Triphenylphosphine → Methyl 4'-(trifluoromethyl)[1,1'-biphenyl]-4-carboxylate

HRID 1867783Notes

Reaction equation

HRID 1867783 reaction equation
[F:1][C:2]([F:13])([F:12])[C:3]1[CH:8]=[CH:7][C:6](B(O)O)=[CH:5][CH:4]=1.Br[C:15]1[CH:24]=[CH:23][C:18]([C:19]([O:21][CH3:22])=[O:20])=[CH:17][CH:16]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[F-].[Cs+]>COCCOC.CO.CC(C)=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:22][O:21][C:19]([C:18]1[CH:23]=[CH:24][C:15]([C:6]2[CH:7]=[CH:8][C:3]([C:2]([F:13])([F:12])[F:1])=[CH:4][CH:5]=2)=[CH:16][CH:17]=1)=[O:20]

Participants

9

Reactant 4

HCID 11776TriphenylphosphineHCID 12081Methyl 4-bromobenzoateHCID 25953Cesium fluorideHCID 27343894-(Trifluoromethyl)phenylboronic acid

Product 1

HCID 4328569Methyl 4'-(trifluoromethyl)[1,1'-biphenyl]-4-carboxylateYield 92%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 180AcetoneSolventHCID 887MethanolSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

Procedure A′: A suspension of 4-(trifluoromethyl)phenylboronic acid (7.3 g, 38.4 mmol), methyl 4-bromobenzoate (7.44 g, 36.4 mmol), triphenylphosphine (1.21 g, 4.6 mmol), cesium fluoride (11.7 g, 76.8 mmol) and palladium acetate (0.26 g, 1.15 mmol) in degassed DME and methanol is heated at reflux for 24 h. The suspension is cooled to room temperature, filtered, and the resulting filtrate concentrated in vacuo to give a dark solid. This material is taken up in acetone and adsorbed on silica gel, and purified by flash filtration using 500 mL each of 2% to 20% ethyl acetate/hexanes in 2% increments. Fractions containing the product are combined to give the title compound in 92% yield. NMR (CDCl3) 8.10 (d, J=8.4 Hz, 2H), 7.99 (d, J=7.9 Hz, 2H), 7.92 (d, J=8.4 Hz, 2H), 7.83 (d, 8.4 Hz, 2H), 3.58 (s, 3H).

Workup

  1. temperatureis heated
  2. temperatureat reflux for 24 h
  3. filtrationfiltered
  4. concentrationthe resulting filtrate concentrated in vacuo
  5. customto give a dark solid
  6. filtrationpurified by flash filtration
  7. additionFractions containing the product

Sources & evidence

ORD record
ord-d38624da69eb4d1b82f5750807af28d8
Source dataset
uspto-grants-2009_12
Patent number
US07632857B2

Reaction notes

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