Cesium fluoride → 5-Acetylthiophene-3-sulfonic acid [2-(4-fluorophenyl)ethyl]-methyl-amide

HRID 1351298Notes

Reaction equation

HRID 1351298 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][N:10]([CH3:20])[S:11]([C:14]2[CH:18]=[C:17](Cl)[S:16][CH:15]=2)(=[O:13])=[O:12])=[CH:4][CH:3]=1.[CH2:21]([O:23]C([Sn](CCCC)(CCCC)CCCC)=C)[CH3:22].[F-].[Cs+]>O1CCOCC1.C(OCC)(=O)C.O1CCCC1.O.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][N:10]([CH3:20])[S:11]([C:14]2[CH:18]=[C:17]([C:21](=[O:23])[CH3:22])[S:16][CH:15]=2)(=[O:13])=[O:12])=[CH:4][CH:3]=1

Participants

9

Reactant 3

HCID 25953Cesium fluorideHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 860714185-Chlorothiophene-3-sulfonic acid [2-(4-fluorophenyl)ethyl]-methyl-amide

Product 1

HCID 860714195-Acetylthiophene-3-sulfonic acid [2-(4-fluorophenyl)ethyl]-methyl-amideYield 43.6%

Reagents, catalysts & solvents 5

HCID 83681Tris(1,1-dimethylethyl)phosphineCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

A solution of 5-chlorothiophene-3-sulfonic acid [2-(4-fluorophenyl)ethyl]-methyl-amide (345 mg), (1-ethoxyvinyl)-tributyltin (448 mg), cesium fluoride (346 mg), tris-hydroxymethyl-aminomethanedibenzylidene acetone-dipalladium(16 mg) and trit-butylphosphine (1.3 mg) in 1,4-dioxane (4 ml) was heated at 100° C. for 4 hours. After the reaction solution was cooled to room temperature, the solution was diluted with ethyl acetate, the resulting insoluble matter was removed by filtration, and washed with ethyl acetate. The filtrate was evaporated in vacuo and crude enol ether was obtained. Enol ether was dissolved in tetrahydrofuran (3 mL)-1N hydrochloric acid (3 mL), and the solution was stirred at room temperature for 30 minutes. After the solution was diluted with water, the solution was extracted with ethyl acetate, and washed with saturated sodium chloride water. After drying with anhydrous sodium sulfate, the residue that was obtained upon removing the solvent by evaporation was purified by silica gel column chromatography (hexane/ethyl acetate), and the title compound (154 mg) was obtained as a yellow oily substance.

Workup

  1. customthe resulting insoluble matter was removed by filtration
  2. washwashed with ethyl acetate
  3. customThe filtrate was evaporated in vacuo
  4. customcrude enol ether was obtained
  5. extractionthe solution was extracted with ethyl acetate
  6. washwashed with saturated sodium chloride water
  7. dry with materialAfter drying with anhydrous sodium sulfate
  8. customthe residue that was obtained
  9. customupon removing the solvent
  10. customby evaporation
  11. customwas purified by silica gel column chromatography (hexane/ethyl acetate)

Sources & evidence

ORD record
ord-844f070eab11463eb4a8743e3d0587b8
Source dataset
uspto-grants-2007_05
Patent number
US07217723B2

Reaction notes

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