Methyl Acrylate → Methyl Cinnamate

HRID 1242823Notes

Reaction equation

HRID 1242823 reaction equation
I[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:8]([O:12][CH3:13])(=[O:11])[CH:9]=[CH2:10].C([O-])(=O)C.[Na+].[Cl-].[NH4+]>CCOCC.CN(C)C(=O)C>[C:8]([O:12][CH3:13])(=[O:11])/[CH:9]=[CH:10]/[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 7294Methyl AcrylateHCID 11575IodobenzeneHCID 25517Ammonium ChlorideHCID 517045Sodium Acetate

Product 1

HCID 637520Methyl CinnamateYield 99%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 31374DimethylacetamideSolvent

Conditions

Temperature
100 °C

Procedure

Compound 5 (30 mg, 2 μmol Pd), iodobenzene (0.20 g, 1 mmol), methyl acrylate (0.13 g, 1.5 mmol), sodium acetate (0.12 g, 1.5 mmol), and N,N-dimethylacetamide (3 mL) were sequentially added to a 15 mL septum-sealed test tube under protection of nitrogen. The reaction mixture was heated at 100° C. for 8 h. After it was cooled to the room temperature, 8 mL of anhydrous ether was added to precipitate compound 5. The mixture was centrifuged and the upper liquid layer was transferred via a syringe into a 20 mL round-bottom flask. Repeated the above precipitation procedure once. The combined liquid layer was concentrated under reduced pressure to give an oily residue. A saturated ammonium chloride solution (5 mL) was then added. The resulting mixture was extracted by ethyl acetate (10 mL×3), dried over anhydrous magnesium sulfate, filtrated, and concentrated to give a crude product. The crude product was further purified by column chromatography (silica gel, hexane/ethyl acetate=4/1) to give 0.16 g (99% yield) of trans-methyl cinnamate. Rf=0.53 (9:1 hexane:ethyl acetate), 1H NMR (300 MHz, CDCl3) δ 3.81 (s, 3H), 6.45 (d, J=15.6 Hz, 1H), 7.29–7.64 (m, 5H), 7.69 (d, J=15.6 Hz, 1H) ppm.

Workup

  1. customseptum-sealed test tube under protection of nitrogen
  2. additionwas added
  3. customto precipitate compound 5
  4. customthe upper liquid layer was transferred via a syringe into a 20 mL round-bottom flask
  5. customthe above precipitation procedure once
  6. concentrationThe combined liquid layer was concentrated under reduced pressure
  7. customto give an oily residue
  8. extractionThe resulting mixture was extracted by ethyl acetate (10 mL×3)
  9. dry with materialdried over anhydrous magnesium sulfate
  10. filtrationfiltrated
  11. concentrationconcentrated
  12. customto give a crude product
  13. customThe crude product was further purified by column chromatography (silica gel, hexane/ethyl acetate=4/1)

Sources & evidence

ORD record
ord-036b8f1e250d49969ff23b0228b37211
Source dataset
uspto-grants-2006_10
Patent number
US07115762B2

Reaction notes

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