• Journal of the Korean Chemical Society
• /
• v.26 no.5
• /
• pp.333-339
• /
• 1982

Substituent effects of substrate and leaving group for the reaction of substituted ${\beta}$-phenylethyl arenesulfonates with pyridine were determined conductometrically in acetonitrile at 50∼70$^{\circ}$C. The substituent effect in substrate is not so significant than expected, but still the electron donating substituent shows the slight acceleration to give a small negative ${\rho}$ value and Hammett plots show slight curvature on the acting substituents, even though it is not so remarkable than that of benzyl system. These results represent a little bit the favorable bond breaking at the transition state by the electron donating substituents. The effects of leaving group in the arenesulfonates in which the rate constants are decreased by electron donating substituents, while electron withdrawing groups presented the reverse effects. Hammett ${\rho}$ value is significantly smaller than that of p-nitrobenzyl arenesulfonates and thus, the mechanism should be closer to tight $S_N2$ one. Especially 2,5-dichlorobenzenesulfonate was more accelerated than expected at the additivity of substituents. This facts showed that dichlorobenzenesulfonate anion is more stabilized by the great electron withdrawing substituents at transition state.

• Journal of the Korean Chemical Society
• /
• v.38 no.5
• /
• pp.391-396
• /
• 1994

The hydrolysis of $\alpha-benzoxystyrene(1)$ in strong acidic solution has been investigated kinetically. In perchloric acid concentration lower than 5.5 M($H_o$ < -3.0), hydration paramer $\omega$ = + 7.6, and $\Phi$ = + 0.54 were obtained. The solvent isotope effect $k_{H_2O}/K_{D_2O}$ is 0.72. The substituent effect was found to conform to the Hammett $\sigma^+$ constant with $\rho$ = -0.60. On the basis of these results and other evidence, the hydrolysis of the enol ester proceeds by $A_{AL}$2 type mechanism. In concentration greater than 5.5 M($H_o$ > -3.0), isotope effect, $k_{H_2O}/_{D_2O}$ is 3.32, substituent effect, $\rho$ is -1.60 and the rate is linear with the acidity function, $H_o$. Thus, the mechanism changes one involving initial, and rate-determining olefin protonation.

• Applied Chemistry for Engineering
• /
• v.28 no.5
• /
• pp.597-600
• /
• 2017

$(C_{10}H_8N_2H)_2Cr_2O_7$ was synthesized by reacting 4,4'-bipyridine and chromium (VI) trioxide. The structure of the product was characterized with FT-IR (infrared spectroscopy) and elemental analysis. The oxidation of benzyl alcohol using $(C_{10}H_8N_2H)_2Cr_2O_7$ in various solvents showed that the reactivity increased with the increase of the solvent dielectric constant, in the order of DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. In the presence of DMF, an acidic catalyst such as $H_2SO_4$ $(C_{10}H_8N_2H)_2Cr_2O_7$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. Hammett reaction constant (${\rho}$) was -0.70 (308 K). The observed experimental data were used to rationalize the hydride ion transfer in the rate determining step.

• Journal of the Korea Academia-Industrial cooperation Society
• /
• v.14 no.1
• /
• pp.499-505
• /
• 2013

Cr(VI)-4-(dimethylamino)pyridine[4-(dimethylamino)pyridinium chlorochromate] was synthesized by the reaction of 4-(dimethylamino)pyridine with chromium trioxide in 6M-HCl, and characterized by IR, ICP. The oxidation of benzyl alcohol using 4-(dimethylamino)pyridinium chlorochromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene$H_2SO_4$ solution), 4-(dimethylamino)pyridinium chlorochromate oxidized benzyl alcohol and its derivatives(p-$OCH_3$, m-$CH_3$, H, m-$OCH_3$, m-Cl, m-$NO_2$) smoothly in DMF. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.68(303K). The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

• Journal of the Korea Academia-Industrial cooperation Society
• /
• v.13 no.7
• /
• pp.3252-3260
• /
• 2012

2,2'-Bipyridinium chlorochromate[$C_{10}H_8N_2HCrO_3Cl$] was synthesized by the reaction of 2,2'- bipyridine with chromium(VI) trioxide in 6M HCl. The structure was characterized by IR and ICP analysis. The oxidation of benzyl alcohol using 2,2'-bipyridinium chlorochromate in various solvents showed that the reactivity increased with the increase in the order of the dielectric constant(${\varepsilon}$), in the order: cyclohexene< chloroform$p-CH_3$, H, m-Br, $m-NO_2$) in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.64(303K). The oxidation reactivity of alcohols can be a useful factor to study about physical properties such as thermal stability, when the polysilsesquioxane solution is ready for an applying coating agent. The observed experimental data was used to rationalized the hydride ion transfer in the rate-determining step.

