• Journal of Convergence for Information Technology
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• v.11 no.9
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• pp.109-114
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• 2021

Cr(VI)-quinoline compound[(C₉H₇NH)₂Cr₂O₇] was synthesized by the reaction between of quinoline and chromium(VI) trioxide, and structure was FT-IR, elemental analysis. The oxidation ability of benzyl alcohol greatly depends upon the dielectric constant of the used organic solvent, where carbon tetrachloride was worst and N,N'-dimethylformamide was best solvent. Noticeably, in N,N'-dimethylformamide solvent, Cr(VI)-quinoline compound oxidized substituted benzyl alcohols. The Hammett reaction constant(ρ)=-0.69(303K). As a resuit, Cr(VI)-quinoline compound was found as efficicent oxidizing agent that converted benzyl alcohol, allyl alcohol, primary alcohol and secondary alcohols to the corresponding aldehydes or ketones. Cr(VI)-quinoline compound was selective oxidizing agent of benzyl alcohol, allyl alcohol and primary alcohol in the presence of secondary alcohol ones.

• Journal of the Mineralogical Society of Korea
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• v.20 no.4
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• pp.313-325
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• 2007

In order to have better insights into adsorption of organic molecules on kaolinite surfaces, we performed quantum chemical calculations of interaction between three different model clusters of kaolinite siloxane surfaces and benzyl alcohol, with emphasis on the effect of size and lattice topology of the cluster on the variation of electron density and magnetic shielding tensor. Model cluster 1 is an ideal silicate tetrahedral surface that consists of 7 hexagonal rings, and model cluster 2 is composed of 7 ditrigonal siloxane rings with crystallographically distinct basal oxygen atoms in the cluster, and finally model cluster 3 has both tetrahedral and octahedral layers. The Mulliken charge analysis shows that siloxane surface of model cluster 3 undergoes the largest electron density transfer after the benzyl alcohol adsorption and that of model cluster 1 is apparently larger than that of model cluster 2. The difference of Mulliken charges of basal oxygen atoms before and after the adsorption is positively correlated with hydrogen bond strength. NMR chemical shielding tensor calculation of clusters without benryl alcohol shows that three different basal oxygen atoms (O3, O4, and O5) in model cluster 2 have the isotropic magnetic shielding tensor as $228.2{\pm}3.9,\;228.9{\pm}3.4,\;and\;222.3{\pm}3.0ppm$, respectively. After the adsorption, the difference of isotropic chemical shift varies from 1 to 5.5 ppm fer model cluster 1 and 2 while model cluster 2 apparently shows larger changes in isotropic chemical shift. The chemical shift of oxygen atoms is also positively correlated with electron density transfer. The current results show that the adsorption of benzyl alcohol on the kaolinite siloxane surfaces can largely be dominated by a weak hydrogen bonding and electrostatic force (charge-charge interaction) and demonstrate the importance of the cluster site and the lattice topology of surfaces on the adsorption behavior of the organic molecules on clay surfaces.

• Proceedings of the Petrological Society of Korea Conference
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• 2006.05a
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• pp.39-41
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• 2006

• Journal of the Korean Chemical Society
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• v.16 no.5
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• pp.284-289
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• 1972

Rates of the reactions of m-and p-ring-substituted thiobenzamides with benzyl bromide in acetone have been determined by an electric conductivity method. The Hammett rule has been adopted for these reactions. It has been observed that an electron-attracting substituent accelerates the reaction while an electron-donating substituent retards the reaction, and a mechanism which accounts for the observed kinetics has been postulated. The activation energies and entropies of activation for these reactions have also been calculated.

• Journal of the Korean Chemical Society
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• v.9 no.3
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• pp.148-151
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• 1965

Kinetics of reactions of chloride and bromide ions with benzyl chloride and bromide have been investigated in 90% ethanol solution. Semi-quantitative analysis of the results shows that the bond-formation is more important than the bond-breaking and furthermore in bond-formation the energy gain due to bond-formation is less than the increase in electron affinity of the nucleophile.

