Ethyl Acetate → methyl (E)-3-[5-(4-tert-butylphenyl)thiophen-2-yl]acrylate

HRID 566068Notes

Reaction equation

HRID 566068 reaction equation
Br[C:2]1[S:6][C:5](/[CH:7]=[CH:8]/[C:9]([O:11][CH3:12])=[O:10])=[CH:4][CH:3]=1.B([O-])([O-])O[C:15]1[CH:20]=[CH:19][C:18]([C:21]([CH3:24])([CH3:23])[CH3:22])=[CH:17][CH:16]=1.C(=O)([O-])[O-].[K+].[K+].C(OCC)(=O)C>C1(C)C=CC=CC=1.C(O)C.O>[C:21]([C:18]1[CH:19]=[CH:20][C:15]([C:2]2[S:6][C:5](/[CH:7]=[CH:8]/[C:9]([O:11][CH3:12])=[O:10])=[CH:4][CH:3]=2)=[CH:16][CH:17]=1)([CH3:24])([CH3:23])[CH3:22]

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 25417100(E)-methyl 3-(5-bromothiophen-2-yl)acrylateHCID 867561654-Tert-butylphenyl borate

Product 1

HCID 86756177methyl (E)-3-[5-(4-tert-butylphenyl)thiophen-2-yl]acrylateYield 85.8%

Reagents, catalysts & solvents 1

HCID 86587398Ethanol toluene waterSolvent

Procedure

Under argon atmosphere, a solution of methyl (E)-3-(5-bromothiophen-2-yl)acrylate (0.23 g), 4-tert-butylphenyl borate (0.3 g) and potassium carbonate (0.26 g) in toluene/ethanol/water (20/2/2 ml) was stirred at room temperature for 1 hour. To the mixture was added tetrakistriphenylphosphine palladium (32 mg), and the mixture was refluxed for 18 hours and then cooled to room temperature. To the organic layer was added ethyl acetate, and the mixture was washed with saturated brine and dried with magnesium sulfate. Under reduced pressure, the mixture was concentrated, and the residue was purified with column chromatography (ethyl acetate/hexane=1:9) to give pale yellow crystals of methyl (E)-3-[5-(4-tert-butylphenyl)thiophen-2-yl]acrylate (240 mg). This compound was used for the following reaction, without subjecting further purification.

Workup

  1. temperaturethe mixture was refluxed for 18 hours
  2. washthe mixture was washed with saturated brine
  3. dry with materialdried with magnesium sulfate
  4. concentrationUnder reduced pressure, the mixture was concentrated
  5. customthe residue was purified with column chromatography (ethyl acetate/hexane=1:9)

Sources & evidence

ORD record
ord-7827b25b656c4b7ea4bbbfbf7b54a35e
Source dataset
uspto-grants-2001_01
Patent number
US06172061B2

Reaction notes

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