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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 27, Number 5
BKCSDE 27(5)
May 20, 2006 

Kinetic and Mechanism of the Addition of Benzylamines to α-Phenyl-β-thiophenylacrylonitriles in Acetonitrile
Jaeyoung Hwang, Kiyull Yang, In Sun Koo*, Dae Dong Sung, Ikchoon Lee
Nucleophilic addition reaction, Cross-interaction constant, Kinetic isotope effects, Four-center cyclic transition state
Nucleophilic addition reactions of p-substitutedbenzylamines (XC6H4CH2NH2) to α-phenyl-β-thiophenylacrylonitriles (YC4SH2CH=C(CN)C6H4Y') have been studied in acetonitrile at 25.0, 30.0, and 35.0 oC. The reactions take place in single step in which the Cβ -N bond formation and proton transfer to Cα of α-phenyl-β-thiophenylacrylonitriles occur concurrently with four-membered cyclic transition structure. These mechanistic conclusions are drawn based on (i) the large negative ρX and large positive ρY' values and also large magnitude of ρX, (ii) the negative sign and large magnitude of the cross-interaction constants (ρXY), (iii) the normal kinetic isotope effects (kH/kD > 1.0), and (iv) relatively low ΔH and large negative ΔS values.
733 - 738
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