Addition of Amines to Conjugated Dienes

Primary amines and secondary amines added to cojugated dienes over solid base, catalysts form unsaturated secondary and tertiary amines, repectively. The general form of the reaction is given below. 

As homogeneous catalysts, alkali metals. Li —amide,and transition metal complexes such as Ni[P(OC2Hs)3]4, Ni acetylacetonate, PdBr2(Ph2PCH2PPh2), 

The heterogeneous catalysts active for addition reactions ture basic type catalysts such as a series of alkaline earth oxides, La203, Th02. Zirconium oxide, which is basic, however, is not active. 

The activity of each catalyst is dependent upon the pretreatment temperature. Table 4.33 summarizes the activities following pretreatment at optimum temperature for each catalyst. Calcium oxide shows markedly high activity. 

Ethylamine, piperidine, aniline, and trimethylamine are less reactive in the addition to 1,3-butadiene. Ethylamine and piperidine addition reactions proceed at 373 K and 453 K, respectively. Addition of aniline or trimethylamine does not take place at 473 K. 

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