Allyl acetate → HCID 18926421, compound

HRID 1600068Notes

Reaction equation

HRID 1600068 reaction equation
C(O[CH2:5][CH:6]=[CH2:7])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N+:27]([C:30]1[C:31](=[O:40])[NH:32][C:33]([C:36]([F:39])([F:38])[F:37])=[CH:34][CH:35]=1)([O-:29])=[O:28]>C1COCC1.C(OCC)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N+:27]([C:30]1[C:31](=[O:40])[N:32]([CH2:7][CH:6]=[CH2:5])[C:33]([C:36]([F:39])([F:37])[F:38])=[CH:34][CH:35]=1)([O-:29])=[O:28]

Participants

7

Reactant 3

HCID 11584Allyl acetate3×HCID 11776Triphenylphosphine3×HCID 10750851HCID 10750851, compound2×

Product 1

HCID 18926421HCID 18926421, compoundYield 33.8%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalyst3×HCID 8028TetrahydrofuranSolvent4×HCID 8857Ethyl AcetateSolvent

Procedure

A solution of allyl acetate (13.5 ml, 125 mmol) in THF (8 ml), was evacuated and purged with argon (3 times). Palladium acetate (122 mg, 0.50mmol) and triphenylphosphine (525 mg, 2.0 mmol) were added as solutions in tetrahydrofuran (1.5 ml each), followed by 3-nitro-6-trifluoromethyl-2-pyridinone (2.6 g, 12.5 mmol) in THF (2 ml). The reaction was heated to reflux for 64 h, and more allyl acetate (13.5 ml, 125 mmol), triphenylphosphine (525 mg, 2.0 mmol), palladium acetate (122 mg, 0.5 mmol), and tetrahydrofuran (13 ml) were added. After a further 24 h and 48 h at reflux addditional allyl acetate (13.5 ml, 125 mmol), palladium acetate (122 mg, 0.5 mmol), and triphenylphosphine (525 mg, 2.0 mmol) were added and the reaction was heated to reflux for a further 24 h. The reaction was cooled and evaported in vacuo to a gum which was purified by flash column chromatography on silica (15% ethyl acetate/hexane) to give the product contaminated with unreacted 3-nitro-6-trifluoromethyl-2-pyridinone. This material was diluted with ethyl acetate and washed with water adjusted to pH 12 with sodium carbonate, dried (Na2SO4), and evaporated in vacuo to give the title compound (1.05 g): 1H NMR (CDCl3) selected signals at δ4.80 (d, J=5.8 Hz, 2H), 5.28-5.33 (m, 2H), 5.86-5.96 (m, 1H), 6.80 (d, J=7.9 Hz, 1H), 8.22 (d, J=7.9 Hz, 1H).

Workup

  1. custompurged with argon (3 times)
  2. temperatureThe reaction was heated
  3. temperatureto reflux for 64 h
  4. additionwere added
  5. temperaturethe reaction was heated
  6. temperatureto reflux for a further 24 h
  7. temperatureThe reaction was cooled
  8. customwas purified by flash column chromatography on silica (15% ethyl acetate/hexane)
  9. customto give the product
  10. washwashed with water
  11. dry with materialdried (Na2SO4)
  12. customevaporated in vacuo

Sources & evidence

ORD record
ord-021cbbce1759454b8e7664bacf55139c
Source dataset
uspto-grants-1998_04
Patent number
US05744486

Reaction notes

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