3-Phenylprop-2-En-1-Ol → methyl 4(E)-cinnamyloxyacetoacetate

HRID 846633Notes

Reaction equation

HRID 846633 reaction equation
[H-].[Na+].Br[CH2:4][C:5](=[O:11])[CH2:6][C:7]([O:9][CH3:10])=[O:8].[Na].[CH2:13]([OH:22])[CH:14]=[CH:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.Cl>C(COC)OC>[CH2:13]([O:22][CH2:4][C:5](=[O:11])[CH2:6][C:7]([O:9][CH3:10])=[O:8])/[CH:14]=[CH:15]/[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1

Participants

7

Reactant 5

HCID 3083-Phenylprop-2-En-1-OlHCID 313Hydrochloric AcidHCID 24758Sodium hydride2×HCID 295655Methyl 4-bromo-3-oxobutanoateHCID 5360545Sodium

Product 1

HCID 13851731methyl 4(E)-cinnamyloxyacetoacetateYield 24.3%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent3×

Conditions

Temperature
-30 °C

Procedure

4 Grams of 60% sodium hydride was suspended in 150 ml of anhydrous dimethoxyethane and the suspension was cooled to -30° C. Then, 19.4 g of methyl 4-bromoacetoacetate was added dropwise to the suspension and stirred for 1 hour. Further, at the same temperature, an anhydrous dimethoxyethane solution of sodium cinnamy alcoholate prepared from 13.4 g of cinnamyl alcohol, 4 g of 60% of sodium hydride and 75 ml of dimethoxyethane was added dropwise thereto, and the reaction mixture was refluxed for 15 hours. After the reaction mixture was cooled to a room temperature, the reaction mixture was poured into 1N-hydrochloric acid being ice-cooled, and the whole mixture was extracted with ether. The ether extract was washed with water and dried with anhydrous sodium sulfate, and the solvent was removed by evaporation. The residue was purified by means of a silica gel column chromatography (eluent: methanol:dichloromethane=1:20) to yield 6 g of methyl 4(E)-cinnamyloxyacetoacetate Refractive index: nD20 1.5402

Workup

  1. additionwas added dropwise
  2. temperaturethe reaction mixture was refluxed for 15 hours
  3. temperatureAfter the reaction mixture was cooled to a room temperature
  4. temperaturecooled
  5. extractionthe whole mixture was extracted with ether
  6. extractionThe ether extract
  7. washwas washed with water
  8. dry with materialdried with anhydrous sodium sulfate
  9. customthe solvent was removed by evaporation
  10. customThe residue was purified by means of a silica gel column chromatography (eluent: methanol:dichloromethane=1:20)

Sources & evidence

ORD record
ord-cf5fbd75a6434da1937125b91ec8cb18
Source dataset
uspto-grants-1992_08
Patent number
US05137889

Reaction notes

Loading…