RESEARCHES ON AMINES. V. THE STRUCTURE OF VITIATINE. SYNTHESIS OF METHYLETHYLENEDIAMINE.1
Treat B. Johnson, George C. Bailey
Journal of the American Chemical Society
Only a little nitrile was obtained. In Expt. 2 the lower layer of the distillate was passed through the apparatus again, but only a small additional amount of nitrile was produced. It appears from Table I1 that most of the nitrile is found in the upper layer and, when 1007~ acid is used, a good yield of the nitrile is obtained even when the lower layer is discarded. As we would expect, in the experiments with weaker acid, particularly the 70% acid, a larger amount, in some cases, half or more
... the nitrile, is found in the lower layer. I t is intended to continue this work, particularly with the study of the formation of other nitriles. Summary. I . It is found that acetic acid vapor, mixed with a moderate excess of ammonia and passed over alumina or thoria at 5 0 0°, gives a large yield, up to 85%, of acetonitrile. 2 . This reaction does not take place in case the catalyst is omitted. 3. The yield depends on the activity of the catalyst and may vary greatly for what appear to be trifling differences in the method of preparation of the catalyst. 4. So far as the present work goes, alumina appears to be the best catalyst and about 500 O the best working temperature. 5 . This method of preparation of acetonitrile is a continuous process requiring very little attention, and is adapted to use for the preparation of large quantities. The only compound conforming in constitution to the expression C6HI4N6, that is recorded in Richter's Lexikon der Kohlenstoffverbindungen is the base Vitiatine whose structure has never been established. This interesting substance was isolated by Kutscher2 from beef extract by precipitation in the form qf its gold salt, which gave analytical values agreeing with that calculated for C~H I~N~.~H C I .~A U C I~. Later, during a careful investigation of the nature of the toxic bases in urine, Kutschers identified the same amine and ascribed its origin, in this case to the metab-This paper was constructed from a Dissertation presented by Mr. George Corbin Bailey to the Faculty of the Graduate School of Yale University, 1916, in candidacy for the Degree of Doctor of Philosophy. a 2. physiol. Chem., 51, 457 (1907). Zentr. Physiol., 21, 33 (1907).