4,4'-Dichlorodibutyl ethe (CAS NO.: ), which is also known as Ether, bis(4-chlorobutyl), could be produced through the following synthetic routes.

In a 2-l. three-necked flask fitted with a mercury-sealed stirrer, a reflux condenser connected to a calcium chloride tube, and a thermometer is placed 360 g. (406 ml., 5 moles) of dry tetrahydrofuran. The flask is surrounded by an ice bath, stirring is started, and 256 g. (153 ml., 1.67 moles) of phosphorus oxychloride is added rapidly. The mixture is cooled to 10–15°, and 50 ml. of concentrated sulfuric acid (sp. gr. 1.84) is added during the course of 3–10 minutes at a rate that does not cause the temperature to rise above 40°. The ice bath is then removed and the mixture is heated cautiously over a low luminous flame until an exothermic reaction becomes evident at about 88–90°. By moderate cooling or warming as may be required the temperature is maintained at 90–100° until the exothermic reaction ceases, as indicated by the increased rate of heating required to maintain the reaction temperature, and thereafter for an additional 10 minutes. Six hundred milliliters of water is added, the mixture is heated under reflux for 30 minutes and then distilled through a downward condenser until the vapor temperature reaches 99–100°.

The dark reaction mixture is cooled to room temperature, transferred to a separatory funnel, and extracted with 225 ml. of ether. The ether extract is washed with four 100-ml. portions of water and dried over anhydrous sodium sulfate or magnesium sulfate. The mixture is filtered, the ether is removed by distillation, and the residual liquid is fractionated under reduced pressure from a modified Claisen flask. The yield of colorless 4,4'-dichlorodibutyl ether, b.p. 84–86°/0.5 mm. (116–118°/10 mm.), n_D25 1.4562, d₄25 1.0690, is 257–268 g. (52–54% based on tetrahydrofuran).

Notice: This preparation should be conducted in a good hood because some hydrogen chloride is evolved.