• Bulletin of the Korean Chemical Society
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• v.8 no.3
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• pp.168-170
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• 1987

The reaction between 1-benzyl-3-carbamoyl-1,4-dihydropyridine (BNAH) 1 and various 1-arylpyridinium salts 2, and the reaction between 1-(4-methylphenyl)-1,4-dihydropyridine 4b and 1-aryl-3-carbamoylpyridinium (1-arylnicotinamide) salts 5 were carried out. The extents of reaction in equilibrium were estimated by nmr integration data. The equilibrium constants for the reactions, K, and the standard Gibbs free energy changes for the reduction of the pyridinium salts to the corresponding 1,4-dihydropyridines ${\Delta}G^{\circ}'$ were evaluated. The Hammett plot of log K for the reaction between 1 and 2, and ${\Delta}G^{\circ}'$ against ${\sigma}_p$ of the substituents in 1-aryl moiety shows linear correlation with the reaction constant ${\rho}$ of 9.4 (for log K vs ${\sigma}_p$) and -54.5 KJ/mole (for ${\Delta}G^{\circ}'$ vs ${\sigma}_p$). It was found that 1-aryl-1,4-dihydropyridines have much higher reducing power than the corresponding 1-aryl-1,4-dihydronicotinamides, and the power is affected greatly by the electron-withdrawing ability of the substituents in aryl group. The reactions were utilized for preparation of 1,4-dihydropyridines bearing highly electron-withdrawing groups such as 4-nitrophenyl and 2,4-dinitrophenyl, which could not be obtained by conventional dithionite reduction of the corresponding pyridinium salts due to the base-labile nature of the salts.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.19 no.8
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• pp.378-384
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• 2018

$C_9H_7NHCrO_3Cl$ was synthesized by reacting $C_9H_7NH$ with chromium (VI) trioxide. The structure of the product was characterized by FT-IR (Fourier transform infrared) spectroscopy and elemental analysis. The oxidation of benzyl alcohol by $C_9H_7NHCrO_3Cl$ in various solvents showed that the reactivity increased with increasing dielectric constant(${\varepsilon}$) in the following order: DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. The oxidation of alcohols was examined by $C_9H_7NHCrO_3Cl$ in DMF. As a result, $C_9H_7NHCrO_3Cl$ was found to be an efficient oxidizing agent that converts benzyl alcohol, allyl alcohol, primary alcohols, and secondary alcohols to the corresponding aldehydes or ketones (75%-95%). The selective oxidation of alcohols was also examined by $C_9H_7NHCrO_3Cl$ in DMF. $C_9H_7NHCrO_3Cl$ was the selective oxidizing agent of benzyl, allyl and primary alcohol in the presence of secondary ones. In the presence of DMF with an acidic catalyst, such as $H_2SO_4$, $C_9H_7NHCrO_3Cl$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, and $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.69 (308K). The observed experimental data were used to rationalize hydride ion transfer in the rate-determining step.

• Bulletin of the Korean Chemical Society
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• v.32 no.5
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• pp.1625-1629
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• 2011

Kinetic studies of the reactions of O,O-diphenyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at 55.0 $^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Bronsted [log $k_2$ vs $pK_a(X)$] plots for substituent X variations in the nucleophiles are biphasic concave downwards with a maximum point at X = H, and the unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are obtained for the strongly basic benzylamines. The sign of the cross-interaction constant (${\rho}_{XZ}$) is negative for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ value is observed with the weakly basic nucleophiles (${\rho}_{XZ}$ = -2.35) compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = -0.03). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a concerted $S_N2$ involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles. The unusual positive ${\rho}_X$ and negative ${\beta}_X$ values with the strongly basic benzylamines are rationalized by through-space interaction between the ${\pi}$-clouds of the electron-rich phenyl ring of benzylamine and the phenyl ring of the leaving group thiophenoxide.

• Bulletin of the Korean Chemical Society
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• v.29 no.4
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• pp.790-794
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• 2008

Nucleophilic addition reaction of benzenethiols (PhSH) to 1-(2-nitrovinyl) benzenes ($\beta$ NS) in the presence of triethylamine (TEA) has been studied in acetonitrile at 25 ${^{\circ}C}$. The rate is first order with respect to [PhSH], [TEA] and [$\beta$ NS]. The reaction is found to proceed with the formation of ion-pair between benzenethiol and TEA. A suitable mechanism with the formation of an adduct between ion-pair and substrate in a slow step followed by its rearrangement to 1,2-addition product in a fast step has been proposed and corresponding rate law derived. From the rate law, the rate constants for the interaction between ion-pair and $\beta$NS have been evaluated. Interestingly, in both para-substituted substrates and benzenethiols the rate increases with the electron-withdrawing power of the substituents. The positive sign of $\rho_x$ in benzenethiols has been explained. The magnitude of cross-interaction constant, $\rho_{xy}$ is small (0.08). The magnitude of the Hammett $\rho_x$ values is higher than that of the Bronsted, $\beta_x$ values for benzenethiols. The kinetic isotope effect, $k_H/k_D$, is found to be greater than unity. A suitable transition state with simultaneous formation of $C_\beta$ -H and $B_\alpha$ -S bonds involving the ion-pair and $\beta$NS in a single concerted step has been proposed to account for these observations.

