A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1923, 3, 79
DOI: 10.15227/orgsyn.003.0079
[Benzene, 1-chloro-3-nitro-]
Submitted by W. W. Hartman and M. R. Brethen.
Checked by C. S. Marvel and C. R. Noller.
1. Procedure
To a solution of 1200 g. (4.8 moles) of crystallized copper sulfate and 400 g. (6.9 moles) of sodium chloride in 4 l. of water at 60–70° is added a concentrated solution of 200 g. (1.7–1.8 moles) of (90–95 per cent) sodium bisulfite (prepared if desired by saturating a solution of 100 g. of sodium carbonate with sulfur dioxide). The white precipitate of cuprous chloride is filtered off, sucked dry as rapidly as possible, and suspended in a mixture of 2 l. of water and 1.5 l. of concentrated hydrochloric acid (sp. gr. 1.19) (Note 1).
In the meantime, 552 g. (4 moles) of good commercial m-nitroaniline, melting at 110° or above (Note 2), is dissolved in a mixture of 500 cc. of hydrochloric acid (sp. gr. 1.19) and 1 l. of hot water; 1100 cc. of hydrochloric acid (sp. gr. 1.19) is then added, and the solution is cooled rapidly, with stirring. It is then surrounded with a freezing mixture, and diazotized at a temperature below 1° by adding, with constant stirring, a solution of 288 g. (4 moles) of technical (95 per cent) sodium nitrite in 700 cc. of water, care being taken to avoid adding an excess over that necessary to produce a distinct reaction with starch-iodide paper (p. 49). This point is reached when all but about 25 cc. of the nitrite solution has been added; the addition requires about one and one-half hours. The cold solution is now filtered in order to remove some amorphous insoluble matter; this solid, when dry, weighs 50–55 g.
The clear filtrate, which has only a pale yellow color, is now run, with stirring, into the cuprous chloride solution in a 12-l. flask, while the temperature is kept at 25–30° (Note 3). A somewhat sticky precipitate first forms, which later becomes crystalline; nitrogen is evolved in a continuous stream. The addition requires about thirty minutes. The mixture is then warmed on a steam bath under an efficient reflux condenser until the evolution of nitrogen ceases. It is then distilled in a current of steam (using the apparatus described on p. 479) until no more chloronitrobenzene passed over; 9–10 l. of distillate collects during this process (Note 4). When quite cold, the water is decanted off, and the solid shaken with 1–2 l. of 1 per cent sodium hydroxide solution at 50°. The mixture is again allowed to cool, and the light yellow alkaline solution is decanted from the solid product, which is then collected on a filter, washed with a little cold water, dried, and distilled under reduced pressure. It boils completely at 116–117°/12 mm. or 124–125°/18 mm., and the distillate solidifies to a pale yellow solid which melts at 44–45° and weighs 430–450 g. (68–71 per cent of the theoretical amount).
2. Notes
1. It is more convenient to prepare cuprous chloride by reducing copper sulfate with sodium bisulfite than by the action of copper upon cupric chloride. It is well to test a sample of the filtrate with sodium bisulfite solution; no further cuprous chloride should separate.
One mole of cuprous chloride should be used with one mole of diazonium salt. If less cuprous chloride is used the yield is decreased.
2. The yield will, of course, depend upon the quality of the nitroaniline. The pure amine should yield none of the insoluble substance on diazotization, but the cost of purification would be prohibitive. It may be noted that if the weight of the insoluble residue be deducted, the yield amounts to 75–78 per cent of the theoretical amount.
3. It is important that the temperature should be held at 25–30° during the addition of the diazonium chloride to the cuprous chloride solution. At lower temperatures the decomposition of the unstable additive compound proceeds too slowly, and would cause too violent an evolution of nitrogen on warming; at higher temperatures the formation of tarry by-product increases.
4. If desired, the steam distillation may be omitted, since the proportion of non-volatile resinous impurities is very low. In this case the reaction mixture is allowed to cool, and the watery solution is decanted; the residue is then dissolved in 1–2 l. of benzene, and the benzene solution washed with water and with dilute alkali, after which the solvent is removed by distillation on the steam bath and the residue distilled under reduced pressure. The yield and purity of the final product are equally satisfactory.
An iron condenser should not be used in the steam distillation of the crude m-chloronitrobenzene, as some reduction takes place and the yield is lowered by 10 to 15 per cent. The product is also deeply colored.
3. Discussion
m-Chloronitrobenzene can be prepared by the chlorination of nitrobenzene with the use of a catalyst such as iodine,1 ferric chloride,2 antimony trichloride3 or iron and iodine;4 and from m-nitroaniline by diazotization.5

References and Notes
  1. Laubenheimer, Ber. 7, 1765 (1874).
  2. Varnholt, J. prakt. Chem. (2) 36, 25 (1887).
  3. Beilstein and Kurbatov, Ann. 182, 102 (1876).
  4. Fierz-David, Naturwissenschaften, 17, 13 (1929).
  5. Griess, Jahresber. 423 (1863) and 457 (1866); Hollemann and Van Der Linden, Rec. trav. chim. 30, 317 (1911); Kohman, J. Phys. Chem. 29, 1052 (1925).

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

diazonium chloride

hydrochloric acid (7647-01-0)

Benzene (71-43-2)

sodium hydroxide (1310-73-2)

iron (7439-89-6)

sodium chloride (7647-14-5)

sodium carbonate (497-19-8)

sulfur dioxide (7446-09-5)

nitrogen (7727-37-9)

copper sulfate (7758-98-7)

sodium nitrite (7632-00-0)

nitrite (14797-65-0)

sodium bisulfite (7631-90-5)

copper (7440-50-8)

iodine (7553-56-2)

Nitrobenzene (98-95-3)

Benzene, 1-chloro-3-nitro-,
m-Chloronitrobenzene (121-73-3)

cuprous chloride (7758-89-6)

chloronitrobenzene (88-73-3)

cupric chloride (7447-39-4)


ferric chloride (7705-08-0)

antimony trichloride (7647-18-9)

m-nitroaniline (99-09-2)