4-Bromo-2-fluoro-1-(trifluoromethoxy)benzene → 3-Fluoro-4-(trifluoromethoxy)benzonitrile

HRID 715679Notes

Reaction equation

HRID 715679 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][C:9]([F:12])([F:11])[F:10])=[C:4]([F:13])[CH:3]=1.[Cu][C:15]#[N:16].[Cu](C#N)C#N>CC(N(C)C)=O>[F:10][C:9]([F:12])([F:11])[O:8][C:5]1[CH:6]=[CH:7][C:2]([C:15]#[N:16])=[CH:3][C:4]=1[F:13]

Participants

5

Reactant 3

HCID 27822174-Bromo-2-fluoro-1-(trifluoromethoxy)benzeneHCID 178418260HCID 178418260, compound2×HCID 178418546HCID 178418546, compound

Product 1

HCID 177506703-Fluoro-4-(trifluoromethoxy)benzonitrile

Reagents, catalysts & solvents 1

HCID 31374DimethylacetamideSolvent

Procedure

49 g 1-Bromo-3-fluoro-4-trifluoromethoxybenzene was stirred into 100 mL dimethylacetamide together with 20 g copper(I)cyanide at 140° C. overnight. Additional 10 g copper cyanide was added and heating was continued at 150° C. for 4 h. Further 12 g copper cyanide was added and stirring continued at 150° C. overnight. After cooling, the mixture was filtered through Celite/Cellulose and washed with ethyl acetate. The filtrate was added to ice water and filtered again through Celite/Cellulose. The filtrate was extracted with ethyl acetate (×3), dried over magnesium sulfate and concentrated to provide a brown oil which was distilled at 7 mbar and 60° C. to yield two product fractions with 23.5 g and 12 g (content 80%) yield.

Workup

  1. temperatureheating
  2. waitcontinued at 150° C. overnight
  3. temperatureAfter cooling
  4. filtrationthe mixture was filtered through Celite/Cellulose
  5. washwashed with ethyl acetate
  6. additionThe filtrate was added to ice water
  7. filtrationfiltered again through Celite/Cellulose
  8. extractionThe filtrate was extracted with ethyl acetate (×3)
  9. dry with materialdried over magnesium sulfate
  10. concentrationconcentrated
  11. customto provide a brown oil which
  12. distillationwas distilled at 7 mbar and 60° C.
  13. customto yield two product fractions with 23.5 g and 12 g (content 80%)
  14. customyield

Sources & evidence

ORD record
ord-002ad2f0bf52484c95d6837d8e6b3a76
Source dataset
uspto-grants-2015_11
Patent number
US09187478B2

Reaction notes

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