• Bulletin of the Korean Chemical Society
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• v.34 no.4
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• pp.1115-1119
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• 2013

A kinetic study is reported for nucleophilic substitution reactions of benzyl 2-pyridyl thionocarbonate (5b) and t-butyl 2-pyridyl thionocarbonate (6b) with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. General-base catalysis, which has often been reported to occur for aminolysis of esters possessing a C=S electrophilic center, is absent for the reactions of 5b and 6b. The Br${\o}$nsted-type plots for the reactions of 5b and 6b are linear with ${\beta}_{nuc}$ = 0.29 and 0.43, respectively, indicating that the reactions of 5b proceed through a stepwise mechanism with formation of a zwitterionic tetrahedral intermediate ($T^{\pm}$) being the rate-determining step while those of 6b proceed through a concerted mechanism. The reactivity of 5b and 6b is similar to that of their oxygen analogues (i.e., benzyl 2-pyridyl carbonate 5a and t-butyl 2-pyridyl carbonate 6a, respectively), indicating that the effect of modification of the electrophilic center from C=O to C=S (i.e., from 5a to 5b and from 6a to 6b) on reactivity is insignificant. In contrast, 6b is much less reactive than 5b, indicating that the replacement of the $PhCH_2$ in 5b by the t-Bu in 6b results in a significant decrease in reactivity as well as a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway). It has been concluded that the contrasting reactivity and reaction mechanism for the reactions of 5b and 6b are not due to the electronic effects of $PhCH_2$ and t-Bu but are caused by the large steric hindrance exerted by the bulky t-Bu in 6b.

• Journal of the Korean Chemical Society
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• v.40 no.12
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• pp.733-740
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• 1996

The rate constants for the hydrolysis of 4'-[N-(9-acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide(AMQD) were determined by ultraviolet visible spectrophotometer in water at $25^{\circ}C.$ The rate equation which could be applied over wide pH ranges were obtained. On the basis of pH-rate profile, Bronsted plot, hydrolysis product analysis, general base catalysis and substituent effect, the plausible hydrolysis mechanism was proposed: Below pH 3.00, the hydrolysis reaction was proceeded by the attack of water to 4'-position of quinonoid after protonation at nitrogen of acridinyl and between pH 3.00 and 9.00, the addition of water and hydroxide occurred competitively. However, above pH 9.00, the rate constants were dependent upon only the concentration of hydroxide ion.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.127-134
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• 1989

The rate constants of the nucleophilic addition reaction of 3-mercaptopropionic acid to the ${\beta},\;{\beta}$-diethoxycarbonylstryene derivatives (H, p-OCH$_3$, 3,4,5-(OCH$_3)_3$, 3,4-methylenedioxy) were determined by ultraviolet spectrophotometry, and rate equation which could be applied over a wide pH range was obtained. On the basis of pH-rate profile and the presence of general base catalysis, a plausible mechanism of this addition reaction was propound:Below pH 6.0 the reaction was initiated by the addition of neutral 3-mercaptopropionic acid molecule, and in the range of pH 6.0∼8.0, a neutral 3-mercaptopropionic acid molecule and a sulfide anion competitively attacked to the double bond. Above pH 8.0, the reaction proceeded through the addition of a sulfide anion.

• Journal of the Korean Applied Science and Technology
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• v.13 no.1
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• pp.99-105
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• 1996

Furfurylidene acetophenone derivatives were synthesis, it was measured that hydrolysis made use of UV at a wide pH $1.0{\sim}13.0$ range in 30% $dioxane-H_2O$ solution, $25{\pm}1^{\circ}C$. On the basis of general base catalysis, substitutent effect, confirmation of hydrolysis products, it was measured the reaction rate of furfurylidene acetophenone derivatives for the pH change. It maybe concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion : Above pH 10.0, It was in proportion to concentration of hydroxide ion, a part having no concern with pH was added to the neutral $H_2O$ molecule. From the result of measurement the reaction rate, hydrolysis 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. Also, From the result of final product, There were furfural and acetophenone. On the basis of these findings, Hydrolysis for the furfurylidene acetophenone derivative was proposed a fitting mechanisms.

• Journal of the Korean Chemical Society
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• v.37 no.8
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• pp.695-701
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• 1993

Rate constants of solvolysis of 2-thiophenesulfonyl chloride were determined in aqueous binary mixtures with methanol, ethanol, acetone in water and in methanol. These data are interpreted using the equation of Grunwald-Winstein and Kivinen relationship. Also, kinetic solvent isotope effects in water and in methanol and product selectivities in alcohol-water mixtures were determined. Kinetic solvent isotope effect for hydrolysis of 2-thiopenesulfonyl chloride was 2.24 and 1.47 for methanol and water, respectively. Selectivity values for formation of ester relative to acid in ethanol-water mixtures show maximum S value. From kinetic solvent isotope effect in methanol and water, selectivity data in aqueous alcoholic solvents and solvent effects, it is proposed that the reaction channel favoured in low polarity solvents is general-base catalysis and/or is possibly addition elimination (S$_A$N) reaction pathway and in high polarity solvents iS S$_N$2 reaction mechanism.

• KSBB Journal
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• v.24 no.3
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• pp.267-272
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• 2009

During a dilute acid hydrolysis, degradation products are formed or liberated by pre-treatment of lignocelluloses depend on both the biomass and the pretreatment conditions such as temperature, time, pressure, pH, redox conditions, and addition of catalysts. In lignocellulosic biomass, sugars can be degraded to furfural which is formed from pentoses and 5-hydroxymethulfurfural (HMF) from hexoses. 5-HMF can be further degraded, forming levulinic acid and formic acid. Acetate is liberated from hemicellulose during hydrolysis. Some decomposed compounds hinder the subsequent bioconversion of the solubilized sugars into desired products, reducing conversion yields and rates during fermentation. In the present work, samples of rapeseed strawwere hydrolyzed to study the optimal pretreatment condition by assessing yields of sugars and decomposed products obtained under different reaction conditions ($H_2SO_4$ 0.5-1.25% (w/w), reaction time 0-20 min and temperature range 150-220 C). A careful analytical investigation of acid hydrolyzate of rapeseed straw has not yet been undertaken, and a well-closed mass balance for the hydrolyzate in general is necessary to verify the productivity and economic predictions for this process.