Methyl Acrylate → HCID 18914440, compound

HRID 1749037Notes

Reaction equation

HRID 1749037 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[C:4]([F:10])[CH:3]=1.[C:11]([O:15][CH3:16])(=[O:14])[CH:12]=[CH2:13].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CC)CC)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.CC(N(C)C)=O>[F:10][C:4]1[CH:3]=[C:2](/[CH:13]=[CH:12]/[C:11]([O:15][CH3:16])=[O:14])[CH:9]=[CH:8][C:5]=1[CH:6]=[O:7]

Participants

8

Reactant 4

HCID 7294Methyl AcrylateHCID 8471TriethylamineHCID 80271Tri-o-tolylphosphine2×HCID 1435174-Bromo-2-fluorobenzaldehyde

Product 1

HCID 18914440HCID 18914440, compoundYield 71%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalyst2×HCID 962WaterSolventHCID 31374DimethylacetamideSolvent

Conditions

Temperature
100 °C

Procedure

4-Bromo-2-fluorobenzaldehyde (20.88 g, 102.87 mmol) and methyl acrylate (13.98 ml, 154.30 mmol) were taken up in thoroughly degassed DMA (150 nil) and tri-o-tolylphosphine (3.13 g, 10.29 mmol), palladium(II) acetate (1.155 g, 5.14 mmol) and triethylamine (28.7 ml, 205.74 mmol) added. The reaction was stirred and heated to 100° C. for 16 hours. More tri-o-tolylphosphine (3.13 g, 10.29 mmol) and palladium(II) acetate (1.155 g, 5.14 mmol) were added and the reaction mixture was heated to 110° C. for a further 2 hours. Water (1 L) was added and the reaction mixture extracted with DCM (2×500 ml). Combined organics were dried (MgSO4), filtered and evaporated to give a brown solid. The crude product was purified by flash silica chromatography, elution gradient 0 to 25% EtOAc in heptane. Pure fractions were evaporated to dryness to afford (E)-methyl 3-(3-fluoro-4-formylphenyl)acrylate (15.20 g. 71.0%) as a yellow solid.

Workup

  1. additionadded
  2. temperaturethe reaction mixture was heated to 110° C. for a further 2 hours
  3. extractionthe reaction mixture extracted with DCM (2×500 ml)
  4. dry with materialCombined organics were dried (MgSO4)
  5. filtrationfiltered
  6. customevaporated
  7. customto give a brown solid
  8. customThe crude product was purified by flash silica chromatography, elution gradient 0 to 25% EtOAc in heptane
  9. customPure fractions were evaporated to dryness

Sources & evidence

ORD record
ord-0215e106347e4a12bc04b60014b5b5e3
Source dataset
uspto-grants-2015_10
Patent number
US09155727B2

Reaction notes

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