Twelve grams (0.18 mole) of ground potassium hydroxide is dissolved in
45 ml. of n-propyl alcohol in a
three-necked 500-ml. flask set on a
steam bath so that the mixture can be warmed. Two necks of the flask are fitted with
dropping funnels. A
Vigreux fractionating column (25 cm. in length and 12 mm. in diameter) is inserted in the third neck of the flask. The column is connected, through a
condenser and
adapter, to a
filter flask set in ice as the receiver. The side arm of the receiver is fitted with a
drying tube. About 1.5 hours is required to dissolve the hydroxide, whereupon an additional amount of alcohol is added to bring the total volume to 50 ml. The solution is then cooled, and
100 ml. of absolute ether is added. Through one
dropping funnel is added dropwise
20 ml. of nitrosomethylurethan1 (equivalent to 0.10 mole of diazomethane; (Note
1)). The flask is warmed on a steam bath so that
diazomethane distils over with
ether while the
nitrosomethylurethan is being added. The addition requires about 20 minutes. During this operation more dry
ether is added as needed, through the second dropping funnel, until the total volume of
ether distillate is 250 ml. When the
ether distilling over is colorless, the distillate is transferred to another
three-necked 500-ml. flask, equipped with a mechanical stirrer, a dropping funnel, and a condenser. To the stirred solution is added, over a period of 15 minutes, a solution of
6.6 ml. (7.7 g., 0.050 mole) of phenylacetyl chloride in
10 ml. of absolute ether. A copious evolution of
nitrogen accompanies this operation.
After standing for 2 hours, the solution of diazoketone is cooled in ice and treated with dry gaseous
hydrogen chloride until the passage of the gas no longer causes evolution of
nitrogen (Note
2). At the end of this time, the original yellow color of the solution has changed to an orange-red. About 100 ml. of water is slowly and cautiously added to the
ether solution in order to cause a separation into two layers. An additional 50 ml. of water is then added to give a more complete separation. The
ether layer is then washed with two
50-ml. portions of a 5% solution of sodium carbonate in water. The
ether solution is dried with anhydrous
calcium chloride or calcium sulfate, the solvent evaporated, and the product distilled. The yield of
benzyl chloromethyl ketone, b.p.
133–135°/19 mm. or
96–98°/1 mm., is
7.0–7.1 g. (
83–85%) (Note
3) and (Note
4).