Lithium Chloride → 2-Hydroxy-4-vinyl-benzoic acid methyl ester

HRID 629469Notes

Reaction equation

Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([OH:12])[CH:3]=1.[CH2:13](C([Sn])=C(CCCC)CCCC)[CH2:14]CC.[Cl-].[Li+].[F-].[K+]>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[OH:12][C:4]1[CH:3]=[C:2]([CH:13]=[CH2:14])[CH:11]=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7]

Participants

Conditions

Temperature: 90 °C

Procedure

To a solution of methyl 4-bromo-2-hydroxybenzoate (3.0 g) in DMF (50.0 mL) were added tributylvinyltin (6.18 g), bis(triphenylphosphine)palladium(II) chloride (0.46 g) and lithium chloride (4.07 g), and the mixture was stirred at 90° C. for 2 hr under argon atmosphere. To the reaction mixture was added aqueous potassium fluoride solution, and the precipitated insoluble substance was removed by filtration through Celite. The filtrate was diluted with ethyl acetate, and the mixture was washed with water and saturated brine. The organic layer was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/hexane) to give the title compound. This compound was used in the next step without an additional purification.

Workup

customthe precipitated insoluble substance was removed by filtration through Celite
additionThe filtrate was diluted with ethyl acetate
washthe mixture was washed with water and saturated brine
dry with materialThe organic layer was dried over anhydrous sodium sulfate
customthe solvent was evaporated under reduced pressure
customThe residue was purified by silica gel column chromatography (ethyl acetate/hexane)

Sources & evidence

ORD record: ord-cd2cb1927ff14a24a95582ab0dd2aba1
Source dataset: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09315458B2

Reaction notes

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