Organic Syntheses | Page 5

surrounded with cracked ice, and the stirrer started; 460 g. of benzaldehyde (U. S. P.) are then added at once. The temperature of the mixture should not be below 15'0 and it should not be allowed to rise above 30'0 during the reaction. If it tends to do so, the stirring is not sufficiently vigorous.
It is advantageous, though not essential, to inoculate the mixture with a little powdered benzalacetophenone after stirring for half an hour. After two to three hours, the mixture becomes so thick that the stirring is no longer effective. The stirrer is then removed and the mixture left to itself in an ice-box for about ten hours. The mixture now is a thick paste composed of small shot-like grains suspended in an almost colorless liquid. It is cooled in a freezing mixture and then either centrifuged or filtered on a large Buchner funnel, washed with water until the washings are neutral to litmus, and finally washed with 200 cc. of alcohol, which has previously been cooled to 0'0. After thorough drying in the air, the crude product weighs about 880 g. (yield 97 per cent of the theoretical amount) and melts at 50-54'0. It is sufficiently pure for most purposes but tenaciously holds traces of water. It is most readily purified by recrystallization from four to four and a half times its weight of 95 per cent alcohol. Eight hundred and eighty grams of crude product give 770 g. (85 per cent of the theoretical amount) of light-yellow material (m. p. 55-57'0) and 40-50 g. that require recrystallization.
2. Notes
The acetophenone should be as pure as possible (m. p. 20'0). Commercial acetophenone contains variable quantities of impurities which reduce the yield. By distilling commercial acetophenone with the help of a good still-head (preferably under diminished pressure) and using only the fraction which boils at 201-202'0 (76-77'0/10 mm.) greater quantities of benzalacetophenone can be obtained than by using the entire sample.
Commercial benzaldehyde can be used in place of the purer product, but the amount used must be increased to make up for the impurities which are present.
If the temperature is too low, or the stirring too slow, the product separates as an oil, which later solidifies in large lumps.
If the temperature is allowed to rise above 30'0, secondary reactions diminish both the yield and the purity of the product. The most favorable temperature is 25'0.
In recrystallizing benzalacetophenone, the alcohol should be saturated at 50'0. If the solution is saturated above this temperature, the benzalacetophenone tends to separate as an oil. The solution should be allowed to cool gradually, and should finally be chilled in a freezing mixture. 3. Other Methods of Preparation
The methods for producing benzalacetophenone are: the action of acids on a mixture of benzaldehyde and acetophenone or on a solution of these substances in glacial acetic acid;[1] the condensation of benzaldehyde and acetophenone with a 30 per cent solution of sodium methylate at low temperatures;[2] the action of sodium hydroxide on an alcoholic solution of benzaldehyde and acetophenone.[3]
The methods based on the use of acids as condensing agents were not considered, because Claisen, who devised them, abandoned them after he found that alkaline condensing agents gave better results. The preliminary experiments showed that condensation with sodium methylate takes a long time and gives a product which it is difficult to handle in large quantities. The method devised by Kostanecki and Rossbach[3] has therefore been developed.
[1] Ber. 14, 2463 (1881).
[2] Ber. 20, 657 (1887).
[3] Ber. 29, 1492 (1896).

II
BENZYL BENZOATE
2 C6H5CHO + C6H5CH2ONa--> C6H5CO2CH2C6H5 + C6H5CH2ONa
Prepared by O. KAMM and W. F. KAMM. Checked by ROGER ADAMS and R. L. JENKINS.
1. Procedure
THREE grams of metallic sodium are dissolved by warming for half an hour in 70 g. of pure benzyl alcohol (see notes), and after the mixture has cooled to room temperature the solution is added gradually, with thorough mixing, to 454 g. of c. p. benzaldehyde (which must contain LESS than 1 per cent of benzoic acid). The reaction mixture has a tendency to become warm, but the temperature should be kept slightly below 50-60'0 by cooling, if necessary. A pasty gelatinous mass results. After about half an hour the temperature of the mixture no longer rises; it is then warmed on the water bath for about one or two hours, with occasional shaking.
The cooled reaction product is treated with 200 cc. of water, the layer of oil separated, washed once with a second portion of water, and subjected to distillation in vacuo. The first fraction of the distillate contains benzyl alcohol together with unchanged aldehyde, as well as a small quantity of water. The temperature then rises rapidly to the boiling-point of benzyl benzoate, when the receivers are changed. The product boils at 184-185'0/15 mm., and analysis by saponification shows it to consist of 99 per cent