Benzaldehyde → 1-Phenylpropyl acetate

HRID 279402Notes

Reaction equation

HRID 279402 reaction equation
NO.[CH:3](=[O:10])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.C([Zn][CH2:14][CH3:15])C.[C:16](OC(=O)C)(=[O:18])[CH3:17]>CCCCCC.CCOCC.C1(C)C=CC=CC=1>[C:16]([O:10][CH:3]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)[CH2:14][CH3:15])(=[O:18])[CH3:17]

Participants

8

Reactant 4

HCID 240BenzaldehydeHCID 787HydroxylamineHCID 7918Acetic AnhydrideHCID 178418750HCID 178418750, compound

Product 1

HCID 1011341-Phenylpropyl acetateYield 86%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Procedure

To a vial containing aminoalcohol 1 (0.05 g, 0.17 mmol) prepared as in Example 1 was added a solution containing benzaldehyde (0.32 g, 3.0 mmol), toluene (3.0 mL), and 1 M diethylzinc in hexane (6.0 mL). After 3 days at room temperature, acetic anhydride (1.2 mL, 13 mmol) was added. After 2 additional days, the mixture was diluted in ether (50 mL) and the reaction was quenched by dropwise addition of half-saturated aqueous ammonium chloride (50 mL). The ether layer separated and the aqueous layer was further extracted with ether (2×50 mL). The combined ether layers were dried over magnesium sulfate whereupon the solvent was removed at reduced pressure. The residue was purified by flash chromatography on 220-400 mesh silica with 90% hexane and 10% ethyl acetate as eluant. The product (+)-1-phenylpropyl acetate (0.46 g, 86%) was isolated as a colorless liquid by distillation of the solvent at reduced pressure. Anal. for C11H14O2. Calcd: C, 74.13; H, 7.92; found: C, 74.32; H, 7.82. 1H NMR (CDCl3/TMS): δ 0.87 (t, 3 H, J=7), 1.79, (m, 1 H), 1.90 (m, 1 H), 2.06 (s, 3 H), 5.66 (t, 1 H, J=7), 7.1-7.7 (m, 5 H). 13C NMR (CDCl3/TMS): δ 9.89, 21.23, 29.30, 77.66, 126.76, 128.81, 128.57, 140.58, 170.36. [α]D25=+103.4, c=2.15 g/100 mL chloroform. Chiral capillary gas chromatographic analysis at 120° C. on Cyclodex B stationary phase (J & W Scientific) indicated that the enantiomeric excess of the product was 98%.

Workup

  1. additionTo a vial containing
  2. additionwas added a solution
  3. customthe reaction was quenched by dropwise addition of half-saturated aqueous ammonium chloride (50 mL)
  4. customThe ether layer separated
  5. extractionthe aqueous layer was further extracted with ether (2×50 mL)
  6. dry with materialThe combined ether layers were dried over magnesium sulfate whereupon the solvent
  7. customwas removed at reduced pressure
  8. customThe residue was purified by flash chromatography on 220-400 mesh silica with 90% hexane and 10% ethyl acetate as eluant

Sources & evidence

ORD record
ord-2406a2687ee643f89c4418ba7bf5d500
Source dataset
uspto-grants-2002_03
Patent number
US06362344B1

Reaction notes

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