9][CH2:10][CH2:11][CH2:12][S:13]([CH3:16])(=[O:15])=[O:14])=[CH:4][C:3]=1[CH3:17].[CH:18]([C:20]1[CH:21]=[C:22](B(O)O)[CH:23]=[CH:24][CH:25]=1)=[O:19].CS(C)=O.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>O.[C].[Pd].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:17][C:3]1[CH:4]=[C:5]([O:9][CH2:10][CH2:11][CH2:12][S:13]([CH3:16])(=[O:15])=[O:14])[CH:6]=[C:7]([CH3:8])[C:2]=1[C:24]1[CH:23]=[CH:22][CH:21]=[C:20]([CH:18]=[O:19])[CH:25]=1

Participants

8

Reactant 4

HCID 679Dimethyl SulfoxideHCID 62657Potassium Phosphate, TribasicHCID 27343563-Formylphenylboronic acidHCID 709269352-Bromo-1,3-dimethyl-5-[3-(methylsulfonyl)propoxy]benzene

Product 1

HCID 593426022',6'-Dimethyl-4'-(3-(methylsulfonyl)propoxy)biphenyl-3-carbaldehydeYield 86%

Reagents, catalysts & solvents 3

HCID 634876Binap, (A+-)-CatalystHCID 178418390HCID 178418390, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

2-Bromo-1,3-dimethyl-5-[3-(methylsulfonyl)propoxy]benzene (100 g), 3-formylphenylboronic acid (56 g), 10% palladium carbon 50% water-containing product (10 g) and 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (4 g) were added to dimethyl sulfoxide (1000 mL). Tripotassium phosphate (132 g) dissolved in water (500 mL) was added, and the mixture was stirred at 80° C. for 1 hr. The reaction mixture was left standing, an oil component was removed, and ethyl acetate was added. The insoluble material was removed by filtration, and washed with ethyl acetate. The filtrate was washed with 10% brine, and the organic layer was concentrated. Ethyl acetate was added, and the mixture was azeotropically distilled with dehydration. To the concentrate were added ethyl acetate and activated carbon (10 g), and the mixture was stirred at 45° C. The insoluble material was removed by filtration, and washed with ethyl acetate. The filtrate was concentrated under reduced pressure, and isopropyl alcohol was added dropwise. The precipitated solid was collected by filtration, and the solid was washed with isopropyl alcohol, and dried under reduced pressure to give 2′,6′-dimethyl-4′-[3-(methylsulfonyl)propoxy]biphenyl-3-carbaldehyde (92.8 g).

Workup

  1. additionwas added
  2. waitThe reaction mixture was left
  3. customan oil component was removed
  4. additionethyl acetate was added
  5. customThe insoluble material was removed by filtration
  6. washwashed with ethyl acetate
  7. washThe filtrate was washed with 10% brine
  8. concentrationthe organic layer was concentrated
  9. additionEthyl acetate was added
  10. distillationthe mixture was azeotropically distilled with dehydration
  11. additionTo the concentrate were added ethyl acetate and activated carbon (10 g)
  12. stirringthe mixture was stirred at 45° C
  13. customThe insoluble material was removed by filtration
  14. washwashed with ethyl acetate
  15. concentrationThe filtrate was concentrated under reduced pressure, and isopropyl alcohol
  16. additionwas added dropwise
  17. filtrationThe precipitated solid was collected by filtration
  18. washthe solid was washed with isopropyl alcohol
  19. customdried under reduced pressure

Sources & evidence

ORD record
ord-3f9e5a419d46421a9ab79b2bb33623a1
Source dataset
uspto-grants-2015_02
Patent number
US08952185B2

Reaction notes

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