Addition of ammonia and its substitution products

Ammonia and amines add to simple olefins only when catalysed and under energetic conditions. For example, jV-methylaniline is obtained in 80-90% yield from aniline and ethylene at 300°/200 atm in the presence of sodium.1 Rather high pressures and catalysts are also necessary for addition of amines to a C-C triple bond 2-4 however, the reaction often does not stop at simple vinylation but gives the Schiff base instead of the expected isomeric vinyl-amine.2-4 Tertiary amines can also be vinylated, as when neurine2 is obtained in good yield from a 2 1 mixture of acetylene and nitrogen at 60-70°/20 atm 5 

Reppe and co-workers, Ann. Chem., 596, 10 (1955), describe the technique for working with acetylene and the necessary protective measures. 

Acid amines can be prepared by addition of ammonia or an amine to ketenes amides of acetoacetic acid are accessible in high yields from diketene in this simple way.14,15 

TV-Halo amines add more easily than unsubstituted amines, and even to only slightly reactive double bonds naturally a halogen atom is introduced at the -position at the same time. W-Halo sulfonamides behave analogously, but iV-halogenated carboxamides react almost exclusively in a quite different manner. 

Diazoalkanes and azides add in some cases quite extraordinarily easily, particularly to activated double bonds. Nitrogen is often split off from the primary products, with formation of a C-C bond, sometimes in the cold, more often on heating. In many cases, however, such addition forms the most elegant route to N-heterocycles. 

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