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

HRID 1988211Notes

Reaction equation

HRID 1988211 reaction equation
[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6](OS(C(F)(F)F)(=O)=O)=[CH:7][C:8](=[O:12])[O:9]2)=[CH:4][CH:3]=1.C([Sn](CCCC)(CCCC)[C:26]([O:28][CH2:29][CH3:30])=[CH2:27])CCC.[Li+].[Cl-]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]([C:26]([O:28][CH2:29][CH3:30])=[CH2:27])=[CH:7][C:8](=[O:12])[O:9]2)=[CH:4][CH:3]=1

Participants

6

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 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 7-bromo-4-trifluoromethanesulfonyloxycoumarin (5.1 g, 13.7 mmol) in dioxane is added tributyl(1-ethoxyvinyl)tin (4.8 mL, 14.2 mmol), (Ph3P)4Pd (0.790 g, 0.7 mmol) and LiCl (1.74 g, 41 mmol). The mixture is refluxed for 4 h, cooled and partitioned between aqueous NH4Cl and EtOAc. The layers are separated and the aqueous phase is extracted with EtOAc. The combined organic layers are washed with brine and dried over anhydrous Na2SO4. The solvent is evaporated and the residue is chromatographed on silica gel (CH2Cl2/EtOAc; 95:5) and triturated in hexane/Et2O to give the title compound.

Workup

  1. temperatureThe mixture is refluxed for 4 h
  2. temperaturecooled
  3. custompartitioned between aqueous NH4Cl and EtOAc
  4. customThe layers are separated
  5. extractionthe aqueous phase is extracted with EtOAc
  6. washThe combined organic layers are washed with brine
  7. dry with materialdried over anhydrous Na2SO4
  8. customThe solvent is evaporated
  9. customthe residue is chromatographed on silica gel (CH2Cl2/EtOAc; 95:5)
  10. customtriturated in hexane/Et2O

Sources & evidence

ORD record
ord-87c3e03c5a54408cb285d11827932609
Source dataset
uspto-grants-2009_06
Patent number
US07553973B2

Reaction notes

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