Methanol → 7-Carbomethoxy-benzopyran-4-one

HRID 1078701Notes

Reaction equation

HRID 1078701 reaction equation
FC(F)(F)S(O[C:7]1[CH:17]=[CH:16][C:10]2[C:11](=[O:15])[CH:12]=[CH:13][O:14][C:9]=2[CH:8]=1)(=O)=O.[CH3:20][OH:21].C(N(CC)CC)C.CN([CH:32]=[O:33])C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2]>[C:20]([C:7]1[CH:17]=[CH:16][C:10]2[C:11](=[O:15])[CH:12]=[CH:13][O:14][C:9]=2[CH:8]=1)([O:33][CH3:32])=[O:21]

Participants

7

Reactant 4

HCID 887MethanolHCID 6228DimethylformamideHCID 8471TriethylamineHCID 219555707-Trifluoromethylsulfonyloxy-benzopyran-4-one

Product 1

HCID 194283227-Carbomethoxy-benzopyran-4-oneYield 94%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)Catalyst

Conditions

Temperature
50 °C

Procedure

To a stirred solution of 7-trifluoromethylsulfonyloxy-benzopyran-4-one (7.89 g, 26.6 mmole) in DMF (54 ml) was added methanol (21.6 ml), palladium acetate (110 mg, 0.533 mmole), DPPF (590 mg, 1,066 mmole) and triethylamine (7.477 ml, 53.3 mmole). Carbon monoxide gas was bubbled through the solution for 5 minutes, and the mixture was stirred at 50° C. for 3 hours under 1 atmosphere of CO. After cooling, the mixture was poured into 120 ml of 1M sulfuric acid and extracted with 2×75 ml of ethylacetate. The combined organic fractions were washed with brine, dried over MgSO4, and filtered. Solvent evaporation in vacuo and chromatography (silica gel 1:1 hexane:ether) gave 5.19 g of the title compound (94% yield).

Workup

  1. customCarbon monoxide gas was bubbled through the solution for 5 minutes
  2. temperatureAfter cooling
  3. additionthe mixture was poured into 120 ml of 1M sulfuric acid
  4. extractionextracted with 2×75 ml of ethylacetate
  5. washThe combined organic fractions were washed with brine
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. customSolvent evaporation in vacuo and chromatography (silica gel 1:1 hexane:ether)

Sources & evidence

ORD record
ord-88a6e51cd1384a18ad5a8e31308dd209
Source dataset
uspto-grants-1996_08
Patent number
US05550152

Reaction notes

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