Toluene → 4-Ethoxy-3,3'-difluoro-4'-propyl-[1,1'-biphenyl]-2,2'-dicarboaldehyde

HRID 718485Notes

Reaction equation

HRID 718485 reaction equation
Br[C:2]1[C:7]([CH:8]=[O:9])=[C:6]([F:10])[C:5]([CH2:11][CH2:12][CH3:13])=[CH:4][CH:3]=1.[CH2:14]([O:16][C:17]1[CH:22]=[CH:21][C:20](B(O)O)=[C:19]([CH:26]=[O:27])[C:18]=1[F:28])[CH3:15].C(=O)([O-])[O-].[Na+].[Na+].C1(C)C=CC=CC=1>CCCC[N+](CCCC)(CCCC)CCCC.[Br-].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.O.C(O)C>[CH2:14]([O:16][C:17]1[C:18]([F:28])=[C:19]([CH:26]=[O:27])[C:20]([C:2]2[C:7]([CH:8]=[O:9])=[C:6]([F:10])[C:5]([CH2:11][CH2:12][CH3:13])=[CH:4][CH:3]=2)=[CH:21][CH:22]=1)[CH3:15]

Participants

9

Reactant 4

HCID 1140TolueneHCID 10340Sodium CarbonateHCID 469186104-Ethoxy-3-fluoro-2-formylphenylboronic acidHCID 866960636-Bromo-2-fluoro-3-propylbenzaldehyde

Product 1

HCID 866960644-Ethoxy-3,3'-difluoro-4'-propyl-[1,1'-biphenyl]-2,2'-dicarboaldehydeYield 80.5%

Reagents, catalysts & solvents 4

HCID 74236Tetrabutylammonium BromideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

Under a nitrogen atmosphere, a mixture of compound (51) (4.9 g, 19.99 mmol), compound (55) (4.9 g, 23.12 mmol), tetrakis(triphenylphosphine)palladium (0.23 g, 0.199 mmol), sodium carbonate (4.9 g, 46.23 mmol) and TBAB (0.96 g, 2.978 mmol) was refluxed in a toluene (30 mL)-ethanol (20 mL)-water (50 mL) solvent for 5 hours. The reaction mixture was extracted with 30 mL of toluene three times. Combined organic layers were washed with a saturated aqueous solution of sodium hydrogencarbonate, water and saturated brine, and then dried over magnesium sulfate, and a solvent was distilled off by an evaporator. The residue was purified by silica gel column chromatography, and thus 4-ethoxy-3,3′-difluoro-4′-propyl-[1,1′-biphenyl]-2,2′-dicarboaldehyde (56) (5.35 g, yield 80.5%) was obtained.

Workup

  1. extractionThe reaction mixture was extracted with 30 mL of toluene three times
  2. washCombined organic layers were washed with a saturated aqueous solution of sodium hydrogencarbonate, water and saturated brine
  3. dry with materialdried over magnesium sulfate
  4. distillationa solvent was distilled off by an evaporator
  5. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-d0c9df6c7a18490ebe6a944bceb474b1
Source dataset
uspto-grants-2015_11
Patent number
US09193908B2

Reaction notes

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