Methyl Acrylate → methyl (E)-3-(4-cyanophenyl)prop-2-enoate

HRID 733514Notes

Reaction equation

HRID 733514 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.[CH3:10][O:11][C:12](=[O:15])[CH:13]=[CH2:14].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(=O)(O)[O-].[Na+]>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2].C(N(CC)CC)C>[C:6]([C:5]1[CH:8]=[CH:9][C:2](/[CH:14]=[CH:13]/[C:12]([O:11][CH3:10])=[O:15])=[CH:3][CH:4]=1)#[N:7]

Participants

8

Reactant 4

HCID 7294Methyl AcrylateHCID 11776TriphenylphosphineHCID 12162Benzonitrile, 4-bromo-HCID 516892Sodium Bicarbonate

Product 1

HCID 11106082methyl (E)-3-(4-cyanophenyl)prop-2-enoateYield 71%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 4-bromobenzonitrile (25 g, 0.136 mol) and methylacrylate (58.6 g, 0.682 mol) in dry DMF (250 mL) was added PPh3 (2.8 g, 0.0106 mol), Pd(OAc)2 (1.3 g, 0.00579 mol), sodium bicarbonate (18 g, 0.214 mol) and triethylamine (25 mL). The reaction mixture was heated to 100° C. for 16 h under nitrogen. The reaction mixture was cooled and the solid was filtered off. The filtrate was diluted with water (1 L) and the product was extracted with diethyl ether (4×200 ml). The combined organic layer was washed with water, brine, dried and evaporated to yield the crude product which was purified by chromatography (SiO2, PetEther/EtOAc (9.5/0.5) as eluent) to yield the title compound as a liquid (18 g, 71%). TLC: PetEther/EtOAc (9.5/0.5); Rf: 0.75

Workup

  1. temperatureThe reaction mixture was cooled
  2. filtrationthe solid was filtered off
  3. additionThe filtrate was diluted with water (1 L)
  4. extractionthe product was extracted with diethyl ether (4×200 ml)
  5. washThe combined organic layer was washed with water, brine
  6. customdried
  7. customevaporated
  8. customto yield the crude product which
  9. customwas purified by chromatography (SiO2, PetEther/EtOAc (9.5/0.5) as eluent)

Sources & evidence

ORD record
ord-6f3577d8bc26411faee05478c5cd234c
Source dataset
uspto-grants-2009_09
Patent number
US07589232B2

Reaction notes

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