• The Journal of the Convergence on Culture Technology
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• v.8 no.6
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• pp.927-933
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• 2022

We synthesized (C₁₀H₈N₂H)₂Cr₂O₇, The structure of the product was characterized with FT-IR(infrared) and elemental analysis. The oxidation of benzyl alcohol by (C₁₀H₈N₂H)₂Cr₂O₇ in organic solvents showed that the reactivity increased with the increase of the dielectric constant. The oxidation of alcohols was examined by (C₁₀H₈N₂H)₂Cr₂O₇ in DMF, acetone. As a resuit, (C₁₀H₈N₂H)₂Cr₂O₇ was found as efficicent oxidizing agent that converted benzyl alcohol, allyl alcohol, primary alcohol and secondary alcohols to the corresponding aldehydes or ketones(65%~95%). The selective oxidation of alcohols was also examined by (C₁₀H₈N₂H)₂Cr₂O₇ in DMF, acetone. (C₁₀H₈N₂H)₂Cr₂O₇ was selective oxidizing agent(15%~95%) of benzyl alcohol, allyl alcohol and primary alcohol in the presence of secondary ones. In the presence of DMF solvent with acidic catalyst such as H₂SO₄. (C₁₀H₈N₂H)₂Cr₂O₇ oxidized benzyl alcohol(H) and its derivatives. The Hammett reaction constant(ρ) was -0.69(308K). The observed experimental data were used to rationalize the hydride ion transfer in the rate determining step.

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3543-3548
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• 2010

A kinetic study on nucleophilic displacement reactions of 2-pyridyl X-substituted benzoates 1a-e with potassium ethoxide (EtOK) in anhydrous ethanol is reported. Plots of pseudo-first-order rate constants ($k_{obsd}$) vs. $[EtOK]_o$ exhibit upward curvature. The $k_{obsd}$ value at a fixed $[EtOK]_o$ decreases steeply upon addition of 18-crown-6-ether (18C6) to the reaction mixture up to [18C6]/$[EtOK]_o$ = 1 and then remains nearly constant thereafter. In contrast, $k_{obsd}$ increases sharply upon addition of LiSCN or KSCN. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ has revealed that ion-paired EtOK is more reactive than dissociated $EtO^-$, indicating that $K^+$ ion acts as a Lewis acid catalyst. Hammett plots for the reactions of 1a-e with dissociated $EtO^-$ and ion-paired EtOK result in excellent linear correlation with $\rho$ values of 3.01 and 2.67, respectively. The $k_{EtOK}/k_{EtO^-}$ ratio increases as the substituent X in the benzoyl moiety becomes a stronger electron-donating group. $K^+$ ion has been concluded to catalyze the current reaction by stabilizing the transition state through formation of a 6-membered cyclic complex.

• Bulletin of the Korean Chemical Society
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• v.30 no.9
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• pp.1939-1945
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• 2009

Kinetic investigations on the oxidation of pyrazine and four 2-substituted pyrazines viz., 2-methylpyrazine, 2-ethylpyrazine, 2-methoxypyrazine and 2-aminopyrazine by bromamine-B (BAB) to the respective N-oxides have been studied in HCl$O_4$ medium at 303 K. The reactions show identical kinetics being first-order each in $[BAB]_o\;and\;[pyrazine]_o$, and a fractional- order dependence on $[H^+]$. Effect of ionic strength of the medium and addition of benzenesulfonamide or halide ions showed no significant effect on the reaction rate. The dielectric effect is positive. The solvent isotope effect was studied using $D_2$O. The reaction has been studied at different temperatures and activation parameters for the composite reaction have been evaluated from the Arrhenius plots. The reaction showed 1:1 stoichiometry and the oxidation products of pyrazines were characterized as their respective N-oxides. Under comparable experimental conditions, the oxidation rate of pyrazines increased in the order: 2-aminopyrazine > 2-methoxypyrazine > 2-ethylpyrazine > 2-methylpyrazine > pyrazine. The rates correlate with the Hammett $\sigma$ relationship and the reaction constant $\rho$ was found to be -0.8, indicating that electron donating centres enhance the rate of reaction. An isokinetic temperature of $\beta$ = 333 K, indicated that the reaction was enthalpy controlled. A mechanism consistent with the experimental results has been proposed in which the rate determining step is the formation of an intermediate complex between the substrate and the diprotonated species of the oxidant. The related rate law in consistent with observed results has been deduced.

• Journal of the Korean Chemical Society
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• v.43 no.1
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• pp.85-91
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• 1999

The second order rate constants for the hydrolysis of substituted phenyl N,N-diethyl-P-benzylphosphonamidates (2,4-$(NO_2)_2$, 4-$NO_2$, 4-CN, 4-Cl, 4-H)in 20% dioxane-water (v/v) have been determined by UV/Vis spectrophotometric method at various temperatures. The activation parameters (Ea, ${\Delta}H^{\neq}$,${\Delta}S^{\neq}$) were calculated from the rate constants and the reaction constant ($\rho$) was also estimated by Hammett equation. The activation entropies of the title reactions show considerably negative values, this result is not consistent with a dissociative mechanism (EA) in which a positive or a slightly negative value of the entropy of activation should be expected. Further, kinetic evidence for an associative mechanism (AE) was obtained from the linear free energy relationship. By the results of kinetic study for the alkaline hydrolysis of substituted phenyl N,N-diethyl-P-benzylphosphonamidates, it may be concluded that these reactions proceed through an associative mechanism.