• Bulletin of the Korean Chemical Society
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• v.34 no.1
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• pp.49-53
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• 2013

Second-order rate constants have been measured spectrophotometrically for the reactions of phenyl Y-substituted-phenyl carbonates 7a-g with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The ${\alpha}$-nucleophile $Ox^-$ is 53-95 times more reactive than the corresponding normal-nucleophile 4-$ClPhO^-$ toward 7a-g, indicating that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect (e.g., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent Y. The cause of the ${\alpha}$-effect for the reactions of 7a-g has been suggested to be ground-state (GS) effect rather than transition-state (TS) stabilization through a six-membered cyclic TS, in which $Ox^-$ behaves a general acid/base catalyst. This idea is further supported by the result that $OH^-$ exhibits negative deviation from the linear Br${\o}$nsted-type plot composed of a series of aryloxides, while $Ox^-$ deviates positively from the linearity. Differential solvation of the GS of $Ox^-$ and 4-$ClPhO^-$ has been suggested to be responsible for the ${\alpha}$-effect exerted by $Ox^-$.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2251-2255
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• 2013

Second-order rate constants ($k_{HOO^-}$) for the nucleophilic substitution reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with $HOO^-$ in $H_2O$ have been measured spectrophotometrically. The ${\alpha}$-nucleophile $HOO^-$ is 10-70 times more reactive than the reference nucleophile $OH^-$ although the former is ca. $4pK_a$ units less basic than the latter, indicating the ${\alpha}$-effect is operative. The Bronsted-type plot for the reactions of 4a-4i with $HOO^-$ is linear with ${\beta}_{lg}=-0.51$, a typical ${\beta}_{lg}$ value for reactions which were reported to proceed through a concerted mechanism. The Yukawa-Tsuno plot is also linear with ${\rho}=1.40$ and r = 0.47, indicating that a negative charge develops partially on the O atom of the leaving group, which can be delocalized to the substituent Y through resonance interactions. Thus, the reactions have been proposed to proceed through a concerted mechanism. The magnitude of the ${\alpha}$-effect (i.e., the $k_{HOO^-}/k_{HO^-}$ ratio) decreases linearly as the leaving-group basicity increases. It has been concluded that solvation effect is not solely responsible for the ${\alpha}$-effect found in this study but the transition-state stabilization through an intramolecular H-bonding interaction is also responsible for the ${\alpha}$-effect.

• Journal of the Korean Applied Science and Technology
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• v.6 no.2
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• pp.59-65
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• 1989

The rate constants of the hydrolysis of cinnamanilide derivatives were determined UV spectrometry in $H_2SO_4\;(5{\sim}20N)$, NaOH($5{\sim}11N)\;at\;50{\sim}110^{\circ}C$ and rate equation could be applied over a strong acid and strong base were obtained. Final product of the hydrolysis was a cinnamic acid. The ${\rho}$ values obtained from the slope of linear plots of log $k_{abs}$ vs. Hammet $t{\sigma}$ constants were slightly negatives, Substituents on cinnamanilide showed a relatively small effect, with hydrolysis facilitated be electron donating group. Activation energy(Ea)was also calculated for the hydrolysis of the cinnamanilide. From this reaction rate equation, substituent effect and experimental of rate constants, that the hydrolysis of cinnamanillde was Initiated by the netural molecule of $H_2O$ which do not dissociate at strong acid, and proceeded by hydroxide ion at strong base.

• Journal of the Korean Chemical Society
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• v.31 no.5
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• pp.395-399
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• 1987

The two dissociation constants of leucine were measured in the temperature range from 15 to 40$^{\circ}$C and pressure up to 2,500 bar by conductometric method. Both constants were increased as the temperature increased but pressure effect was not same as temperature effect. The first constants were increased as pressure increase but the second constants were decreased as pressure increase in the law temperature range but increased in some higher temperature range. These phenomena were discussed from the thermodynamic properties of the dissociation reactions.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2613-2617
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• 2010

Chloroprene is a chlorine substituent of 1,3-butadiene. Butadiene rubber (BR) and chloroprene rubber (CR) composites were thermally aged at 60, 70, 80, and $90^{\circ}C$ for 2 - 185 days in a convection oven and changes of the crosslink densities by the accelerated thermal aging were investigated. The crosslink densities increased as the aging time elapsed and as the aging temperature became higher. Degrees of the crosslink density changes of the BR composite were on the whole larger than those of the CR one except the short-term thermal aging at 60 and $70^{\circ}C$. The crosslink densities abnormally increased after themal aging at high temperatures for a long time. Activation energies for the crosslink density changes of the rubber composites tended to increase with increase of the aging time and the variation showed a local minimum. The activation energies of the CR composite were lower than those of the BR one. The experimental results were explained with a role of ligand of chlorine atom of CR in a zinc complex, steric hindrance by chlorine atom of CR, and oxidation of rubber chain.

• 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 Applied Science and Technology
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• v.12 no.2
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• pp.93-98
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• 1995

The rate constant of Nucleophilic addition of sodium thiophenoxide to nitrone were determined by UV Spectrophotometry and a rate equation which can be applied over wide pH range was obtained. Base on the rate equation, general base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Blow pH 3.0, the reaction was initiated of thiophenol, and in the range of pH $3.0{\sim}10.0$, proceeded by the competitive addition of thiophenol and thiophenoxide anion. Above the pH 10.0, the reaction proceeded through the addition of a thiophenoxide anion.

• Journal of the Korean Applied Science and Technology
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• v.12 no.2
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• pp.85-92
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• 1995

The rate constant of the nucleophilic addition of 1-propanethiol to ${\alpha}-phenyl-N-iso-propylnitrone$ derivatives were determined at various pH and a rate equation which can be applied over wide pH range is obtained. Final product of the addition reaction was ${\alpha}-thiopropyl-p-phenylbenzylideneamine$. Base on the rate equation, general base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Below pH 3.0, the reaction was initiated by the addition of 1-propanthiol, and in the range of pH 3.0-10.0, proceeded by the competitive addition of 1-propanethiol and propanethiolate. Above the pH 10.0, the reaction proceeded through the addition of propanethiolate.

• Applied Chemistry for Engineering
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• v.23 no.5
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• pp.510-513
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• 2012

Palladium particles were synthesized by conventional chemical reduction method with ionic liquids. The size and shape of palladium particles were significantly affected by the cation parts of ionic liquids. This is mainly attributed to the different stabilities of the ionic liquid structure formed by the physical bond between the cation parts. Among ionic liquids with [$BF_{4}$] as an anion part, the hexyl substituent in the cation parts was more effective to synthesize palladium particles with the smaller size and more uniform shape.

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2233-2239
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• 2009

In the present study, firstly, the variations of the geometric parameters induced by different substituents on boroxine skeleton (symmetrically H, $CH_3$, Cl, F, $NO_2$ substituted boroxines) are investigated by using B3LYP/6-31G(d,p), RHF/6-31G(d,p), and MP2/6-31G(d,p) levels of the theory. The second objective is to estimate the substituent effect on the molecular aromaticity of boroxine derivatives using energetic and NICS criteria. Moreover, the effects of different theoretical levels on NICS values have been investigated in a systematic approach. Lastly, a rotational analysis has been performed to investigate the effect of rotation around the B-Me and B-$NO_2$ bonds on total energy of the system. It has been found that electron withdrawing substituents contribute the aromaticity of boroxine affirmatively. Conversely, electron donors make the system less aromatic. Also, the theoretical vibrational spectra for these boroxine derivatives are presented and compared with the experimental data from the literature.