Benzaldehyde → Methyl 3-hydroxy-3-phenylpropanoate

HRID 395903Notes

Reaction equation

HRID 395903 reaction equation
C[Si](C)(C)Cl.[CH:6](=[O:13])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.Br[CH2:15][C:16]([O:18][CH3:19])=[O:17].Cl>C(OC(C)C)(=O)C.[Zn]>[OH:13][CH:6]([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)[CH2:15][C:16]([O:18][CH3:19])=[O:17]

Participants

7

Reactant 4

HCID 240BenzaldehydeHCID 313Hydrochloric AcidHCID 6397ChlorotrimethylsilaneHCID 60984Methyl bromoacetate

Product 1

HCID 347841Methyl 3-hydroxy-3-phenylpropanoate

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 7915Isopropyl AcetateSolvent

Conditions

Temperature
65 °C

Procedure

At room temperature, a three-necked flask fitted with reflux condenser, internal thermometer, dropping funnel and stirrer was charged, under nitrogen protective gas, with 5.7 g of zinc powder (87 mmol) in 35 ml of isopropyl acetate. After 1.65 ml of trimethylchlorosilane (13 mmol) had been added, the mixture was heated at 65° C. for 30 min. Following cooling to 60° C., 6.2 g of benzaldehyde (58 mmol) were added and, over the course of 4 min, 10.6 g of methyl bromoacetate (70 mmol) were added dropwise at 55° C., the temperature being maintained at 55° C. by external cooling. The mixture was then stirred at 55° C. for 5 min and, after cooling to 0° C., acidified with 40 ml of 2 N hydrochloric acid to a pH of 1 and stirred for 30 min. Excess zinc was removed by filtration and the organic phase separated. The organic phase was then stirred at 0° C. with 40 ml of 0.5 N hydrochloric acid and finally washed with 20 ml of saturated sodium hydrogen carbonate solution. Following phase separation and drying over sodium sulfate, the solvent was distilled off under reduced pressure. Methyl 3-hydroxy-3-phenylpropionate was obtained in a yield of 8.9 g (85% of theory) with a boiling point of 76° C. (0.07 mbar).

Workup

  1. customAt room temperature, a three-necked flask fitted
  2. temperaturewith reflux condenser
  3. temperatureFollowing cooling to 60° C.
  4. additionwere added dropwise at 55° C.
  5. temperaturethe temperature being maintained at 55° C. by external cooling
  6. temperatureafter cooling to 0° C.
  7. stirringstirred for 30 min
  8. customExcess zinc was removed by filtration
  9. customthe organic phase separated
  10. stirringThe organic phase was then stirred at 0° C. with 40 ml of 0.5 N hydrochloric acid
  11. washfinally washed with 20 ml of saturated sodium hydrogen carbonate solution
  12. customFollowing phase separation
  13. dry with materialdrying over sodium sulfate
  14. distillationthe solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-044fe6760ed146048d43d8e6d2cef5d7
Source dataset
uspto-grants-2003_08
Patent number
US06605716B2

Reaction notes

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