Methyl Acrylate → HCID 123194218, compound

HRID 1773126Notes

Reaction equation

HRID 1773126 reaction equation
[CH3:1][O:2][C:3]1[CH:10]=[CH:9][C:8](I)=[CH:7][C:4]=1[CH:5]=[O:6].C(N(CC)CC)C.[C:19]([O:23]C)(=[O:22])[CH:20]=[CH2:21]>C(#N)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>[CH:5]([C:4]1[CH:7]=[C:8]([CH:9]=[CH:10][C:3]=1[O:2][CH3:1])[CH:21]=[CH:20][C:19]([OH:23])=[O:22])=[O:6]

Participants

7

Reactant 3

HCID 7294Methyl AcrylateHCID 8471TriethylamineHCID 2622405-iodo-2-methoxybenzaldehyde

Product 1

HCID 123194218HCID 123194218, compound

Reagents, catalysts & solvents 3

HCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
67.5 °C

Procedure

2-Methoxy-5-iodobenzaldehyde (1.0 g, 3.82 mmol) is dissolved in 25 ml of acetonitrile and oxygen is removed by bubbling nitrogen through the solution. Triethylamine (3.71 ml, 26.7 mmol) and methyl acrylate (0.686, ml, 7.63 mmol) are added dropwise with stirring to the solution, followed by four portions of 0.0214 g of tri-o-tolylphosphine (0.095 mmol) and 0.008 g of palladium (II) acetate (0.047 mmol) at 1 hour intervals. The mixture is then heated at 65-70° C. for 4 hours, volatiles are removed by distillation and the residue is dissolved in dichloromethane. The resulting solution is percolated through silica gel eluting with a mixture of hexane-ethyl acetate (6:4). The percolate is evaporated to dryness, re-dissolved in 20 ml of methanol and 10 ml of 20% aqueous potassium carbonate solution added. The mixture is stirred for 6 hours at room temperature and concentrated under reduced pressure to a third of its volume. The solution is taken to a pH value of 1 with concentrated hydrochloride acid and the precipitate is filtered and recrystallized from isopropanol, to give 0.472 g of 3-formyl-4-methoxycinnamic acid (2.29 mmol) as a crystalline white solid. A second harvest obtained by concentration of the mother liquor gave an additional 0.105 g.

Workup

  1. customoxygen is removed
  2. customby bubbling nitrogen through the solution
  3. customvolatiles are removed by distillation
  4. dissolutionthe residue is dissolved in dichloromethane
  5. additionThe resulting solution is percolated through silica gel eluting with a mixture of hexane-ethyl acetate (6:4)
  6. customThe percolate is evaporated to dryness
  7. dissolutionre-dissolved in 20 ml of methanol
  8. addition10 ml of 20% aqueous potassium carbonate solution added
  9. stirringThe mixture is stirred for 6 hours at room temperature
  10. concentrationconcentrated under reduced pressure to a third of its volume
  11. filtrationthe precipitate is filtered
  12. customrecrystallized from isopropanol

Sources & evidence

ORD record
ord-8efa08cf96dc442e8e45616ca65b7e48
Source dataset
uspto-grants-2016_02
Patent number
US09255071B2

Reaction notes

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