• Journal of the Korea Academia-Industrial cooperation Society
• /
• v.14 no.11
• /
• pp.6000-6007
• /
• 2013

Cr(VI)-heterocyclic complex[Cr(VI)-isoquinoline] was synthesized by the reaction between of heterocyclic compound(isoquinoline) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using Cr(VI)-isoquinoline in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order : cyclohexene$CH_3$, m-Br, m-$NO_2$). Electron- donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.69(308K). The observed experimental data have been ratiolized. The hydride ion transfer causes the prior formation of a chromate ester in the rate-determining step.

• Journal of the Korean Chemical Society
• /
• v.25 no.2
• /
• pp.110-118
• /
• 1981

Kinetics and mechanism for the reaction of substituted phenacyl bromides with substituted pyridines have been determined at 25, 35 and $45^{\circ}C$ in methanol and dimethylformamide by the conductivity method. The rate constants for the reaction of various pyridines with phenacyl bromide shown that electron-donating substituents in the pyridine increase the rate, while electron-attracting one decrease in both solvents. The effect of substituents in substrate, the rate being increased by electron-attracting substituents. This is as expected for nucleophilic attack of amines on the carbon atom. Isokinetic and $Br{\psi}nsted$ linear relationship were shown in the reaction of phenacyl bromide with pyridines in both solvent in which isokinetic temperature were obtained 614, $202^{\circ}K$ and ${\beta}$ values were 0.29, 0.36 in methanol and dimethylformamide respectively. In the case of the reaction of substituted phenacyl bromide with pyridines, isokinetic temperature decreases with increasing electron-attracting ability of the substituents in the phenacyl bromide, while the ${\beta}$ values were reverse. From the above results, it can be inferred that N…C bond formation decreases progressively from p-chloro- to p-methoxyphenacyl bromide and the bond formation predominates in DMF than methanol. The ${\rho}$ values of Hammett equation of the reaction of phenacyl bromide with substituted pyridines are negative in both solvent, but its value was larger negative in DMF than methanol and the ${\rho}$ value of that of substitutted substrates with pyridine was 0.3, the low value is ascribed to direct $S_N2$ attack of the nitrogen atom in pyridine ring at the methylene carbon.

• Journal of the Korean Chemical Society
• /
• v.33 no.5
• /
• pp.468-476
• /
• 1989

Kineties for the reactions of pyridines with 1-anthracenesulfonyl chloride (1-ASC) and 3-phenanthrenesulfonyl chloride (3-PSC) was investigated in methanol as solvent. Structural variation in pyridine followed $Br{\o}$ nsted and Hammett relations for both 1-ASC and 3-PSC; the corresponding coefficients, {\beta}\;and\;{\rho}\;at\;20^{\circ}C$ were 0.55, -3.5 for 1-ASC, and 0.43, -2.6 for 3-PSC respectively. Reactivity-selectivity principle was checked in competition system 1-ASC/3-PSC. As a result, this principle was found to hold at experimental temperatures, whereas to break down over in the range of isoselective temperature ($34.3^{\circ}C$). Judging from the above results and activation parameters, we concluded that these reactions proceeded by synchronous $S_n2$ mechanism in rate-determining step.

• Journal of the Korean Chemical Society
• /
• v.27 no.2
• /
• pp.133-141
• /
• 1983

The kinetics of the acid-catalyzed hydrolysis of a series of 1-aryl-2-pyrrylideneaniline (3) have been studied in 20% MeOH solution using UV spectrophotometer. Substituents in 3 showed a relatively small effect, with hydrolysis facilitated by electron withdrawing group. By obtaing linear plots of $log k_{obs}$ against Hammett ${\sigma}$ constants, it was able to show that substituents had a considerable contribution to the aromaticity of pyrrole compounds. The small positive ${\rho}$ values were consistent with the rate-determining addition of water to the protonated schiff base in the buffer solution of pH 4 to 8, whereas the addition of water to the free imine seemed to be the rate-determining in the solution of acidities greater than pH 8.

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