Synthesis of m-nitrochlorobenzene

Prepration of m-nitrochlorobenzene

Prepration of m-nitrochlorobenzene

Prepration of m-nitrochlorobenzene

Chlorination of nitrobenzene in the laboratory requires very careful operation and succeeds only if the reaction is carried out in the complete absence of moisture. Even traces of water prevent the chlorination or retard it excessively. It is essential, therefore, that the apparatus and the starting materials be dried thoroughly.
Anhydrous ferric chloride is the most satisfactory chlorine carrier. The commercial material is heated under reduced pressure in a round-bottomed flask through which a gentle stream of dry chlorine or hydrogen chloride is drawn. When the material begins to sublime, it is transferred to a bottle with a tight glass stopper.
The nitrobenzene is dried by heating for several hours in a round-bottomed flask at 80-100°C. while a stream of dry air is drawn through it by means of a wide capillary tube.
The apparatus for the chlorination is shown below:

A glass apparatus for the preparation of m-nitrochlorobenzene

A glass apparatus for the preparation of m-nitrochlorobenzene

A batch of 246 grams of nitrobenzene is used for chlorination. The reaction vessel should be arranged so that it can be heated easily, preferably in a water bath, and also cooled if necessary. The hydrogen chloride generated is passed through a calcium chloride drying tower and then absorbed with sodium hydroxide solution. 5 grams of the prepared ferric chloride suffices as the carrier. The reaction temperature should be kept between 40 and 45°C; larger amounts of by-products are formed at higher temperatures. The rate of chlorine absorption is much lower and at least 6 hours being required for the completion of the reaction. The progress of the reaction is followed by weighing the reaction flask, and the chlorination is continued until the weight has increased 85 grams. Because of the appreciable solubility of chlorine and hydrogen chloride in the reaction mixture, this weight increase corresponds to about 2 moles of chlorine actually reacted.

The chlorine stream is interrupted, and the reaction mixture is allowed to stand for a short time, then it is poured into a separatory funnel and washed thoroughly with hydrochloric acid, soda solution, and water. If part of the mixture has not already precipitated as a white crystalline solid, the mixture is transferred to a beaker until part of it solidifies, then it is filtered, cooled to about 10°, and centrifuged. About 95 grams of practically pure m-nitrochlorobenzene is obtained. The filtrate and the liquid from the centrifuge are combined and subjected to fractional distillation in vacuo. For this purpose, a column should be used which is about 80 cm. in length and provided with a partial condenser. Approximately the following fractions are collected:

(1) About 40 grams of liquid boiling at 85-106° at 9 mm. This fraction consists of nitrobenzene and some chloronitrobenzene.
(2) About 130 grams of solidifying material, boiling at 106-108° at 9 mm. This material gives on cooling and centrifuging about 100 grams of pure m-chloronitrobenzene. The liquid residue from the centrifuge yields only traces of chloronitrobenzene on redistillation and consists largely of a mixture of by-products (3,6-dichloronitrobenzene, p-chloronitrobenzene, o-chloronitrobenzene, etc.).
(3) Material boiling higher than 108°, and the residue. This fraction consists of the by-products mentioned. Sometimes so much hexachlorobenzene is present that it separates after long standing.

The yield of m-chloronitrobenzene is about 60%, or 75% allowing for the recovered nitrobenzene. The pure product boils at 107° at 9 mm. and melts at 44.5°C.

The fundamental processes of dye chemistry, by H. E. Fierz-David, 116-117, 1949





InChI Key


Canonical SMILES


MeSH Synonyms

1-chloronitrobenzene, 3-chloronitrobenzene, 5-chloronitrobenzene, chloronitrobenzene, terrafun

Depositor-Supplied Synonyms

1-Chloro-3-nitrobenzene, 121-73-3, m-Chloronitrobenzene, 3-Chloronitrobenzene, m-Nitrochlorobenzene, 3-Nitrochlorobenzene, BENZENE, 1-CHLORO-3-NITRO-, Chloro-m-nitrobenzene, 3-Chloro-1-nitrobenzene, Metachloronitrobenzene, 1-Chloro-3-nitro-benzene, 1-Chloronitrobenzene, NSC 5502, 1-Nitro-3-chlorobenzene, CCRIS 3094, CHEBI:82420, HSDB 1323, KMAQZIILEGKYQZ-UHFFFAOYSA-N, EINECS 204-496-1, AI3-15386, DSSTox_CID_1971, DSSTox_RID_76434, DSSTox_GSID_21971, CAS-121-73-3, 3-chloro-nitro-benzene, ACMC-209aey, AC1Q5APH, Nitrochlorobenzene, meta-, WLN: WNR CG, UNII-8XSA3GF8O1, AC1L1R3V, 8XSA3GF8O1, ghl.PD_Mitscher_leg0.940, KSC490M5T, SCHEMBL249999, 218758_ALDRICH, 45957_RIEDEL, CHEMBL166812, 25480_FLUKA, 45957_FLUKA, CTK3J0659, NSC5502, MolPort-001-779-788, LTBB002345, NSC-5502, ZINC1686983, Tox21_201330, Tox21_302825, ANW-17768, AR-1J6798, LS-653, MFCD00007202, ZINC01686983, AKOS000120747, Chloronitrobenzenes meta or para, solid, CS20664, MCULE-3444165814, MP-2187, RP22134, RTR-032512, TRA0061725, NCGC00091171-01, NCGC00091171-02, NCGC00256340-01, NCGC00258882-01, AJ-29867, AK116919, AN-43404, CJ-06385, CJ-27872, KB-78288, OR034392, ST2408748, TL8000580, TR-032512, C19364, 3B4-1310, S01-0564, Chloronitrobenzenes meta or para, solid [UN1578] [Poison], Chloronitrobenzenes meta or para, solid [UN1578] [Poison], InChI=1/C6H4ClNO2/c7-5-2-1-3-6(4-5)8(9)10/h1-4

Removed Synonyms

Chloronitrobenzene, Benzene, chloronitro-, Nitrochlorobenzene, solid, C6H4ClNO2, UN 1578 (Related), CID8489, UN1578, c0221, 123-67-1, 25167-93-5

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