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Org. Synth. 1946, 26, 21
DOI: 10.15227/orgsyn.026.0021
DI-(p-CHLOROPHENYL)ACETIC ACID
[Acetic acid, di-(p-chlorophenyl)]
Submitted by Oliver Grummitt, Allen Buck, and Richard Egan.
Checked by Lee Irvin Smith, R. T. Arnold, and Paul N. Craig.
1. Procedure
A mixture of 400 ml. of diethylene glycol (Note 1) and 49.5 g. (0.14 mole) of 1,1-di-(p-chlorophenyl)-2,2,2-trichloroethane (Note 2) is placed in a 1-l. three-necked flask fitted with a stirrer, a reflux condenser, and a thermometer. To this is added a solution of 63 g. (1.12 mole) of potassium hydroxide in 35 ml. of water. The mixture is stirred and refluxed for 6 hours at such a rate that the temperature is maintained at 134–137° (Note 3) and (Note 4). The mixture is allowed to cool and, with vigorous stirring, is poured into 1 l. of cold water. The insoluble material is filtered and washed twice with 50-ml. portions of warm water (Note 5). The filtrate is then boiled gently for 5 minutes with 2 g. of Norit; the carbon is removed, the filtrate is acidified to litmus with 20% sulfuric acid (approximately 120 ml.), and then an additional 30 ml. of acid is added. The mixture is cooled to 0–5°; the precipitate is collected by filtration under suction, washed free of sulfate ions with water, and dried at 100–110°. The product is di-(p-chlorophenyl) acetic acid melting at 163–165°; it weighs 27–28.5 g. (69–73%). For purification, this material is dissolved in 100 ml. of boiling 95% ethanol, the solution is filtered, and approximately 45 ml. of water is added to the boiling filtrate until it just becomes turbid. The solution is then cooled to 0–5°, and the solid is removed by suction filtration. The material weighs 25–26 g. and melts at 164–166°.
2. Notes
1. Diethylene glycol with a boiling range of 230–270°, from Carbide and Carbon Chemicals Corporation, is satisfactory.
2. A purified grade of 1,1-di-(p-chlorophenyl)-2,2,2-trichloroethane (DDT) melting at 105–106° should be used. It can be obtained by crystallizing the technical material from ethanol. Thus, 100 g. of technical DDT melting at 81–96°, when crystallized from 550 ml. of 95% ethanol, gave about 70 g. of material melting at 105–106°.
3. The intermediate product, 1,1-di-(p-chlorophenyl)-2,2-dichloroethylene,1,2 can be isolated readily. The mixture is gradually (7–8 minutes) heated to reflux temperature and is then refluxed 2 minutes. The mixture is cooled and poured into 1 l. of cold water, and the product is removed by suction filtration, washed well with water, and dried. The yield of crude product melting at 83–86° is 43.5 g. (97%). This may be purified by crystallization from 200 ml. of 95% ethanol; the product weighs 39.5 g. and melts at 86.5–88°.
4. Longer reaction times or higher temperatures favor the formation of di-(p-chlorophenyl) methane; see Note 5.
5. The insoluble material consists of silica, 1,1-di-(p-chlorophenyl)-2,2-dichloroethylene and a small amount of di-(p-chlorophenyl) methane3 (melting at 54–55° when purified), formed by decarboxylation of the acid.
3. Discussion
Di-(p-chlorophenyl) acetic acid has been made by the action of alcoholic potassium hydroxide on 1,1-di-(p-chlorophenyl)-2,2-dichloroethane;2,4 by the action of barium hydroxide on DDT in ethylene glycol;4 and by the condensation of chlorobenzene with glyoxylic acid.4
This preparation is referenced from:

References and Notes
  1. Zeidler, Ber., 7, 1181 (1874).
  2. Grummitt, Buck, and Stearns, J. Am. Chem. Soc., 67, 156 (1945).
  3. Montagne, Rec. trav. chim., 25, 379 (1906).
  4. White and Sweeney, Public Health Repts. U. S., 60, 66 (1945).

Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

silica

1,1-di-(p-chlorophenyl)-2,2,2-trichloroethane (DDT)

alcoholic potassium hydroxide

ethanol (64-17-5)

sulfuric acid (7664-93-9)

carbon,
Norit (7782-42-5)

chlorobenzene (108-90-7)

potassium hydroxide (1310-58-3)

ethylene glycol (107-21-1)

barium hydroxide (17194-00-2)

glyoxylic acid (298-12-4)

diethylene glycol (111-46-6)

Di-(p-chlorophenyl)acetic acid,
Acetic acid, di-(p-chlorophenyl) (83-05-6)

1,1-di-(p-chlorophenyl)-2,2,2-trichloroethane (50-29-3)

1,1-Di-(p-chlorophenyl)-2,2-dichloroethylene (72-55-9)

di-(p-chlorophenyl) methane (101-76-8)

Di-(p-chlorophenyl) acetic acid

1,1-di-(p-chlorophenyl)-2,2-dichloroethane (72-54-8)