Experimental:n-Butyl hypochlorite was prepared by adding 67 ml of n-butyl alcohol, 400 ml benzene, and 67 ml. of acetic acid to a
mixture of 1000 ml of 0.76 M sodium hypochlorite and 200 g. of ice. The benzene solution of n-butyl hypochlorite was separated, and the aqueous
fraction washed twice with 50 ml portions of benzene. The combined benzene solution was washed with aqueous sodium bicarbonate and dried over
anhydrous sodium sulfate. The resulting dry benzene solution (550 ml.) was 1.14 M in n-butyl hypochlorite, as determined by iodometric titration.
Seventy grams of dry powdered sodium bicarbonate was added and the resulting slurry was heated under reflux until the evolution of carbon dioxide gas
ceased (1 hr). The solids were removed by filtration and the benzene was distilled. Butanol was detected by gas chromatography in the distillate.
The residue was fractionally distilled and the fractions were assayed by gas chromatography.
The caluclated yield of tetramethylene chlorohydrin was 16%. The infrared spectrum of Fraction 3 confirmed that it was chiefly tetramethylene
chlorohydrin. When a portion of Fraction 3 was treated with hot aqueous 10 M sodium hydroxide, tetrahydrofuran, bp 60-68C was obtained.....
In a similar experiment, condusted in the absence of sodium bicarbonate, the total reaction mixture was treated with potassium hydroxide and
tetrahydrofuran was obtained directly. |