• Bulletin of the Korean Chemical Society
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• v.30 no.1
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• pp.253-256
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• 2009

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.749-752
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• 2009

• Bulletin of the Korean Chemical Society
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• v.27 no.1
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• pp.143-146
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• 2006

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1873-1876
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• 2006

• Bulletin of the Korean Chemical Society
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• v.29 no.6
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• pp.1195-1198
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• 2008

Kinetic studies of the additions of benzylamines to a noncyclic dicarbonyl group activated olefin, methyl $\alpha$-acetyl-$\beta$ -phenylacrylates (MAP), in acetonitrile at 30.0 ${^{\circ}C}$ are reported. The rates are lower than those for the cyclic dicarbonyl group activated olefins. The addition occurs in a single step with concurrent formation of the $C_\alpha$ -N and $C_\beta$ -H bonds through a four-center hydrogen bonded transition state. The kinetic isotope effects ($k_H/k_D$ > 1.0) measured with deuterated benzylamines ($XC_6H_4CH_2ND_2$) increase with a stronger electron acceptor substituent ($\delta\sigma$ X > 0) which is the same trend as those found for other dicarbonyl group activated series (1-4). The sign and magnitude of the cross-interaction constant, ρXY, is comparable to those for the normal bond formation processes in the $S_N2$ and addition reactions. The relatively low ${\Delta}H^\neq$ and large negative ${\Delta}S^\neq$ values are also consistent with the mechanism proposed.

• Bulletin of the Korean Chemical Society
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• v.25 no.7
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• pp.1041-1045
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• 2004

Kinetic studies of the pyridinolysis $(XC_5H_4N)$ of aryl dithiomethylacetates $(CH_3CH_2C(=S)SC_6H_4Z,\;1)$ are carried out in acetonitrile at $60.0^{\circ}C$. A biphasic Bronsted plot is obtained with a change in slope from a large $({\beta}X\;{\cong}\;0.8)$ to a small $({\beta}X\;{\cong}\;0.2)$ value at $pK_a^{\circ}$ = 5.2, which is attributed to a change in the rate limiting step from breakdown to formation of a zwitterionic tetrahedral intermediate, $T^{\pm}$, in reaction path as the basicity of the pyridine nucleophile increases. This mechanism is supported by the change of the cross-interaction constant ${\rho}xz$ from a large positive ( ${\rho}xz$ = +1.36) for the weakly basic pyridines to a small negative ( ${\rho}_xz$ = -0.22) value for the strongly basic pyridines. The magnitudes of ${\rho}z$ and activation parameters are also consistent with the proposed mechanism.

• Bulletin of the Korean Chemical Society
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• v.24 no.8
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• pp.1135-1140
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• 2003

The kinetics and mechanism of the pyridinolysis $(XC_5H_4N)$ of Y-aryl phenyl isothiocyanophosphates (1;$(YC_6H_4O)\;(C_6H_5O)$P(=O)NCS) are investigated in acetonitrile at 55.0 ℃. The Hammett plots for substituent (Y) variations in the substrate (log k₂ vs σY) exhibit a convex upward biphasic type with breaks at Y = H. For electron-donating Y groups the Hammett coefficients, ρY, are positive and cross-interaction constant ρXY is negative, while those for electron-withdrawing Y groups ρY values are negative with a positive ρXY. These results are interpreted to indicate mechanistic change at the breakpoint (σY = 0) from a concerted to a stepwise mechanism with rate-limiting expulsion of the $^-NCS$ group from a trigonal bipyramidal pentacoordinated (TBP-5C) intermediate. Biphasic plots of log k₂ vs σX or $pK_a$(X) with steeper slopes for the more basic nucleophiles are obtained suggesting an equatorial nucleophilic attack in contrast to an apical attack for the less basic nucleophiles with smaller magnitude of ρX or βx.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.221-224
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• 2002

Nucleophilic addition reactions of benzylamines (BA; $XC_6H_4CH_2NH_2$) to ethyl-${\alpha}$-cyanocinnamates (ECC;$YC_6H_4CH$=C(CN)COOEt) have been investigated in acetonitrile at $30.0^{\circ}C$. The rate is first order with respect to BA and ECC. The rate is slower than that expected from the additive effect of ${\sigma}^-$ or $R^-$ for the activating groups (CN and COOEt). Natural. bond orbital ${\pi}^{\ast}_{c=c}$ 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 (${\rho}_{xy}$ = -0.22) indicate that the addition occurs in a single step. The kinetic isotope effects ($k_H/k_D$=2.5-2.8) involving deuterated BA ($XC_6H_4CH_2ND_2$) nucleophiles and activation parameters (${\Delta}H^{\neq}=4{\sim}6\;kcal\;mol^{-1};{\Delta}S^{\neq}=-45{\sim}-52\;e.u.$) suggest a cyclic transition state in which N-$C_{\alpha}$ and H-$C_{\beta}$ bonds are formed concurrently.

• Bulletin of the Korean Chemical Society
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• v.24 no.2
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• pp.193-196
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• 2003

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.

• Bulletin of the Korean Chemical Society
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• v.23 no.10
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• pp.1459-1462
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• 2002

The kinetics of the addition of X-substituted benzylamines (BA) to Y-substituted Benzylideneacetylacetones (BAA) have been investigated in acetonitrile at $25.0^{\circ}C$. The reaction is studied under pseudo-first-order conditions by keeping a large excess of BA over BAA. The addition of BA to BAA occurs in a single step in which the addition of BA to $C_\alpha$ of BAA and proton transfer from BA to $C_\beta$ of BAA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($p_X$) and Bronsted ($\beta_x$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the cross-interaction constant, $p_{XY}$ (= -0.49), is comparatible to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($K_H/K_D$ > 1.0) and relatively low $\Delta$H^{${\neq}$}$ and large negative $\Delta$S^{${\neq}$}$ values are also consistent with the mechanism proposed.