Reactions of alpha -aminonitriles. VI. Reactions of aliphatic-substituted alpha -aminoacetonitriles with metallic sodium in toluene

Abstract

To 17.2 g. Na in 250 ml. PhMe 0.75 mole I in 250 ml. PhMe was added dropwise with slow shaking, and the mixt. shaken 4 hrs. at 120 Deg to give mixts. of II and III (R, R1, b.p. II, % yield II, b.p. III, and % yield III given): H, Me, b720 130-2 Deg, 43.3, b15 148 Deg, 21.8; H, Pr, b725 171-8 Deg, 42.1, b15 173-5 Deg, 21.2; Me, Me, b720 145-8 Deg, 51.9, b0.4 110-13 Deg, 7.8; Me, Et, b715 173-5 Deg, 54.3, b0.7 152 Deg, 7.2. The reaction of I (R = H, R1 = Pr) with Na also yielded 20 mole % piperidine and 10-15 mole % PrCHO. A mechanism is discussed in which I loses CN to form a carbonium ion, which dimerizes or disproportionates to give III and II, resp.