Benzaldehyde → HCID 9964892, compound

HRID 395902Notes

Reaction equation

HRID 395902 reaction equation
C[Si](C)(C)Cl.[C:6]1([CH2:12][CH2:13][C:14](=[O:18])[CH2:15][CH2:16][CH3:17])[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.C(=O)C1C=CC=CC=1.CC(=O)CCC.C1(C=CC(=O)CCC)C=CC=CC=1.Br[CH2:47][C:48]([O:50][CH3:51])=[O:49].Cl>C(OCC)(=O)C.[Zn]>[OH:18][C:14]([CH2:13][CH2:12][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)([CH2:15][CH2:16][CH3:17])[CH2:47][C:48]([O:50][CH3:51])=[O:49]

Participants

10

Reactant 7

HCID 240BenzaldehydeHCID 313Hydrochloric AcidHCID 6397ChlorotrimethylsilaneHCID 78952-PentanoneHCID 60984Methyl bromoacetateHCID 1225021-Phenylhexan-3-oneHCID 227280HCID 227280, compound

Product 1

HCID 9964892HCID 9964892, compound

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8857Ethyl 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 5.6 g of zinc powder (85 mmol) in 35 ml of ethyl acetate. After 1.61 ml of trimethylchlorosilane (12.6 mmol) had been added, the mixture was heated at 65° C. for 30 min, then left to cool to 60° C., following which 10 g of neat 1-phenylhexan-3-one prepared by base-catalyzed aldol condensation of benzaldehyde and pentan-2-one and subsequent hydrogenation of the resulting 1-phenylhex-1-en-3-one were added. Subsequently, over the course of 5 min, 10.4 g of methyl bromoacetate (68 mmol) were added dropwise, the temperature being maintained at 65° C. by external cooling. The mixture was stirred for 30 min at 60° C., and following cooling to 0° C., acidified with 35 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 30 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 removed by distillation under reduced pressure. Methyl 3-hydroxy-3-(2′-phenylethyl)caproate was obtained in a yield of 13.5 g (95% of theory) and a purity of greater than 97% (HPLC).

Workup

  1. customAt room temperature, a three-necked flask fitted
  2. temperaturewith reflux condenser
  3. waitleft
  4. temperatureto cool to 60° C.
  5. additionwere added
  6. temperaturethe temperature being maintained at 65° C. by external cooling
  7. temperaturefollowing cooling to 0° C.
  8. stirringstirred for 30 min
  9. customExcess zinc was removed by filtration
  10. customthe organic phase separated
  11. stirringThe organic phase was then stirred at 0° C. with 30 ml of 0.5 N hydrochloric acid
  12. washfinally washed with 20 ml of saturated sodium hydrogen carbonate solution
  13. customFollowing phase separation
  14. dry with materialdrying over sodium sulfate
  15. customthe solvent was removed by distillation under reduced pressure

Sources & evidence

ORD record
ord-99da56748a7249a3b274b8df758b4d96
Source dataset
uspto-grants-2003_08
Patent number
US06605716B2

Reaction notes

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