Hydrogen Peroxide → HCID 12017758, compound

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Reaction Steps

A solution of 88.7 g (392.5 mmol) of the trimethylsilyl ether of 9-decyn-1-ol (from Example 1) in 100 ml of THF is cooled to -70°. To this is added, dropwise, 245.3 ml (392.5 mmol) of n-butyllithium (1.6 in hexane), after which the mixture is warmed to -40° and poured into the hexenyldicyclohexylborane solution from above. This mixture is stirred at 0° for 30 min. and then cooled to -35°. Tri-n-butyltin chloride (128 g, 124 ml) is added, and the mixture is allowed to warm to ~20° and stirred for 1.5 hours. Acetic acid (186 ml) is then added dropwise and the mixture is stirred overnight at 50°. 2 N sulfuric acid (80 ml) is then added. After 30 min., the mixture is cooled and 392.5 ml of 6 N sodium hydroxide is added, followed by the addition, in portions, of 94.2 ml of 30% hydrogen peroxide at ~30°. The reaction mixture is worked up by dilution with water and extraction with hexane. The hexane layer is washed with concentrated aqueous sodium bisulfite and with brine, dried, and stripped of solvent and cyclohexanol under vacuum (0.05 mm). The crude product is chromatographed on a column of silica gel, eluting with hexane, then 10% ether/hexane and finally 20% ether/hexane. Recrystallization from 400 ml of hexane (3X) at -60° gives (9Z, 11E)-9,11-hexadecadien-1-ol containing about 8% of the E, E isomer. This product is further purified by dissolving it in 150 ml THF, adding a solution of 3 g of tetracyanoethylene in 80 ml of THF and stirring the mixture overnight at room temperature. The THF is stripped under vacuum and the product is purified by chromatography on a column of silica gel, eluting with hexane, then 10% ether/hexane and finally 20% ether/hexane. Low temperature recrystallization (-60°) from hexane (3X 500 ml) yields the product (9Z, 11E)-9,11-hexadecadien-1-ol.

Provenance & Evidence