A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1932, 12, 26
DOI: 10.15227/orgsyn.012.0026
[Cyclohexane, 1,2-dibromo-]
Submitted by H. R. Snyder and L. A. Brooks.
Checked by Lee Irvin Smith, R. T. Arnold, and John Ryan.
1. Procedure
In a 2-l. three-necked, round-bottomed flask, fitted with a 500-cc. separatory funnel, a mechanical stirrer, and a thermometer, is placed a solution of 123 g. (1.5 moles) of cyclohexene (Note 1) in a mixture of 300 cc. of carbon tetrachloride and 15 cc. of absolute alcohol. The flask is surrounded by an ice-salt bath. The stirrer is started, and, when the temperature has reached −5°, a solution of 210 g. (67 cc., 1.3 moles) of bromine in 145 cc. of carbon tetrachloride is added from the separatory funnel at such a rate that the temperature of the reaction mixture does not exceed −1° (Note 2). The addition requires about three hours.
When the bromine has been added the contents of the flask are transferred directly to a 1-l. modified Claisen flask and the carbon tetrachloride and excess cyclohexene are distilled from a water bath (Note 3), (Note 4), and (Note 5). The water bath is replaced by an oil bath and the product distilled under reduced pressure. There is a small low-boiling fraction, and then pure dibromocyclohexane distils at 99–103°/16 mm. (108–112°/25 mm.). The yield is 303 g. (95 per cent of the theoretical amount) (Note 6) and (Note 7).
2. Notes
1. Cyclohexene boiling over a two-degree range is satisfactory for this preparation. Directions for preparing cyclohexene are given in Org. Syn. Coll. Vol. I, 1941, 183 and on p. 152 above.
2. Unless the temperature is controlled carefully, the yield is poor because of substitution reactions. Even at this low temperature some substitution occurs unless the excess of cyclohexene is used.
3. The three-necked flask may be rinsed with a little carbon tetrachloride.
4. The dibromide decomposes on continued exposure to the air and becomes very dark. Hence the product should be distilled at once.
5. The low-boiling distillate contains a trace of the dibromide as shown by the fact that it darkens on exposure to the air.
6. The product is stored best in sealed bottles with as little exposure to the air as possible.
7. A product which will not darken may be obtained by the following purification: The crude dibromide is shaken for five minutes with about one-third its volume of 20 per cent ethyl alcoholic potassium hydroxide. The mixture is diluted with its own volume of water and the organic layer is washed free of alkali, dried, and distilled. Material so treated will stay clear indefinitely. The loss in the purification is about 10 per cent. (Wm. Von Eggers Doering and Aldrich Durant, Jr., private communication.)
3. Discussion
1,2-Dibromocyclohexane has been prepared from cyclohexene by the addition of bromine in chloroform,1 carbon tetrachloride,2 ether,3 glacial acetic acid,4 aqueous sodium bromide,5 and in the absence of a solvent.6 The bromination in carbon tetrachloride containing a little alcohol is more satisfactory than the bromination in carbon tetrachloride which is described in an earlier volume.2
This preparation is referenced from:

References and Notes
  1. Baeyer, Ann. 278, 108 (1894); Hofmann and Damm, Mitt. schlesischen Kohlenforsch. Kaiser Wilhelm Ges. 2, 97 (1925) [C. A. 22, 1249 (1928)]; Rothstein, Ann. chim. (10) 14, 542 (1930).
  2. Coffey, Rec. trav. chim. 42, 398 (1923); Greengard, Org. Syn. 12, 27.
  3. Fortey, J. Chem. Soc. 73, 948 (1898).
  4. Harries and Splawa-Neyman, Ber. 42, 695 (1909).
  5. Markownikoff, Ann. 302, 29 (1898); Swarts, Bull. soc. chim. Belg. 46, 13 (1937):
  6. Truffault, Bull. soc. chim. (5) 1, 398 (1934).

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

ethyl alcoholic potassium hydroxide

alcohol (64-17-5)

acetic acid (64-19-7)

ether (60-29-7)

chloroform (67-66-3)

Cyclohexene (110-83-8)

bromine (7726-95-6)

sodium bromide (7647-15-6)

carbon tetrachloride (56-23-5)

Cyclohexane, 1,2-dibromo- (5401-62-7)