Lithium Chloride → 7-bromo-4-(1-ethoxyvinyl)-2H-chromen-2-one

HRID 2422517Notes

Reaction equation

HRID 2422517 reaction equation
FC(F)(F)S(O[C:7]1[C:16]2[C:11](=[CH:12][C:13]([Br:17])=[CH:14][CH:15]=2)[O:10][C:9](=[O:18])[CH:8]=1)(=O)=O.C([Sn](CCCC)(CCCC)[C:26]([O:28][CH2:29][CH3:30])=[CH2:27])CCC.[Cl-].[Li+]>O1CCOCC1.C(OCC)(=O)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Br:17][C:13]1[CH:12]=[C:11]2[C:16]([C:7]([C:26]([O:28][CH2:29][CH3:30])=[CH2:27])=[CH:8][C:9](=[O:18])[O:10]2)=[CH:15][CH:14]=1

Participants

7

Reactant 3

HCID 433294Lithium ChlorideHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 194269487-bromo-2-oxo-2H-chromen-4-yl trifluoromethanesulfonate

Product 1

HCID 233702047-bromo-4-(1-ethoxyvinyl)-2H-chromen-2-one

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 7-bromo-2-oxo-2H-chromen-4-yl trifluoromethanesulfonate (prepared as described in U.S. Pat. No. 5,552,437) (5 g, 13.4 mmol) and tributyl(1-ethoxyvinyl)tin (4.75 mL, 14.1 mmol) in 1,4-dioxane (50 mL), lithium chloride (1.7 g, 40.2 mmol) was added. The reaction flask was then purged twice with nitrogen and tetrakis(triphenylphosphine) palladium(0) (774 mg, 0.7 mmol) was added. The reaction was then heated 4 hours at 80° C. After cooling, the reaction mixture was concentrated under reduced pressure and the crude residue obtained was diluted with ethyl acetate, washed with a saturated ammonium chloride aq. solution, water and brine, dried over MgSO4, filtered and concentrated. The crude residue obtained was purified by column chromatography (hexanes/CH2Cl2/acetone, 25:75:0 to 0:95:5) to afford the title compound. 1H NMR (400 MHz, acetone-d6): 7.83 (d, 1H), 7.60 (s, 1H), 7.52 (d, 1H), 6.46 (s, 1H), 4.67 (s, 2H), 4.05 (q, 2H), 1.38 (t, 3H).

Workup

  1. additionwas added
  2. temperatureAfter cooling
  3. concentrationthe reaction mixture was concentrated under reduced pressure
  4. customthe crude residue obtained
  5. washwashed with a saturated ammonium chloride aq. solution, water and brine
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude residue obtained
  10. customwas purified by column chromatography (hexanes/CH2Cl2/acetone, 25:75:0 to 0:95:5)

Sources & evidence

ORD record
ord-a7a796a9055c463bafede1648a8aa13b
Source dataset
uspto-grants-2011_06
Patent number
US07960409B2

Reaction notes

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