Dichlorodibutyl Ether

Checked by Arthur C. Cope, Malcolm Chamberlain, and Mark R. Kinter. 

Caution This preparation should be conducted in a good hood 

In a 2-1. three-necked flask fitted with a mercury-sealed stirrer (Note 1), a reflux condenser connected to a calcium chloride tube, and a thermometer is placed 360 g. (406 ml., 5 moles) of dry tetrahydrofuran (Note 2). 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° (Note 3). 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 (Note 4). Six hundred milliliters of water is added, the mixture is heated under reflux for 30 minutes and then distilled through a downward condenser until t lie vapor temperature reaches 99-100° (Note 5). 

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 47-dichlorodibutyl ether, b.p. 84-86 70.5 mm. (116-118710 mm.), n 1.4562, df 1.0690, is 257-268 g. (52-54% based on tetrahydrofuran) (Note 6). 

---

Dichloro-2-aminobenzoic acid, 31,96 J>-Di-(chloro-ferf-butyl)-benzene, 32, 91 4,4 -Dichlorodibutyl ether, 30, 27... 

The same yield of 4,4 -dichlorodibutyl ether was obtained from redistilled tetrahydrofuran dried over sodium or a good-quality commercial grade obtained from the Electrochemicals Department of the E. I. du Pont de Nemours and Company and dried over Drierite. 

Dichlorodibutyl ether, 27 Diels-Alder reaction of butadiene with maleic anhydride, 93 Diene synthesis of cis-A -tetrahydro-phthalic anhydride, 93 Diethyl benzalmalonate, 84 Diethyl carbonate, 44 Diethyl fumarate, 46 Diethyl cis-HEXAiiYDROPiiTHALATE, 29 Diethyl malonate, 70 Diethyl o-nitrobenzoylmalonatc, 71 Diethyl sodium phthalimidomalonate, 7... 

The procedure described is based on one reported by Alexander and Schniepp. 4,4 -Dichlorodibutyl ether has also been prepared by the action of thionyl chloride on tetrahydrofuran and by heating 4-chlorobutanol and hydrogen chloride under pressure. ... 

Bis(4-chlorobutyl) ether [4,4 -dichlorodibutyl ether 1,1 -oxy di-4-chlorobutane oxybis(4-chlorobutane)] [6334-96-9] C8H16CI2O 199.14 CI-CH2-CH2-CH2-CH2- O-CH2-CH2-CH2-CH2-CI Low oral toxicity in mice target organs — central nervous system, liver, and gastrointestinal tract caused muscle contraction and ulceration LD50 oral (mice) 1250 mg/kg Noncombustible liquid... 

---