Benzonitrile, 4-bromo- → 4-(Pentafluoroethyl)benzonitrile

HRID 1869759Notes

Reaction equation

HRID 1869759 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.[F:10][C:11]([F:19])([F:18])[C:12]([F:17])([F:16])C([O-])=O.[Na+]>CN(C=O)C.O.CCOCC.[Cu]I>[F:16][C:12]([F:17])([C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1)[C:11]([F:19])([F:18])[F:10]

Participants

7

Reactant 2

HCID 12162Benzonitrile, 4-bromo-HCID 2733305Sodium pentafluoropropionate

Product 1

HCID 147741854-(Pentafluoroethyl)benzonitrile

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

4-Bromobenzonitrile (10 g, 54.9 mmol), sodium pentafluoropropionate (26.5 g, 0.143 mol) and copper (I) iodide (27.1 g, 0.142 mol) were heated to 150° C. in dry DMF (130 ml) for 4 h. The reaction mixture was diluted with water and Et2O and kieselgur filter aid was added. This bi-phasic mixture was stirred for 5 min, filtered and separated. The aqueous phase was extracted with Et2O. The combined organic phases were washed with water and aq. NH3, then dried over MgSO4, filtered and concentrated under reduced pressure to give the crude product as a brown oil. This was purified by flash chromatography (silica gel, 20-30% DCM in iso-hexanes) to give the title compound, 7.5 g (62%). 1H NMR (500 MHz, CDCl3): δ 7.75 (2H, d, J 8.3), 7.83 (2H, d, J 8.6), 19F NMR (470 MHz, CDCl3): δ −84.5, −116.

Workup

  1. filtrationfilter aid
  2. additionwas added
  3. filtrationfiltered
  4. customseparated
  5. extractionThe aqueous phase was extracted with Et2O
  6. washThe combined organic phases were washed with water and aq. NH3
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customto give the crude product as a brown oil
  11. customThis was purified by flash chromatography (silica gel, 20-30% DCM in iso-hexanes)

Sources & evidence

ORD record
ord-732ec2b3d66240d59260d6edf1165d25
Source dataset
uspto-grants-2009_12
Patent number
US07638629B2

Reaction notes

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