Acetic Acid → 3-Chloro-2-hydroxypropyl acetate

関与物質

反応条件

反応手順

Epichlorohydrin (92.5 g, 1.0 mol) was dissolved in 61.2 g (1.0 mol) of glacial acetic acid and 0.35 g of ferric chloride was added. The mixture was stirred at 65° C. overnight. Another 0.35 g of ferric chloride was added and the mixture was stirred another day. It was then concentrated by evaporation under reduced pressure to obtain 153 g 3-chloro-2-hydroxypropyl acetate as an oil. A few crystals of p-toluenesulfonic acid were added and then 81.5 g (1.13 mol) of ethyl vinyl ether was added dropwise with stirring and cooling with an ice bath to keep the temperature below about 35° C. When the addition was complete, the mixture was stirred overnight at 40° C. The dark oily product was presumed to be 3-chloro-2-(1-ethoxyethoxy)propyl acetate. This oil was added dropwise with stirring to a mixture of 110 g (2.75 mol) of sodium hydroxide in 110 mL of water heated to 105° C. When the addition was complete, the mixture was heated at 105° C. with stirring for 4 hours. It was then cooled and poured into 500 mL of water. The resulting mixture was extracted with 2×500 mL of diethyl ether and the ethereal extract was washed with concentrated aqueous sodium chloride, dried over sodium sulfate, and concentrated by evaporation under reduced pressure at 30° C. to obtain a dark oil. This oil was distilled at 5 mm Hg (665 pascals) pressure. The 40 g portion boiling at 60-68° C., which was 3-(1-ethoxyethoxy)oxetane, was collected. This fraction was dissolved in 100 mL of methanol and 25 mg of p-toluenesulfonic acid was added with stirring at about 10° C. The mixture was stirred for 2 hours at ambient temperature and then 1.0 g of solid sodium bicarbonate was added with stirring. After 5 min, the mixture was filtered and concentrated by evaporation under reduce pressure. The colorless oil residue was distilled at 5 mm Hg (665 pascals) pressure and the 1.9 g fraction boiling at 50-56° C., which was the title compound, a colorless liquid, was collected.

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