Salicylic Acid → HCID 10058953, compound

Participants

Reaction Steps

Geranyl acetate was oxidized as described previously with some modification (21). Forty milliliters (0.36 mol) of 90% tert-butyl hydroperoxide was added to a stirred suspension of 1.11 g (0.01 mol) of SeO2, 1.4 g (0.01 mol) of salicylic acid, and 75 ml of CH2Cl2 in a 250 ml round bottom flask covered in aluminum foil. The resulting solution was allowed to stir to homogeneity at room temperature before being placed at 0° C. After ten minutes, 21.5 ml (0.10 mol) of geranyl acetate (4) was introduced dropwise. The mixture was stirred for 5 h at 0° C., and then for 20 h at rt. TLC analysis indicated the presence of starting material and two oxidized products (Rf 0.38 aldehyde, Rf 0.19 alcohol). The solution was diluted with 100 ml toluene, and solvents were removed under reduced pressure. The residue was then dissolved in toluene, washed with 5% NaHCO3 to remove H2SeO3, saturated CuSO4, saturated aqueous Na2S2O3 (2×), water, brine, dried over MgSO4 and filtered. The solvent was removed under reduced pressure affording a crude oil, which was dissolved in 100 ml dry CH2Cl2 and cooled to 0° C. 40.95 g (0.47 mol) of activated MnO2 was added, and the suspension was stirred for 5 h at 0° C., then overnight at rt. The mixture was filtered over a short bed of Celite, and washed thoroughly with dry CH2Cl2. Solvent was evaporated under reduced pressure to yield a crude, pale yellow oil which was purified by flash chromatography on silica gel (5% EtOAc in hexane) affording 10.68 g (51 %) of 5 as a colorless oil; 1H NMR (C6H6, 200 MHz) δ9.47 (s, 1H), 5.98 (t, 1H, J=6.9 Hz), 5.48 (t, 1H, J=6.9 Hz), 4.75 (d, 2H, J=6.8 Hz), 2.11 (q, 2H, J=7.3 Hz), 1.92 (t, 2H, J=7.3 Hz), 1.91 (s, 3H), 1.79 (s, 6H), 1.59 (s, 3H); 13C NMR (50.3 MHz) δ195.47, 171.39, 153.70, 140.73, 140.08, 120.01, 61.48, 38.13, 27.33, 21.37, 16.77, 9.62.

Provenance & Evidence