Stannane, tributyl(1-ethoxyethenyl)- → HCID 11770492, compound

HRID 1736253Notes

Reaction equation

HRID 1736253 reaction equation
Br[C:2]1[CH:14]=[CH:13][C:5]([NH:6][C:7](=[O:12])[C:8]([CH3:11])([CH3:10])[CH3:9])=[C:4]([F:15])[CH:3]=1.[CH2:16]([O:18]C([Sn](CCCC)(CCCC)CCCC)=C)[CH3:17]>C1(C)C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[F:15][C:4]1[CH:3]=[C:2]([C:16](=[O:18])[CH3:17])[CH:14]=[CH:13][C:5]=1[NH:6][C:7](=[O:12])[C:8]([CH3:11])([CH3:10])[CH3:9]

Participants

5

Reactant 2

HCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 4149902N-(4-bromo-2-fluorophenyl)-2,2-dimethylpropanamide

Product 1

HCID 11770492HCID 11770492, compoundYield 99.3%

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

70.6 g (258 mmol) of the above 4-bromo-2-fluoro-N-pivaloylaniline was dissolved in 500 mL of toluene under argon atmosphere, 108 mL (310 mmol) of 1-ethoxyvinyltributyltin and 1.80 g (2.57 mmol) of bis(triphenylphosphine)palladium (II) chloride were added, and the mixture was stirred at 100° C. for 5 hours. The reaction solution was cooled on ice, 500 mL of 2N HCL was added, and the mixture was stirred at room temperature for 2 hours. The insoluble matters were filtered off and the filtrate was extracted once with ethyl acetate. 500 mL of a 10% aqueous solutiuon of ammonium fluoride was added to the organic layer and the mixture was stirred at room temperature for 3 hours. The insoluble matters were filtered off and the organic layer was washed once with water and once with an aqueous saturated solution of sodium chloride and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=6:1-4:1), to give 60.8 g of 3'-fluoro-4'-pivaloylaminoacetophenone (yield: 99%).

Workup

  1. temperatureThe reaction solution was cooled on ice, 500 mL of 2N HCL
  2. additionwas added
  3. stirringthe mixture was stirred at room temperature for 2 hours
  4. filtrationThe insoluble matters were filtered off
  5. extractionthe filtrate was extracted once with ethyl acetate
  6. addition500 mL of a 10% aqueous solutiuon of ammonium fluoride was added to the organic layer
  7. stirringthe mixture was stirred at room temperature for 3 hours
  8. filtrationThe insoluble matters were filtered off
  9. washthe organic layer was washed once with water and once with an aqueous saturated solution of sodium chloride
  10. dry with materialdried over anhydrous sodium sulfate
  11. distillationThe solvent was distilled off under reduced pressure
  12. customthe residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=6:1-4:1)

Sources & evidence

ORD record
ord-9e1a8a9de0a9450188d7f008d3334da8
Source dataset
uspto-grants-1996_07
Patent number
US05539112

Reaction notes

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