Hydrogen Peroxide → HCID 56619791, compound

Participants

Reaction Steps

422 mg (1.17 mmol) of 4-(3,7-dimethyl-6-octen-1-yl)-5-(6-methoxycarbonylhexylidene)-2-cyclopentenone was dissolved in 4 ml of methanol. With ice cooling and stirring, 600 μl (5.85 mmol) of 30% aqueous hydrogen peroxide and further 40 μl (40 mmol) of an aqueous solution of 1N sodium hydroxide were added thereto. After the mixture was stirred at 0° C. for 45 minutes, a saturated aqueous solution of ammonium chloride was added to the reaction mixture, the mixture was extracted with hexane, dried over anhydrous sodium sulfate, filtrated, and concentrated. 408 mg of the thus obtained oily product was dissolved in 4 ml of acetone. With ice cooling and stirring, 800 μm of concentrated hydrochloric acid was added to the solution and the mixture was stirred at 0° C. for 10 minutes and then at room temperature for 2 hours. A saturated saline solution was added thereto and the pH of the mixture was adjusted to 4 with an aqueous solution of 5N sodium hydroxide and extracted with ethyl acetate. The collected organic layer was washed with a saturated saline solution, dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to silica gel column chromatography (silica gel, 45 g; eluent, cyclohexane:ethyl acetate=30:1→1:2) to obtain 28 mg (yield 6%) of a low polar isomer (Z-form) of 2-chloro-4-(3,7-dimethyl-6-octenyl)-5-(6-methoxycarbonylhexylidene)-2-cyclopentenone, 168 mg (yield 36%) of its high polyer isomer (E-form), 46 mg (yield 9%) of 2-chloro-4-)6-chloro-3,7-dimethyloctyl)-5-(6-methoxycarbonylhexylidene)-2-cyclopentenone, and 34 mg (yield 8%) of 2-chloro-4-(3,7-dimethyl-6-octenyl)-5-(6-carboxyhexylidene)-2-cyclopentenone.

Provenance & Evidence