Triethylamine → Ethyl 3-(4-cyanophenyl)prop-2-enoate

HRID 899112Notes

Reaction equation

HRID 899112 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.[C:10]([O:14][CH2:15][CH3:16])(=[O:13])[CH:11]=[CH2:12].C(N(CC)CC)C>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>[CH2:15]([O:14][C:10](=[O:13])[CH:11]=[CH:12][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1)[CH3:16]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 8821Ethyl AcrylateHCID 12162Benzonitrile, 4-bromo-

Product 1

HCID 367207Ethyl 3-(4-cyanophenyl)prop-2-enoateYield 99.4%

Reagents, catalysts & solvents 3

HCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
97.5 °C

Procedure

To a solution of 4-bromobenzonitrile (50 g, 0.275 mol) and ethyl acrylate (35.4 g, 0.412 mol) in dry DMF (250 mL), palladium acetate (0.61 g, 0.0027 mol), tris-o-tolylphosphine (3.34 g, 0.011 mol) and triethylamine (57.3 mL, 0.412 mol) were added and refluxed at 95-100° C. for 2 h under an argon atmosphere. The reaction was quenched by adding water (250 mL) and extracted with ether (3×250 mL). The combined extract was washed with 1.5 N HCl (250 mL), water and brine and dried over sodium sulfate (anhydrous). Solvent evaporation under reduced pressure and purification by column chromatography over neutral alumina, using ethyl acetate in petroleum ether as eluent, yielded 55 g (90%) of the sub-title compound as an off-white solid.

Workup

  1. customThe reaction was quenched
  2. additionby adding water (250 mL)
  3. extractionextracted with ether (3×250 mL)
  4. extractionThe combined extract
  5. washwas washed with 1.5 N HCl (250 mL), water and brine
  6. dry with materialdried over sodium sulfate (anhydrous)
  7. customSolvent evaporation
  8. customunder reduced pressure and purification by column chromatography over neutral alumina

Sources & evidence

ORD record
ord-ca75078f91ca4060bd3f87da22f88fab
Source dataset
uspto-grants-2008_04
Patent number
US07354917B2

Reaction notes

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