Preparation of 1-bromohexane (n-bromohexane)
With cooling, 1 mole of the 1-hexyl alcohol is treated first with 0.5 mole of concentrated sulfuric acid and then with 1.25 mole of hydrogen bromide (in the form of the 48%, constant-boiling, acid), and the obtained mixture is boiled for 6 hours under reflux. Then it is steam-distilled and the 1-bromohexane is separated off in the separating funnel. The crude 1-bromohexane is twice shaken carefully with about one-fifth of its volume of cold concentrated sulfuric acid or the same volume of concentrated hydrochloric acid in the separating funnel to dissolve the dihexyl ether produced as a by-product. The crude 1-bromohexane is washed with water then it is freed from acid with sodium bicarbonate solution, washed again with water, dried over calcium chloride, and distilled through a 20-cm Vigreux column. The yield of 1-bromohexane is 80%, n20/D 1.448; mp.p −85 °C; b.p. 154-158 °C; d=1.176 g/mL at 25 °C.
Organicum. Practical Handbook of Organic Chemistry, by Heinz Becker, Werner Berger and Günter Domschke, Addison-Wesley Pub. Co, 195-196, (1973)