Water → tert-Butyl 3-(4-hydroxyphenyl)prop-2-enoate

HRID 525634Notes

Reaction equation

HRID 525634 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][CH:3]=1.[C:9]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])(=[O:12])[CH:10]=[CH2:11].C(=O)([O-])[O-].[K+].[K+].O>CN1CCCC1=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.ClCCl>[OH:8][C:5]1[CH:6]=[CH:7][C:2]([CH:11]=[CH:10][C:9]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])=[CH:3][CH:4]=1

Participants

8

Reactant 4

HCID 962WaterHCID 78084-BromophenolHCID 11430Potassium CarbonateHCID 15458tert-Butyl acrylate

Product 1

HCID 54464479tert-Butyl 3-(4-hydroxyphenyl)prop-2-enoateYield 133.5%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6344DichloromethaneSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
120 °C

Procedure

4-Bromophenol (30.0 g), 33.5 g of tert-butyl acrylate, 50 mg of palladium acetate, and 27.9 g of potassium carbonate were dissolved in 300 mL of N-methylpyrrolidone, followed by stirring at 120° C. for 3 hours. The reaction solution was cooled to room temperature and 900 mL of water and 300 mL of dichloromethane were added thereto. The organic layer was separated and the water layer was extracted with 100 mL of dichloromethane twice. The organic layer was collected, washed with a 10% hydrochloric acid, saturated sodium bicarbonate water, and saturated saline, and dried by adding sodium sulfate. Sodium sulfate was removed and the mixture was purified by column chromatography (alumina/silica gel, dichloromethane), and the solvent was distilled away under a reduced pressure. As a result, tert-butyl 4-hydroxycinnamate (51 g) was obtained as a white solid.

Workup

  1. temperatureThe reaction solution was cooled to room temperature
  2. customThe organic layer was separated
  3. extractionthe water layer was extracted with 100 mL of dichloromethane twice
  4. customThe organic layer was collected
  5. washwashed with a 10% hydrochloric acid, saturated sodium bicarbonate water, and saturated saline
  6. customdried
  7. additionby adding sodium sulfate
  8. customSodium sulfate was removed
  9. customthe mixture was purified by column chromatography (alumina/silica gel, dichloromethane)
  10. distillationthe solvent was distilled away under a reduced pressure

Sources & evidence

ORD record
ord-9900123722d840659ed67280071022b8
Source dataset
uspto-grants-2016_05
Patent number
US09340634B2

Reaction notes

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