Preparation of Diethylamine from Ethanol

Preparation of Diethylamine from Ethanol by Robert Bottoms Louisville, Kentucky June 18,1935 

The reaction between the alcohol and the ammonium chloride or other halide is preferably carried out with proportions about those which are necessary to form the secondary amine, since the secondary amine is the most desirable commercially... 

The reaction mixture is preferably placed in an autoclave or closed reaction vessel capable of withstanding high pressure and capable of enabling a relatively high temperature being applied, as for example, substantially above 200° and, if desired, up to 400° C, with an optimum range between 275° and 325°. 

The alkyl amines as prepared are usually in the form of their hydrochlorides or other hydrohalides, and consist of a mixture of primary, secondary and tertiary amines... I have disclosed methods (see below) by which the primary, secondary and tertiary amines may be separated from each other. 

920 grams (20 moles) ethyl alcohol, 535 grams (10 moles) ammonium chloride, 500 cc. water and 5 grams ferric chloride are placed in an autoclave and heated to 275°-280° C for 2 hours. The autoclave is then cooled, and the reaction mixture neutralized and made alkaline by adding a 50% water solution of 1,000 grams sodium hydroxide. The excess alkali is not essential, but serves to salt out the free amine which is separated and distilled. Diethylamine in better than 80% sdeld results. Source Bottoms 1937 

---