A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1939, 19, 55
DOI: 10.15227/orgsyn.019.0055
[Benzene, iodo-]
Submitted by H. J. Lucas and E. R. Kennedy.
Checked by John R. Johnson and P. L. Barrick.
1. Procedure
In a 3- or 5-gallon stoneware crock are placed 950 cc. (1130 g., 11.7 moles) of concentrated hydrochloric acid (sp. gr. 1.19), 950 cc. of water, 200 g. (196 cc., 2.15 moles) of aniline, and 2 kg. of ice (Note 1). The mixture is agitated by a mechanical stirrer, and, as soon as the temperature drops below 5°, a chilled solution of 156 g. (2.26 moles) of sodium nitrite in a measured volume (700–1000 cc.) of water is introduced fairly rapidly from a separatory funnel, the stem of which projects below the surface of the reaction mixture. The addition should not be fast enough to cause the temperature to rise to 10° or to cause evolution of oxides of nitrogen. The last 5 per cent of the nitrite solution is added more slowly, and the reaction mixture is tested with starch-iodide paper at intervals until an excess of nitrous acid is indicated.
Stirring is continued for ten minutes, and if necessary the solution is filtered rapidly through a loose cotton plug in a large funnel. An aqueous solution of 358 g. (2.16 moles) of potassium iodide is added and the reaction mixture allowed to stand overnight. The mixture is transferred to a large flask (or two smaller flasks) and heated on a steam bath, using an air-cooled reflux condenser, until no more gas is evolved, then allowed to cool and stand undisturbed until the heavy organic layer has settled thoroughly. A large part of the upper aqueous layer is siphoned off, and discarded (Note 2). The residual aqueous and organic layers are made alkaline by the cautious addition of strong sodium hydroxide solution (100–125 g. of solid technical sodium hydroxide is usually required) and steam-distilled at once. The last one-third of the steam distillate is collected separately and combined with the aqueous layer separated from the earlier portions of the distillate. This mixture is acidified with 5–10 cc. of concentrated sulfuric acid and steam-distilled again. The iodobenzene from this operation is combined with the main portion and dried with 10–15 g. of calcium chloride (Note 3) and (Note 4). Distillation under reduced pressure gives 327–335 g. (74–76 per cent of the theoretical amount) of iodobenzene, b.p. 77–78°/20 mm. or 63–64°/8 mm. (Note 5).
2. Notes
1. If more ice is used a portion remains unmelted after the diazotization is completed.
2. If a good separation has been made not more than 1–2 g. of iodobenzene is lost with the upper layer.
3. An appreciable amount of iodobenzene is retained by the solid calcium chloride. By treating the spent drying agent with water 8–12 g. of iodobenzene can be recovered.
4. The crude iodobenzene weighs 350–355 g. (80 per cent of the theoretical amount) and is pure enough for many purposes without redistillation.
5. If the distillation is carried too far, the distillate will be colored.
3. Discussion
The preparation of iodobenzene by iodination of benzene, with iodine and nitric acid, and a survey of preparative methods have been given in an earlier volume.1 The present procedure, based upon the method of Gattermann,2 gives a purer product.
This preparation is referenced from:

References and Notes
  1. Org. Syn. Coll. Vol. I, 1941, 323.
  2. Gattermann-Wieland, "Laboratory Methods of Organic Chemistry," p. 283. Translated from the twenty-fourth German edition by W. McCartney, The Macmillan Company, New York, 1937.

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

oxides of nitrogen

calcium chloride (10043-52-4)

sulfuric acid (7664-93-9)

hydrochloric acid (7647-01-0)

Benzene (71-43-2)

aniline (62-53-3)

sodium hydroxide (1310-73-2)

nitric acid (7697-37-2)

potassium iodide (7681-11-0)

sodium nitrite (7632-00-0)

nitrous acid (7782-77-6)

iodine (7553-56-2)

Benzene, iodo- (591-50-4)