Hydroxylamine → 3-Octyl acetate

Participants

Reaction Steps

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%.

Provenance & Evidence