Kinetics and Mechanism of the Addition of Benzylamines to Ethyl-α-cyanocinnamates in Acetonitrile

Nucleophilic addition reactions of benzylamines (BA; ) to ethyl--cyanocinnamates (ECC;=C(CN)COOEt) have been investigated in acetonitrile at . The rate is first order with respect to BA and ECC. The rate is slower than that expected from the additive effect of or for the activating groups (CN and COOEt). Natural. bond orbital calculations show that the contribution of COOEt group may not be fully effective despite the coplanar molecular structure. The selectivity parameters including the cross-interaction constant ( = -0.22) indicate that the addition occurs in a single step. The kinetic isotope effects (=2.5-2.8) involving deuterated BA () nucleophiles and activation parameters () suggest a cyclic transition state in which N- and H- bonds are formed concurrently.

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