反应详情

76 g (480 mmoles) of 4 methoxycyclohexane carboxylic acid (cis/trans mixture) were boiled for 7 hours with refluxing in 350 ml of thionyl chloride to which several drops of dimethyl formamide had been added. The obtained 4 methoxycyclohexane carboxylic acid chloride was composed almost completely of the trans compound. After distilling off of the thionyl chloride the residue was incorporated into 75 ml of dry tetrahydrofuran. At a temperature of from 0° to 5° C. this solution was slowly added dropwise to a solution of 158.4 g (1440 mmoles) of hydroquinone in 650 ml of tetrahydrofuran and 375 ml of pyridine. When, after this addition, the mixture had attained room temperature, it was poured onto ice and concentrated sulphuric acid. Extraction with dichloromethane, evaporation of the dichloromethane, and, in succession, conversion of the evaporation residue to the crystallised form from an ethanol-water mixture and from toluene gave a yield of 24.45 g (20%) of pure trans 4 hydroxyphenyl 4'methoxycyclohexyl carboxylate. 24.3 g (97 mmoles) of the above compound were boiled, with refluxing, for 24 hours with 17.6 g of allyl bromide (145 mmoles) and 13.4 g (97 mmoles) of potassium carbonate in 350 ml of methylethyl ketone. After cooling the reaction mixture was poured into 1 .right brkt-top.of ice water, which was extracted with the aid of diethyl ether. After drying and evaporation of the diethyl ether 28.9 g (97%) of 4 allyloxyphenyl 4'methoxycyclohexyl carboxylate were obtained. To 28.7 g (99 mmoles) of said compound in 250 ml of dichloromethane there were added 32.9 g of chloroperbenzoic acid, and the mixture was stirred for 24 hours under an atmosphere of nitrogen. After being diluted with dichloromethane the reaction mixture was washed with sodium carbonate solution and water. After drying the dichloromethane was distilled off, and the residue was purified on a column filled with silica gel and eluted with a hexane-ethyl acetate mixture (75/25). The yield was 20.8 g (66%) of 4(2,3 epoxypropyl oxy)phenyl 4'methoxycyclohexyl carboxylate.

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