• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.589-597
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• 1992

The rate constants of hydrolysis of phenyl-N-benzoylchlorothioformimidates were determined by UV spectrophotometry in 30% (v/v) aqueous dioxane at $25^{\circ}C$. On the basis of rate equation, general base catalysis, solvent effect, substituent effect, thermodynamic parameters, frontier orbital interaction and hydrolysis product analysis, it may be concluded that the hydrolysis of phenyl-N-benzoylchlorothioformimidates proceeds through $S_N1$ mechanism via azocarbocation intermidiate below pH 10.0, while above pH 10.00 the hydrolysis proceeds through nucleophilic addition-elimination ($Ad_{N-E}$) mechanism. In the range of pH from 10.0 to 11.0 these two reaction occur competitively.

• Bulletin of the Korean Chemical Society
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• v.18 no.11
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• pp.1186-1191
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• 1997

Solvolyses of methanesulfonyl chloride (CH3SO2Cl) in water and methanol have been studied theoretically using ab initio self-consistent reaction field (SCRF) molecular orbital method. All stationary structures including transition state on the potential energy surface in solution have been found and compared with the gas phase structures. The overall reaction occurs via a concerted SN2 mechanism with a non-cyclic trigonal bipyramidal transition state, and the activation barrier is lowered significantly in solution. The transition state for the hydrolysis reaction is looser than that for the methanolysis reaction, and this is in accord with the experimental findings that an SN2 type mechanism, which is shifted toward an SN1 process or an SAN process in the hydrolysis and alcoholysis reaction, respectively, takes place. The catalytic role of additional solvent molecules appears to be a purely general-base catalysis based on the linear transition structures. Experimental barrier can be estimated by taking into account the desolvation energy of nucleophile in the reaction of methanesulfonyl chloride with bulk solvent cluster as a nucleophile.

• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.584-588
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• 1992

The rate constants of hydrolysis of ${\alpha}$-(n-butyl)-N-phenylnitrone and its derivatives have been determined by UV spectrophotometry at 25$^{\circ}C$ and a rate equation which can be applied over a wide pH range was obtained. On the basis of rate equations derived and judging from the hydrolysis products obtained and from general base and substituent effects, plausible mechanisms of hydrolysis in various pH range have been proposed. Below pH 4.5, the hydrolysis was initiated by the protonation and followed by the addition of water to ${\alpha}$-carbon. Above pH 10.0, the hydrolysis was proceeded by the addition of hydroxide ion to ${\alpha}$-carbon. In the range of pH4.5∼10.0, the addition of water to nitrone is rate controlling step.

• Journal of the Korean Chemical Society
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• v.40 no.2
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• pp.128-134
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• 1996

The kinetics of the hydrolysis of dihydro-1, 4-oxathiin derivatives were investigated by ultraviolet spectrophotometry in H2O at $25^{\circ}C.$ A rate equation which can be applied over a wide pH range was obtained. The substituent effects on the hydrolysis of dihydro-1, 4-oxathiin derivatives were studied and the rate of hydrolysis was shown to be accelerated by electron accepting groups. Final product of the hydrolysis was 2-(2-hydroxyethylthio)acetoacet-anilide enol form. On the basis of rate equations derived and judging from hydrolysis products obtained and from general base effect and substituent effects, plausible mechanism of the hydrolysis in various pH range have been proposed. Below pH 3.5, the hydrolysis was initiated by the protonation and followed by the addition of water to 2-carbon. Above pH 10.0, the hydrolysis was proceeded by the addition of hydroxide to 2-carbon. In the range of pH 4.0∼10.0, the addition of water to dihydro-1,4-oxathiin is rate controlling step.

• Journal of the Korean Chemical Society
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• v.34 no.5
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• pp.483-489
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• 1990

The rate of hydrolysis of insecticidal 2-chloro-l-(2,4,5-trichlorophenyl)-vinyldimethylphosphate(Gardona) have been investigated in 25${\%}$ aqueous methanol. Studies at varying pH suggest that the hydrolysis of Gardona proceeds through the bimolecular (Ad$_{N-E}$) mechanism involving the transition state and carbanion intermediate as evidenced by solvent effect (m < 0.4, n < 0.7, [m] ${\ll}$ [l](associative SN$_2$ type)), thermodynamic parameters (${\{Delta}S^{\neq}$ = -27∼-32 e.u. & ${\{Delta}H^{\neq}$ = 13∼18 Kcal/mole), hydrolysis rate equation (k = k$_A+_B$ [OH-]), general base catalysis and hydrolysis product analysis, respectively.

