Triethylamine → 2-Cyano-α-(ethoxymethylene)-5-fluorobenzeneacetonitrile

HRID 2244072Notes

Reaction equation

HRID 2244072 reaction equation
Br[C:2]1[CH:9]=[C:8]([F:10])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5].[CH2:11]([O:13][CH:14]=[CH:15][C:16]#[N:17])[CH3:12].C(N(CC)CC)C>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:16]([C:15]([C:2]1[CH:9]=[C:8]([F:10])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5])=[CH:14][O:13][CH2:11][CH3:12])#[N:17]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 436013-Ethoxy-2-propenenitrileHCID 1189392-Bromo-4-fluorobenzonitrile

Product 1

HCID 675306412-Cyano-α-(ethoxymethylene)-5-fluorobenzeneacetonitrileYield 94%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

Palladium acetate (II) (0.556 g, 2.5 mmol) is added to a degassed solution of 2-bromo-4-fluoro-benzonitrile (10 g, 50 mmol), 3-ethoxyacrylonitrile (10.3 mL, 100 mmol) and triethylamine (14 mL, 100 mmol) in toluene (75 mL). The reaction mixture is stirred in an oil bath at 100° C. for 1 day. The reaction mixture is cooled to RT, filtered through a pad of Celite, and the filter cake is rinsed with EtOAc. After evaporation of the solvent, the residue is purified using a Biotage column eluted with 0-50% EtOAc/hexanes (20 CV) to afford 8.77 g (94%) of 2-(1-cyano-2-ethoxy-vinyl)-4-fluoro-benzonitrile. LC/MS: RT=3.38 min, no ionization.

Workup

  1. temperatureThe reaction mixture is cooled to RT
  2. filtrationfiltered through a pad of Celite
  3. washthe filter cake is rinsed with EtOAc
  4. customAfter evaporation of the solvent
  5. customthe residue is purified
  6. washeluted with 0-50% EtOAc/hexanes (20 CV)

Sources & evidence

ORD record
ord-c056709694b64d90b717c34fba0d39a8
Source dataset
uspto-grants-2010_03
Patent number
US07678803B2

Reaction notes

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