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Acetone, 6.2 g, was dissolved in 50 mL of DMF and allowed to react with 17.0 g of chlorine (~10% excess) which was bubbled into the reaction mixture from a trap cooled in a dry ice-acetone bath. The reaction mixture was cooled in an ice bath. The temperature was kept below 50 °C. Chlorine addition took ~2.0 h. The major product, 1,1-dichloroacetone, could be distilled directly from the crude reaction mixture, yield 17.9 g (64%).
Alternatively, the reaction could be worked up by extraction with 50 mL of carbon tetrachloride and 100 mL of 2 N HCl. The organic phase was washed two additional times with water and dried over anhydrous magnesium sulfate. Gas chromatographic mass spectral analysis showed only two products, 1,1-dichloroacetone and 1,1,1-trichloroacetone (95:5).
In the course of 5 hours a rapid stream of chlorine gas (~34 L/h) was passed into 160 g of acetone. The temperature was kept at 25—30° by cooling with water. Distillation of the reaction product, 285 g, gave three fractions: a) 150 g of b.p. 119—125°, b) 35 g of b.p. 125—150°, c) 100 g of b.p. 115° (100 mm). Refractionation of fraction a) gave 105 g of a fraction of b.p. 118—119°. Judging from the chlorine content (54.5%), 8% of monochloroacetone was still present. The product was subsequently saturated with chlorine in the dark at 60° and again distilled. A main fraction was obtained, b.p. 118.4—118.8° (770 mm), 53.7—53.9° (80 mm), n(25, D) 1.4430, d(25/4) 1.3267; M.R. 25.79. Theor. 25.80.
Analysis. Calc. for C3H4OCl2: Cl 55.8. Found: Cl 55.5.
Determination of the Raman spectrum showed that lines of monochloroacetone were absent.
© Collected Ruslan Anatolievich Kiper, burewestnik@mail.ru