Hydrochloric Acid → 2,2-bis(fluoromethyl)-N-(2-cyanoethyl)-6-trifluoromethyl-2H-1-benzopyran-4-carboxamide

HRID 1282419Notes

Reaction equation

HRID 1282419 reaction equation
Br[C:2]1[C:7]2[CH:8]=[C:9]([C:12]([F:15])([F:14])[F:13])[CH:10]=[CH:11][C:6]=2[O:5][C:4]([CH2:18][F:19])([CH2:16][F:17])[CH:3]=1.[C:20]([CH2:22][CH2:23][NH2:24])#[N:21].[I-].[K+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Cl.CN(C)[C:49](=[O:51])C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:20]([CH2:22][CH2:23][NH:24][C:49]([C:2]1[C:7]2[CH:8]=[C:9]([C:12]([F:15])([F:14])[F:13])[CH:10]=[CH:11][C:6]=2[O:5][C:4]([CH2:18][F:19])([CH2:16][F:17])[CH:3]=1)=[O:51])#[N:21]

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 16473-AminopropionitrileHCID 4875Potassium IodideHCID 11776TriphenylphosphineHCID 31374DimethylacetamideHCID 184244094-bromo-2,2-bis(fluoromethyl)-6-trifluoromethyl-2H-1-benzopyran

Product 1

HCID 99507522,2-bis(fluoromethyl)-N-(2-cyanoethyl)-6-trifluoromethyl-2H-1-benzopyran-4-carboxamide

Reagents, catalysts & solvents 1

HCID 167845palladium(II) acetateCatalyst

Conditions

Temperature
100 °C

Procedure

A mixture of 4-bromo-2,2-bis(fluoromethyl)-6-trifluoromethyl-2H-1-benzopyran (1.73 g), 2-cyanoethylamine (1.44 g), potassium iodide (0.86 g), triphenylphosphine (26 mg), palladium acetate (11 mg) and N,N-dimethylacetamide (10 ml) was stirred under a CO atmosphere at 100° C. for 3 hours. To the reaction mixture, 2 N HCl was added and the precipitating crystals were recovered by filtration. To the recovered crystals, ethyl acetate was added and the insoluble matter was filtered off; the filtrate was washed with a saturated aqueous solution of sodium thiosulfate and a saturated aqueous solution of sodium chloride, dried with anhydrous sodium sulfate and concentrated under reduced pressure; the resulting residue was recrystallized with an ethanol/water mixed solvent, thereby giving N-(2-cyanoethyl)-2,2-bis(fluoromethyl)-6-trifluoromethyl-2H-1-benzopyran-4-carboxamide (1.46 g) having a melting point of 129-131° C.

Workup

  1. filtrationthe precipitating crystals were recovered by filtration
  2. additionTo the recovered crystals, ethyl acetate was added
  3. filtrationthe insoluble matter was filtered off
  4. washthe filtrate was washed with a saturated aqueous solution of sodium thiosulfate
  5. dry with materiala saturated aqueous solution of sodium chloride, dried with anhydrous sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customthe resulting residue was recrystallized with an ethanol/water mixed solvent

Sources & evidence

ORD record
ord-b202dfddb9ef489a88d2ce1bb8e10769
Source dataset
uspto-grants-2002_09
Patent number
US06455708B1

Reaction notes

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