Hydroxylamine → 3-Octyl acetate

HRID 279403Notes

Reaction equation

HRID 279403 reaction equation
NO.[CH:3](=[O:9])[CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].C([Zn][CH2:13][CH3:14])C.[C:15](OC(=O)C)(=[O:17])[CH3:16]>CCCCCC.CCOCC.C1(C)C=CC=CC=1>[C:15]([O:9][CH:3]([CH2:4][CH2:5][CH2:6][CH2:7][CH3:8])[CH2:13][CH3:14])(=[O:17])[CH3:16]

Participants

8

Reactant 4

HCID 787HydroxylamineHCID 6184HexanalHCID 7918Acetic AnhydrideHCID 178418750HCID 178418750, compound

Product 1

HCID 5212383-Octyl acetateYield 66%

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 freshly distilled hexanal (0.30 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 was 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 95% hexane and 5% ethyl acetate as eluant. The product (+)-3-octyl acetate (0.34 g, 66%) was isolated as a colorless liquid by distillation of the solvent at reduced pressure. Anal. for C10H20O2. Calcd: C, 69.72; H, 11.70; found: C, 70.08; H, 11.86. 1H NMR (CDCl3/TMS): δ 0.86 (t, 6 H, J=7), 1.22-1.33 (br m, 6 H), 1.45-1.60 (m, 4 H), 2.03 (s, 3 H), 4.80 (m, 1 H). 13C NMR (CDCl3/TMS): δ 9.58, 14.00, 21.25, 22.57, 25.02, 26.98, 31.62, 33.60, 75.57, 170.97. [α]D25=+7.0, c=2.01 g/100 mL chloroform. Chiral capillary gas chromatographic analysis at 100° C. on Cyclodex B stationary phase (J & W Scientific) indicated that the enantiomeric excess of the product was 86%.

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 was 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 95% hexane and 5% ethyl acetate as eluant

Sources & evidence

ORD record
ord-195276a86d85449ba90215841090124d
Source dataset
uspto-grants-2002_03
Patent number
US06362344B1

Reaction notes

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