• 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.

• Applied Biological Chemistry
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• v.40 no.1
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• pp.53-57
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• 1997

The rate of hydrolysis of insecticidal 1-(6-chloro-3-pyridylmethyl) -2-nitro-iminoimidazolidine (common name; imidacloprid) have been investigated in 15%(v/v) aqueous dioxane at $45^{\circ}C$. From the kinetics and non-kinetics data such as pH-effect, solvent effect(m=0.04, n=0.30 IT m<${\Delta}H^{\neq}=16.14kcal{\cdot}mol^{-1}\;&\;{\Delta}S^{\neq}=-0.03e.u.$), rate equation ($k_{obs.}=4.56{\times}10^{-3}[OH^-]$) and analysis of hydrolysis product, 1-(6-chloro-3-pyridylmethyl-2)-imidazolidinon, the hydrolysis mechanism of imidacloprid is proposed that the specific base catalyzed hydrolysis($K_{OH^-}$) through nucleophilic addition-elimination ($Ad_N-E$) mechanism proceed via intermediate, 1-(6-chloro-3- pyridylmethyl)-2-hydroxy-2-imidazolidinylisonitraminate (I) and ${\beta}$-3-(6-chloro-3-pyridylmethyl)aminoethyl-1-nitrourea(III). And the half-life(t1/2) of hydrolytic degradation at pH 8.0 and $45^{\circ}C$ was about 4.5 months.

• Journal of the Korean Applied Science and Technology
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• v.6 no.2
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• pp.67-74
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• 1989

The Kinetics of the Hydrolysis of benzalacetophenone derivatives has been investigated by ultraviolet spectrophotometry in 5% dioxane - $H_2O$ at $50^{\circ}C$. A rate equation which can be applied over wide pH range was obtained. The substituent effect on the hydrolysis of benzalacetophenone derivatives were facilitated by electron attracting groups. Based on the rate equation, substituent effect, general base effect, activation parameters and final product, the hydrolysis of benzalacetophenone derivatives seems to be initiated by the netural molecule of $H_2O$ which does not dissociate at below pH 9.0 but proceeded by the hydroxide ion at above pH 11.0. In the range of pH $9.0{\sim}11.0$ these two reactions occur competitively.

• Journal of the Korean Applied Science and Technology
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• v.10 no.1
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• pp.75-81
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• 1993

The hydrolysis kinetics of 2-furyl chalcone derivatives $[I]{\sim}[V]$ was investigated by ultraviolet spectrophotometery in 30% dioxane-$H_{2}O$ at $25^{\circ}C$ and the structure of these compounds were ascertained by means of ultraviolet, infrared and NMR spectra. The rate equations which were applied over a wide pH range(pH $1.0{\sim}12.0$) were obtained. The substituent effects on 2-furyl chalcone derivatives $[I]{\sim}[V]$ were studied, and the hydrolysis were facilitated by the electron attrecting groups. On the basis of the rate equation, substituent effect, general base effect and final product. the plausible hydrolysis mechaism was proposed: Below pH 4.0, it was only proportional to concentration of hydronium ion, at pH $4.0{\sim}9.0$, neutral $H_{2}O$ molecule competitively attacked on the double bond. By contrast, above pH 9.0, it was proportional to concentration of hydroxide ion.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.120-126
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• 1989

The Kinetics of hydrolysis of styrylphenylsulfone derivatives in 50% methanol-water at 25$^{\circ}$C and ionic strength of 0.10 was investigated by UV spectrophotometry in the pH range of 0.0-14.0. The rate equations, which can be applied over a wide pH range, were obtained. The Hammett rho constants for the hydrolysis are 1.85 at pH 7.0 and 1.54 at pH 13.0, respectively. On the basis of the evidence, it is proposed that the general base-catalysis occurs in the hydrolysis of styrylphenylsulfone derivatives; above pH 11.0, Michael type nucleophilic addition take place, while below pH 9.0, the reaction is initiated by addition of water and from pH 9.0 to pH 11.0 these two reactions occur com-petitively.