Methyl Acrylate → HCID 58288194, compound

HRID 1476088Notes

Reaction equation

HRID 1476088 reaction equation
[C:1]([O:5][CH3:6])(=[O:4])[CH:2]=[CH2:3].Br[C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([N+:14]([O-:16])=[O:15])[C:9]=1[CH3:17].C(N(CC)CC)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[Cl-].[NH4+]>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:17][C:9]1[C:10]([N+:14]([O-:16])=[O:15])=[CH:11][CH:12]=[CH:13][C:8]=1/[CH:3]=[CH:2]/[C:1]([O:5][CH3:6])=[O:4]

Participants

8

Reactant 5

HCID 7294Methyl AcrylateHCID 8471TriethylamineHCID 25517Ammonium ChlorideHCID 80271Tri-o-tolylphosphineHCID 1235372-Bromo-6-nitrotoluene

Product 1

HCID 58288194HCID 58288194, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
125 °C

Procedure

Under argon, 119.5 g (1.39 mol) of methyl acrylate were added dropwise to a mixture of 100 g (0.463 mol) of 2-bromo-6-nitrotoluene, 323 ml (2.31 mol) of triethylamine, 28.2 g (92.6 mmol) of tri-2-tolylphosphine and 10.4 g (46.3 mmol) of palladium(II) acetate in 2.0 liters of DMF, and the mixture was then stirred at 125° C. for 36 h. After cooling to room temperature, the reaction mixture was stirred with 4 liters of saturated aqueous ammonium chloride solution and extracted three times with a total of 5 liters of diethyl ether. The combined organic phases were washed with water and saturated sodium chloride solution and dried over sodium sulphate. After filtration, the solvent was removed to dryness under reduced pressure. The residue obtained was purified by flash chromatography on silica gel (mobile phase petroleum ether/ethyl acetate 6:1). The product was triturated with heptane, and the solid obtained was filtered off with suction and dried under high vacuum. This gave 48.7 g of the title compound (46.6% of theory).

Workup

  1. temperatureAfter cooling to room temperature
  2. extractionextracted three times with a total of 5 liters of diethyl ether
  3. washThe combined organic phases were washed with water and saturated sodium chloride solution
  4. dry with materialdried over sodium sulphate
  5. filtrationAfter filtration
  6. customthe solvent was removed to dryness under reduced pressure
  7. customThe residue obtained
  8. customwas purified by flash chromatography on silica gel (mobile phase petroleum ether/ethyl acetate 6:1)
  9. customThe product was triturated with heptane
  10. customthe solid obtained
  11. filtrationwas filtered off with suction
  12. customdried under high vacuum

Sources & evidence

ORD record
ord-d9cc69c0a4524c639498d47b9545ae5a
Source dataset
uspto-grants-2015_04
Patent number
US09018414B2

Reaction notes

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