Lithium Chloride → methyl 5-(4-(1H-pyrazol-1-yl)benzyl)-3-fluoro-4-methyl-2-vinylbenzoate

HRID 629442Notes

Reaction equation

HRID 629442 reaction equation
[N:1]1([C:6]2[CH:32]=[CH:31][C:9]([CH2:10][C:11]3[C:12]([CH3:30])=[C:13]([F:29])[C:14](OS(C(F)(F)F)(=O)=O)=[C:15]([CH:20]=3)[C:16]([O:18][CH3:19])=[O:17])=[CH:8][CH:7]=2)[CH:5]=[CH:4][CH:3]=[N:2]1.[CH2:33](C([Sn])=C(CCCC)CCCC)[CH2:34]CC.[Cl-].[Li+].[F-].[K+]>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.CN(C=O)C>[N:1]1([C:6]2[CH:32]=[CH:31][C:9]([CH2:10][C:11]3[C:12]([CH3:30])=[C:13]([F:29])[C:14]([CH:33]=[CH2:34])=[C:15]([CH:20]=3)[C:16]([O:18][CH3:19])=[O:17])=[CH:8][CH:7]=2)[CH:5]=[CH:4][CH:3]=[N:2]1

Participants

7

Reactant 4

HCID 433294Lithium ChlorideHCID 522689Potassium FluorideHCID 53438229Tri(butyl)vinyltinHCID 118468332methyl 5-(4-(1H-pyrazol-1-yl)benzyl)-3-fluoro-4-methyl-2-(((trifluoromethyl)sulfonyl)oxy)benzoate

Product 1

HCID 118468164methyl 5-(4-(1H-pyrazol-1-yl)benzyl)-3-fluoro-4-methyl-2-vinylbenzoateYield 91.2%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of methyl 5-(4-(1H-pyrazol-1-yl)benzyl)-3-fluoro-4-methyl-2-(((trifluoromethyl)sulfonyl)oxy)benzoate (11.8 g), tributylvinyltin (11.9 g), trans-dichlorobis(triphenylphosphine)palladium(II) (0.88 g), lithium chloride (7.84 g) and DMF (240 mL) was stirred at 90° C. for 1.5 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 saturated brine. The organic layer was dried over anhydrous magnesium 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 (7.98 g).

Workup

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

Sources & evidence

ORD record
ord-66959453d3cd4a639cd701ccf1f08e57
Source dataset
uspto-grants-2016_04
Patent number
US09315458B2

Reaction notes

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