Sodium Bicarbonate → Ethyl 4-oxo-4-(3-thienyl)butyrate

HRID 2356766Notes

Reaction equation

HRID 2356766 reaction equation
[Cl-].[CH2:2]([O:4][C:5](=[O:11])[CH2:6][CH2:7][C:8]([OH:10])=O)[CH3:3].C([Sn](CCCC)(CCCC)[C:17]1[CH:21]=[CH:20][S:19][CH:18]=1)CCC.C(=O)([O-])O.[Na+]>O1CCOCC1.[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[S:19]1[CH:20]=[CH:21][C:17]([C:8](=[O:10])[CH2:7][CH2:6][C:5]([O:4][CH2:2][CH3:3])=[O:11])=[CH:18]1

Participants

6

Reactant 3

HCID 516892Sodium BicarbonateHCID 10959689Stannane, tributyl-3-thienyl-HCID 77519041Succinic acid monoethyl ester monochloride

Product 1

HCID 24723426Ethyl 4-oxo-4-(3-thienyl)butyrateYield 59.9%

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

Under argon atmosphere, a mixture of succinic acid monoethyl ester monochloride (2.0 g), tributyl(3-thienyl) tin (5.44 g) and bis (triphenylphosphine) palladium chloride (853 mg) in dioxane (40 ml) was refluxed for 3 hours. After cooling, to the residue was added a saturated aqueous sodium hydrogen carbonate solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:ethyl acetate=6:1), and recrystallized from ethyl acetate-hexane to obtain ethyl 4-(3-thienyl)-4-oxobutyrate (1.4 g) as pale yellowish powder.

Workup

  1. temperaturewas refluxed for 3 hours
  2. temperatureAfter cooling, to the residue
  3. extractionthe mixture was extracted with ethyl acetate
  4. washThe organic layer was washed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. customthe solvent was removed under reduced pressure
  7. customThe resulting residue was purified by silica gel column chromatography (solvent: hexane:ethyl acetate=6:1)
  8. customrecrystallized from ethyl acetate-hexane

Sources & evidence

ORD record
ord-88e15231b2ed49ee87ac13bad7a38140
Source dataset
uspto-grants-2010_07
Patent number
US07759373B2

Reaction notes

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