A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1928, 8, 46
DOI: 10.15227/orgsyn.008.0046
[Benzene, 1-bromo-3-nitro-]
Submitted by John R. Johnson and C. G. Gauerke.
Checked by Frank C. Whitmore and T. Otterbacher.
1. Procedure
In a 3-l. three-necked, round-bottomed flask, provided with an efficient reflux condenser bearing an outlet tube held above a surface of water, a 100-cc. separatory funnel, and a mercury-sealed mechanical stirrer (Note 1), is placed 270 g. (2.2 moles) of freshly distilled dry nitrobenzene (Note 2). The joints in the apparatus are made of asbestos paper covered with water glass (see Note 5, p. 19). The flask is heated in an oil bath maintained at 135–145°, and 26 g. of iron powder and 562 g. (180 cc., 3.5 moles) of dry bromine (Note 3) are added in the following manner: Eight grams of iron powder ("ferrum reductum") (Note 4) is added through the side neck to the stirred nitrobenzene. From the separatory funnel 60 cc. of bromine is added at such a rate that the bromine vapors do not traverse the condenser. This addition requires about one hour, and the mixture is stirred and heated for another hour before the addition of a second portion of iron and bromine. Two portions, each of 8 g. of iron powder and 60 cc. of bromine, are added under the same conditions as the first addition, and the mixture is stirred and heated for one hour between the completion of one addition and the beginning of another. The evolution of hydrogen bromide slackens considerably toward the last of the heating, and there is practically no more bromine vapor in the condenser. A final addition of 2 g. of iron powder is made, and the heating continued for one hour longer.
The reaction product, which is a dark reddish-brown liquid, is poured or siphoned (Note 5) into 1.5 l. of water to which 50 cc. of a saturated solution of sodium bisulfite has been added (Note 6). The mixture is distilled with steam (p. 479) and the first portion of the distillate is collected separately to remove a small amount of unchanged nitrobenzene. It is necessary to collect about 12 l. of distillate in order to obtain all the m-bromonitrobenzene. The yellow crystalline solid is filtered with suction and pressed well on the funnel to remove water and traces of nitrobenzene. The yield of crude product varies from 270 to 340 g. (60–75 per cent of the theoretical amount). It melts at 51.5–52° and boils at 117–118°/9 mm. This product is satisfactory for most purposes. If a purer material is desired, the crude m-bromonitrobenzene may be distilled under reduced pressure. The recovery on purification is about 85 per cent. Brühl recorded the b.p. as 138°/18 mm. and the m.p. as 56° for pure m-bromonitrobenzene.1
2. Notes
1. With small amounts, up to 90 g. of nitrobenzene, mechanical stirring is not essential, and occasional shaking is sufficient.
2. The nitrobenzene is dried by distillation under atmospheric or reduced pressure, by rejecting the first 5 per cent of the distillate.
3. The bromine is dried by shaking with an equal volume of concentrated sulfuric acid and separating.
4. A number of other forms of iron were used, but none gave as good results as the "ferrum reductum."
5. If a series of successive runs is to be made, it is convenient to siphon the reaction product, and carry out a second preparation in the same apparatus without dismantling it.
6. The sodium bisulfite is added to remove any free bromine. A large excess should not be used as secondary reactions may occur during the steam distillation.
3. Discussion
m-Bromonitrobenzene can be obtained through m-nitrobenzenediazonium salts2 and by elimination of the amino group from 4-bromo-2-nitroaniline.3 It has been prepared by the bromination of nitrobenzene in the presence of various catalysts.4 The procedure given is adapted from that described by Wheeler and McFarland.5

References and Notes
  1. Brühl, Z. physik. Chem. 22, 379 (1897).
  2. Griess, Phil. Trans. Roy. Soc. London 154, III, 711 (1864); Jahresber. 457 (1866); Fittig and Mager, Ber. 8, 364 (1875).
  3. Wurster, Ber. 6, 1543 (1873); Wurster and Grubenmann, Ber. 7, 416 (1874).
  4. Scheufelen, Ann. 231, 165 (1885).
  5. Wheeler and McFarland, Am. Chem. J. 19, 366 (1897).

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

nitrobenzenediazonium salts

sulfuric acid (7664-93-9)

iron (7439-89-6)

hydrogen bromide (10035-10-6)

bromine (7726-95-6)

sodium bisulfite (7631-90-5)

Nitrobenzene (98-95-3)

Benzene, 1-bromo-3-nitro-,
m-Bromonitrobenzene (585-79-5)

Bromonitrobenzene (577-19-5)

4-bromo-2-nitroaniline (875-51-4)