A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1927, 7, 6
DOI: 10.15227/orgsyn.007.0006
Submitted by Carl N. Webb
Checked by C. S. Marvel and P. L. Salzberg.
1. Procedure
In a 3-l. round-bottomed flask are placed 750 g. (8.1 moles) of aniline (Note 1) and 1 kg. (8.2 moles) of benzoic acid. When about two-thirds of the benzoic acid is in the flask the mixture is melted to make room for the rest. The flask is placed in a large oil bath and connected to a condenser for distillation. The temperature of the oil is raised quickly to 180–190°, at which point distillation starts. The bath is held at this temperature until practically no more aniline and water distil (about two hours), and then the temperature is slowly raised to 225° and maintained at this temperature until no further distillation takes place (one to two hours). The oil bath is now removed and the contents of the flask are allowed to cool below 180° and 550 g. (5.9 moles) of aniline is added. The distillations at 190° and 225° are repeated (about six hours). The hot mixture is poured into two 20-cm. evaporating dishes (Hood) and is allowed to cool. The crude product weighs 1600–2000 g., depending on the amount of aniline retained.
The purplish-gray solid is ground (Note 2) in a large mortar and is poured with vigorous stirring into a 12-l. (3-gallon) crock containing 6 l. of approximately normal hydrochloric acid (5.5 l. of water and 500 cc. of concentrated hydrochloric acid). The stirring is continued for one hour after all the benzanilide has been added, and then the solid is filtered on a 20-cm. Büchner funnel. The process of stirring with acid and filtering is repeated twice to remove the excess of aniline. The solid is stirred for two hours with 6 l. of water and is filtered. It is stirred for one hour with 6 l. of normal sodium hydroxide solution to remove the excess of benzoic acid and is then filtered. The stirring with alkali and filtering is repeated. The solid is next stirred for two hours with 7 l. of water and is filtered, sucked dry, and air-dried overnight on paper.
After drying on paper the purplish solid is dried to constant weight in three 20-cm. evaporating dishes at 90–100° (about two days) and is then repowdered. The product is light purplish-gray and weighs 1270–1325 g. (80–84 per cent of the theoretical amount). It melts at 157–160°. The product is pure enough for use in the preparation of p-dimethylaminobenzophenone (p. 217) and for most synthetic purposes. When 100 g. of benzanilide is dissolved in 750 cc. of hot alcohol (Note 3) and the solution is boiled with about 10 g. of decolorizing carbon (Norite), filtered, and cooled at 10° overnight, 80–86 g. of an almost colorless product melting at 160–161° separates. A second crystallization from alcohol using decolorizing carbon gives a white product with approximately the same loss in the mother liquors as in the first crystallization.
2. Notes
1. The ordinary "pure" aniline of commerce gives as good yields and as pure a product as redistilled aniline.
2. The benzanilide must be finely ground in order that aniline and benzoic acid may be completely extracted.
3. Very little of the solid fails to go into solution. The hot solution must be filtered rapidly as the benzanilide crystallizes easily.
3. Discussion
Benzanilide can be prepared by the treatment of aniline with benzoyl chloride,1 benzoic anhydride,2 or benzoic acid.3. Benzanilide has also been prepared from benzamide, aniline, and boron fluoride.4 The method described in the procedure is essentially that of Nägeli.3
This preparation is referenced from:

References and Notes
  1. Gerhardt, Ann. 60, 311 (1846); Dehn and Ball, J. Am. Chem. Soc. 36, 2096 (1914).
  2. Meyer and Sundmacher, Ber. 32, 2123 (1899).
  3. Hübner, Ann. 208, 291 (1881); Nägeli, Bull. soc. chim. (3) 11, 892 (1894).
  4. Sowa and Nieuwland, J. Am. Chem. Soc. 59, 1202 (1937).

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

alcohol (64-17-5)

hydrochloric acid (7647-01-0)

aniline (62-53-3)

sodium hydroxide (1310-73-2)

Benzoic acid (65-85-0)

Benzanilide (93-98-1)

decolorizing carbon (Norite),
carbon (7782-42-5)

benzoyl chloride (98-88-4)

Benzoic anhydride (93-97-0)

benzamide (55-21-0)

boron fluoride (7637-07-2)

p-Dimethylaminobenzophenone (530-44-9)