反应详情

Under nitrogen atmosphere, to a solution of lithium aluminum hydride (1.09 g, 28.8 mmol) in anhydrous THF (100 mL) was added dropwise a solution of 8-hydroxy-2-(6-hydroxy-5,5-dimethylhexyl)-7,7-dimethyloctanoic acid (3.64 g, 11.5 mmol) in THF (40 mL) at room temperature. The reaction mixture was heated at reflux for 5 h and kept at room temperature overnight. Water (100 mL) was added carefully to the reaction mixture under cooling with a water bath. The pH was adjusted to 1 with 2 N hydrochloric acid. The product was extracted with diethyl ether (3×60 mL). The combined organic layers were washed with water (2×50 mL) and brine (50 mL). The ethereal solution was dried over sodium sulfate and concentrated in vacuo to furnish the crude product (3.2 g), which was purified by chromatography on silica (hexanes:ethyl acetate=50:50) to yield 7-hydroxymethyl-2,2,12,12-tetramethyltridecane-1,13-diol (3.0 g, 86%) as a yellow oil. 1H NMR (300 MHz, CD3OD/TMS): δ (ppm): 4.88 (s, 3H), 3.44 (d, 2H, J=4.8 Hz), 3.23 (s, 4H), 1.5-1.1 (m, 17H), 0.85 (s, 12H). 13C NMR (75 MHz, CD3OD/TMS): δ (ppm): 72.0, 65.7, 41.7, 40.0, 36.0, 32.2, 29.0, 25.4, 24.7, 24.6. HRMS (LSIMS, gly): Calcd. for C18H39O3 (MH+): 303.2899. found 303.2901. HPLC: 94.6% purity.

1. temperatureThe reaction mixture was heated
2. temperatureat reflux for 5 h
3. temperatureunder cooling with a water bath
4. extractionThe product was extracted with diethyl ether (3×60 mL)
5. washThe combined organic layers were washed with water (2×50 mL) and brine (50 mL)
6. dry with materialThe ethereal solution was dried over sodium sulfate
7. concentrationconcentrated in vacuo
8. customto furnish the crude product (3.2 g), which
9. customwas purified by chromatography on silica (hexanes:ethyl acetate=50:50)