Org. Synth. 1923, 3, 45
DOI: 10.15227/orgsyn.003.0045
DIPHENYLACETIC ACID
[Acetic acid, diphenyl-]
Submitted by C. S. Marvel, F. D. Hager, and E. C. Caudle.
Checked by J. B. Conant and A. W. Sloan.
1. Procedure
In a
1-l. round-bottomed flask are placed
250 cc. of glacial acetic acid, 15 g. of red phosphorus, and 5 g. of iodine. The mixture is allowed to stand for fifteen to twenty minutes until the
iodine has reacted, and then 5 cc. of water
(Note 1) and
100 g. (0.44 mole) of benzilic acid (p. 89) are added. A
reflux condenser is attached, and the mixture is boiled continuously for at least two and one-half hours. After the reaction is complete, the hot mixture is filtered with suction to remove the excess
red phosphorus (Note 2). The hot filtrate is slowly poured into a cold, well-stirred, filtered solution of
20–25 g. of sodium bisulfite in 1 l. of water
(Note 3). This procedure removes the excess
iodine and precipitates the
diphenylacetic acid as a fine white or slightly yellow powder
(Note 4). The product is filtered with suction, washed with cold water, and dried thoroughly on
filter paper. The yield is
88–90 g. (
94–97 per cent of the theoretical amount) of a solid melting at
141–144° (Note 5). If a crystalline product is desired, the acid is dissolved in about
500 cc. of hot 50 per cent alcohol and then cooled. The melting point after recrystallization is
144–145°.
2. Notes
1.
In place of
phosphorus,
iodine, and water, a dilute solution of
hydriodic acid and
phosphorus may be used.
2.
If difficulties are encountered in filtering the hot
acetic acid solution through filter paper, an
asbestos filter may be prepared and used to advantage.
3.
Some samples of
sodium bisulfite caused part of the
diphenyl-acetic acid to dissolve. This can always be avoided if, after the solution of
sodium bisulfite is prepared, a current of
sulfur dioxide is passed in, until the solution is acid to litmus.
4.
Sometimes, if the
acetic acid solution is poured into the water too rapidly, the product will be slightly pink and a reprecipitation from
acetic acid solution will be necessary.
5.
The melting points of
benzilic acid and
diphenylacetic acid lie very close together. However, it is very easy to test for complete reduction by treating a little of the product with cold concentrated
sulfuric acid. If even a trace of
benzilic acid remains the
sulfuric acid will turn red.
3. Discussion
Diphenylacetic acid can be prepared by the reduction of
benzilic acid with
hydriodic acid and
red phosphorus,
1 by carbonation of the reaction product of
phenylsodium and
diphenylmethane,
2 and by hydrolysis of
1,1-dichloro-2,2-diphenylethylene.
3
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
red phosphorus
alcohol (64-17-5)
sulfuric acid (7664-93-9)
acetic acid (64-19-7)
sulfur dioxide (7446-09-5)
PHOSPHORUS (7723-14-0)
sodium bisulfite (7631-90-5)
iodine (7553-56-2)
Benzilic acid (76-93-7)
Diphenylmethane (101-81-5)
hydriodic acid (10034-85-2)
Diphenylacetic acid,
Acetic acid, diphenyl-,
diphenyl-acetic acid (117-34-0)
phenylsodium
1,1-dichloro-2,2-diphenylethylene
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