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http://dx.doi.org/10.5012/bkcs.2003.24.2.193

Kinetics and Mechanism of the Addition of Benzylamines to Benzylidene Meldrum's Acids in Acetonitrile  

Oh, Hyuck-Keun (Department of Chemistry, Chonbuk National University)
Kim, Tae-Soo (Department of Chemistry, Chonbuk National University)
Lee, Hai-Whang (Department of Chemistry, Inha University)
Lee, Ik-Choon (Department of Chemistry, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.24, no.2, 2003 , pp. 193-196 More about this Journal
Abstract
Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)$ to benzylidene Meldrum's acids (BMA; $YC_6H_4CH=C(COO)_2C(CH_3)_2$) have been investigated in acetonitrile at 20.0 ℃. The rates of addition are greatly enhanced due to the abnormally high acidity of Meldrum's acid. The magnitudes of the Hammett $({\rho}_X\;and\;{\rho}_Y)$ and Bronsted $({\rho}_X$)$ coefficients are rather small suggesting an early transition state. The sign and magnitude of the cross-interaction constant, ${\rho}_{XY}$ (= -0.33), and kinetic isotope effects $(k_H/k_D\;{\stackrel}{~}{=}\;1.5-1.7)$ involving deuterated benzylamine nucleophilies $(XC_6H_4CH_2ND_2)$ are indicative of hydrogen-bonded cyclic transition state. The activation parameters, ${\Delta}H^{\neq}\;{\stackrel}{~}{=}\;4\;kcal\;mol^{-1}\;and\;{\Delta}S^{\neq}\;{\stackrel}{~}{=}\;-37\;e.u.$, are also in line with the proposed mechanism.
Keywords
Benzylidene Meldrum's acid; Nucleophilic addition reaction; Cross-interaction constant;
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