• Journal of the Korean Chemical Society
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• v.38 no.4
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• pp.328-332
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• 1994

• Journal of the Korean Chemical Society
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• v.38 no.12
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• pp.915-920
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• 1994

The Menschutkin type reactions of substituted (Z)-benzyl (X)-arenesulfonates with substituted(Y)-pyridines were studied by the electroconductometric method in acetonitrile at $35\circC$. Hammett $\rho$ values were calculated by the second order rate constants for the reaction of substituted (Z)-benzyl (X)-arenesulfonates with substituted (Y)-pyridines. The negative $\rho_Y$ values meant positive charge development on the nitrogen of pyridine at transition state owing to the charge development on the oxygen atom of benzenesulfonate. And the negative $\rho_Z$ values meant positive charge development on the benzylic carbon. Application of the multi-Hammett interaction,│$\rho_YZ$│ > │$\rho_XY$│ > │$\rho_ZX$│, the Menschutkin type reaction of substituted benzyl arenesulfonates with substituted pyridines was shown to be dissociative $S_N2$ mechanism.

• Applied Chemistry for Engineering
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• v.26 no.3
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• pp.372-376
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• 2015

6-MQCC (Cr(VI)-6-methylquinoline) complex was synthesized by the reaction of 6-methylquinoline with chromium(VI) trioxide in 6 M HCl. The structure was characterized using IR (Infrared Spectroscopy) and ICP (Inductively Coupled Plasma) analysis. The oxidation of benzyl alcohol using 6-MQCC in various solvents showed that the reactivity increased with the increase of the dielectric constant, in descending order of DMF > acetone > chloroform > cyclohexene. In the presence of DMF solvent with acidic catalyst such as sulfuric acid ($H_2SO_4$), 6-MQCC oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$) were effectively oxidized. Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.69 (308 K). The observed experimental data was used to rationalize the fact that the hydride ion transfer occurred at the rate-determining step.

• Applied Chemistry for Engineering
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• v.16 no.1
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• pp.153-157
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• 2005

4-(Dimethylamino)pyridinium dichromate was synthesized by the reaction of 4-(dimethylamino)pyridine with chromium(VI)trioxide in $H_2O$, and characterized by IR, EA and ICP. The oxidation of benzyl alcohol using 4-(dimethylamino)pyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: cyclohexen < chloroform < acetone < N,N-dimethylformamide. In the presence of hydrochloric acid(HCl), 4-(dimethylamino)pyridinium dichromate oxidized benzyl alcohol and its derivatives ($p-CH_3$, H, m-Br, $m-NO_2$) smoothly in N,N-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron-withdrawing groups retarded the reaction. The Hammett reaction constant($\rho$) was -0.70 at 303K. The observed experimental data have been rationalized as follows: the proton transfer occurs after the prior formation of a chromate ester in the rate-determining step.

• Journal of the Korean Chemical Society
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• v.30 no.3
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• pp.301-306
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• 1986

The rate constants for the solvolysis reactions of p-methoxybenzylchloride in ethanol-water mixtures were determined at 2$^{\circ}$ and 10$^{\circ}C$ up to 1600bar. Rates of reaction were increased with increasing temperature and pressure, and decreased with increasing solvent composition of ethanol mole fraction. From the rate constants, the values of the activation parameters (${{\Delta}V_o}^{\neq},\;{\Delta}{\beta}^{\neq},\;{\Delta}H^{\neq},\;and\;{\Delta}S^{\neq}$) were evaluated. The values of ${{\Delta}V_o}^{\neq}$ and ${\Delta}{\beta}^{\neq}$ exhibit the extremum behavior at about 0.30 mole fraction of ethanol. This behavior is discussed in terms of solvent structure variation. From these results, it could be postulated that the reaction proceeds through $S_N1$ mechanism.