• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2036-2040
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• 2013

Reactions of 4-nitrophenyl 2-thiophenecarboxylate (1a-e) with $R_2NH/R_2NH{_2}^+$ in 20 mol % DMSO (aq) have been studied kinetically. The $2^{nd}$ order kinetics, ${\beta}_{nuc}$ = 0.88-0.98, and linear Hammett and Yukawa-Tsuno plots observed for these reactions indicate an addition-elimination mechanism in which the $2^{nd}$ step is rate limiting. The ${\beta}_{nuc}$ value increased with a stronger electron-withdrawing 5-thienyl substituent, the Hammett plots are linear except for X = MeO, and Yukawa-Tsuno plots are linear with ${\rho}$ = 0.79-1.32 and r = 0.28-0.93, respectively. The ${\rho}$ value increased and r value decreased with a stronger nucleophile, indicating an increase in the electron density at the C=O bond and a decrease in the resonance demand. These results have been interpreted with enhanced N-C bond formation in the transition state with the reactivity increase.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.39 no.4
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• pp.359-370
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• 2015

The present study aims to numerically investigate the behavior of liquid droplet driven by capillarity force imbalance on horizontal surfaces ranging from hydrophilic to hydrophobic, under various conditions. The droplet behavior has been simulated using an in-house solution code(PowerCFD), which employs an unstructured cell-centered method based on a conservative pressure-based finite-volume method with interface capturing method(CICSAM) in a volume of fluid(VOF) scheme for phase interface capturing. The detailed droplet behavior was obtained under various conditions for droplets with different initial shapes, contact angles and surface tension forces(or Bond number). The mechanism of droplet transport was examined using the numerical results on the droplet shapes.

• Journal of the Korean Chemical Society
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• v.41 no.1
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• pp.22-46
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• 1997

Kinetic studies on nucleophilic substitution reaction of phenacyl bromide and phenacyl chloride with pyridines were conducted at 25℃ and 35℃ in methanol-acetonitrile solvents mixtures. It was shown that the reaction proceeds via an SN2 reaction mechanism based on the transition state parameters, ΔH≠ and ΔS≠ and Bro nsted β values. Quantum mechanical model predicted a product-like transition state, where bond-formation is much more progressed than bond breaking, upon changing the leaving group to that with a better leaving ability.

• 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.32 no.6
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• pp.2063-2069
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• 2011

We studied the interaction of 3,3',3'',3'''-ethylenetetrakis-4-hydroxycoumarin (EHC) with bovine serum albumin (BSA) in acetate buffer and phosphate buffer with different pH values by UV-vis absorption spectrometry and fluorescence spectrometry respectively. It was found that the pH values of the buffer solutions had an effect on the interaction process. In acetate buffer of pH 4.70, the carbonyl groups in EHC bound to the amino groups in BSA by means of hydrogen bond and van der Waals force, which made the extent of peptide chain in BSA changed. By contrast, in phosphate buffer of pH 7.40, hydrophobic force played a major role in the interaction between EHC and BSA, while the hydrogen bond and van der Waals force were also involved in the interaction. The results of spectrometry indicated that BSA could enhance the fluorescence intensity of EHC by forming a 1:1 EHC-BSA fluorescent complex through static mechanism at pH 4.70 and 7.40 respectively. Furthermore, EHC bound on site 1 in BSA.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1921-1924
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• 2011

Nitrile-forming eliminations from $(E)-2,4,6-(NO_2)_3C_6H_2CH=NOC_6H_4-2-X-4-NO_2$ (1) promoted by $R_3NH/R_3NH^+$ in 70 mol % MeCN(aq) have been studied kinetically. When X = $NO_2$, the reactions exhibited second-order kinetics as well as Br$\"{o}$nsted ${\beta}$ = 0.63 and ${\mid}{\beta}_{lg}{\mid}$ = 0.34-0.46, and an E2 mechanism is evident. As the leaving group was made poorer (X = H, Cl, and $CF_3$), Br$\"{o}$nsted ${\beta}$ value increased from 0.63 to 0.85-0.89 without much change in the ${\mid}{\beta}_{lg}{\mid}$ value E2, indicating that structure of the transition state changed to an E1cb-like with extensive $C_{\beta}-H$ bond cleavage, significant negative charge development at the ${\beta}$-carbon, and limited $C_{\alpha}$-OAr bond cleavage.

• Journal of the Korean Chemical Society
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• v.9 no.1
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• pp.23-28
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• 1965

Halogen exchanges between benzyl chloride and chloride ion have been studied in 90% ethanol-water mixture, and activation parameters in the exchange reaction have been determined; ${\Delta}H^{\neq}$ = 18. 50 Kcal and ${\Delta}S^{\neq}$ = -22. 09 e. u. Results indicated that the reaction proceeded via a typical bimolecular mechanism. The importance of nucleophilic ability of attacking anion in $S_N2$ process has been stressed giving some experimental evidence. The order of reactivity of halides in the exchange reaction is better explained with the Swain's nucleophilic parameter than with the bond dissociation energies.

• Journal of the Korean Chemical Society
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• v.21 no.4
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• pp.262-269
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• 1977

The solvolysis of 1-naphthalene-and 2-naphthalenesulfonyl chlorides in acetone-water mixtures have been studied by means of conductometry. The solvent effect and mechanism have been discussed in terms of variation in solvent composition and activation parameters. The reaction was predominantly $S_N2$ type, but bond breaking increased with the increase of water content. The rate constant for 1-naphthyl compound was smaller than that of 2-naphthyl compound due to the ground state stabilization effect and peri-hydrogen effect, and the latter effect was similar to that in ethanol-water mixtures.

• Journal of the Korean Applied Science and Technology
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• v.14 no.1
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• pp.27-32
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• 1997

Furfurylidene acetophenone derivatives were synthesis, it was measured that nucleophilic addition made use of UV at a wide pH 1.0${\sim}$13.0 range in 30% dioxane-$H_2O$ solution, 25$^{\circ}C$. On the basis of general base catalysis, substitutent effect, confirmation of nucleophilic addition products, it was measured the reaction rate of furfurylidene acetophenone derivatives for the pH change. It may be concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion: Above pH 10.0. sulfide anion adds to the double bond (Michael type addition), a part having no concern with pH, addition reaction to double bond is initiated by addition of neutral thiourea molecule. From the result of measurement the reaction rate, nucleophilic addition of furfurylidene acetophenone derivatives confirmed to the irreversible first order. Through measurement the substituent effect. It found that reaction rate was accelerated by electron attracting group. On the basis of these findings, nucleophilic addition of thiourea for the furfurylidene acetophenone derivative was proposed a fitting mechanisms.

• Journal of the Korean Chemical Society
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• v.33 no.4
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• pp.413-418
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• 1989

The rates for the reaction of substituted 2-phenylethyl tosylates with substituted pyridines were measured in acetonitrile and that of 2-PNS with substituted pyridines were investigated in both acetonitrile and methanol. The substitutent effect was accelerated by an electron-donating substituent on both substrate and nucleophile. Results showed that More O'Ferrall and quantum mechanical model of predicting transition state structure suggest the reaction proceeds via an $S_N2$ mechanism, in which bond-breaking is more advanced than bond-formation. Transition state variation predicted with the quantum mechanical model is consistent with the experimental results, whereas the predictions provided by the More O'Ferrall plots is found to be inconsistent in leaving group. In the reaction of 2-PNS, the rate constants in acetonitrile were larger than that in methanol.