Trichloroethyl alcohol (CAS NO.: ) could be produced through the following synthetic routes.

In a 2-l. three-necked flask immersed in an oil bath are placed 250 g. (1.7 moles) of anhydrous chloral, 650 cc. of anhydrous alcohol, and 75 g. (0.46 mole) of pure aluminum ethoxide. An efficient fractionating column is attached to the flask through a cork in the central neck, and through one of the side necks is passed a tube leading to the bottom of the flask for the introduction of dry nitrogen. The remaining neck is tightly stoppered. It is used to withdraw portions of liquid for testing.

To the outlet of the column is attached a U-tube and a Peligot tube each of about 100-cc. capacity. The U-tube is immersed in a freezing mixture, and the Peligot tube is filled with saturated sodium bisulfite solution. The oil bath is then heated to 135° and a slow current of gas is admitted. The mixture boils vigorously, but the alcohol is returned by the refluxing device whereas the acetaldehyde formed by the reaction is allowed to pass through and is caught in the freezing mixture and the Peligot tube.

The end of the reaction is easily determined by removing a few drops of the reaction mixture and treating with water in a test tube. After the aluminum hydroxide settles, the clear liquid is decanted and a few drops of yellow ammonium sulfide are added to it. So long as chloral is present, even in traces, a dark brown coloration will be produced on heating to incipient boiling. If the liquid collecting in the U-tube is removed every few hours, the completion of the reaction will be readily noticed by the diminishing quantity of acetaldehyde coming over. After twenty-three or twenty-four hours of heating (over a period of two or three days) the reaction is complete. The temperature of the bath is then allowed to fall to 120° and the alcohol is distilled through an ordinary condenser which replaces the fractionating column. When the residue of aluminum trichloroethoxide is nearly dry, the flask is removed from the oil bath and the solid is treated with 250 cc. of 20 per cent sulfuric acid and stirred thoroughly to ensure complete decomposition.

The mixture is then subjected to steam distillation until no more trichloroethyl alcohol passes over. About 4 l. of distillate is obtained. The oil is separated from the aqueous layer, which is saturated with sodium sulfate and extracted with three 200-cc. portions of ether. The ether solution is added to the main portion of the alcohol, and the whole is dried over anhydrous sodium sulfate.

The ether is removed by distillation and the product distilled under reduced pressure. There is obtained 215 g. (84 per cent of the theoretical amount) of trichloroethyl alcohol boiling at 94–97°/125 mm. and melting at 16–17°. A purer compound can be obtained by refractionating under reduced pressure and pressing the crystals on a cooled porous plate. Pure trichloroethyl alcohol has a melting point of 19°.