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

HRID 1282442Notes

Reaction equation

HRID 1282442 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+].Cl.CN(C)[C:30](=[O:32])C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:20]([CH2:22][CH2:23][NH:24][C:30]([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:32])#[N:21]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 16473-AminopropionitrileHCID 4875Potassium IodideHCID 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 2

HCID 11776TriphenylphosphineCatalystHCID 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 and water mixed solvent to give N-(2-cyanoethyl)-2,2-bis(fluoromethyl)-6-trifluoromethyl-2H-1-benzopyran-4-carboxamide (1.46 g) represented by the formula (C1-1) and 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 and water mixed solvent

Sources & evidence

ORD record
ord-1142e45ee77b494ea176e6096221c298
Source dataset
uspto-grants-2002_09
Patent number
US06455708B1

Reaction notes

Loading…