• Journal of the Korean Chemical Society
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• v.32 no.3
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• pp.260-266
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• 1988

The rate constants for the nucleophilic addition reactions of thioglycolic acid and cysteine to ${\beta},\;{\beta}$-dichlorostyrene derivatives(p-H, p-Cl, $p-CH_3,\;and\;p-OCH_3$) were photochemically determined at various pH and a rate equation which can be applied over a wide pH range was obtained. On the bases of rate equation, general base catalysis and substituent effect, the plausible addition reaction mechanism was proposed: Above pH 9.0, the reaction was initiated by the addition of sulfide anion, and in the range of pH 7.0 to 9.0, the neutral molecules and it's anions attacked to the double bond, competitively. However, below pH 7.0, only the neutral molecules of thioglycolic acid or cysteine added to the carbon-carbon double bond.

• Journal of the Korean Applied Science and Technology
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• v.4 no.1
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• pp.61-66
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• 1987

2,4,6-Triamino-5-nitrosopyrimidine was prepared using malononitrile and guanidine carbonate, and acetylated refluxing in acetic acid with acetic anhydride in order to activate the nitroso group for nucleophilic attack. Nucleophilic attack of phenylpyrimidium bromide on the nitroso group of 2,4,6-triacetamido-5-nitrosopyrimidine gave the intermediate, which lost pyrdidine to give the nitrone derivative. Addition of the methanethiol anion to nitrone gave 2,4-diacetamido-7-phenyl-6-methylthiopteridine which was hydrolyzed to give 2,4-diamino-7-phenyl-6-methylthiopteridine. Spectral data (IR, M.S, NMR) were provided to identify the reaction products during synthesis.

• Archives of Pharmacal Research
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• v.17 no.1
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• pp.39-41
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• 1994

Various N,N'-disubstituted ureas 5 were easily prepared from the corresponding primary amide 1 by tratment with N-Bromophthalimide $(NBP)-AgOAc-RNH$_{2}$ 4 in dry N,N-dimrthylformamide (DMF). This reaction envolved the intemediate formation of isocyanate 3 from amide 1 via Hofmann rearrangement by treatment with AgOAc and NBP and nucleophilic addition of amine 4 to this isocyante 3. This method is simple enough to be applied to the synthesis of various N,N'-disubstututed ureas scale conviently.

• Nuclear Engineering and Technology
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• v.7 no.4
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• pp.311-316
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• 1975

Kinetic studies on the halide exchange reactions of substituted benzoyl chlorides have been carried out. The experimental result has been explained reasonably in terms of HSAB principle and EH-Theory, and addition elimination mechanism has been proposed for this type of reaction.

• Bulletin of the Korean Chemical Society
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• v.7 no.1
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• pp.23-25
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• 1986

Reaction of ${\alpha}-cyano-{\beta}-phenylacrylic$ acid derivatives (Ⅰ) with thioglycolic acid in the molar ratio of 1:2 in saturated sodium bicarbonate solution yielded 3-(4'-oxo-2'-thiazolin-2'-yl)-2-phenyl-4-oxotetrahydrothiophene derivatives (V). Thioglycolic acid was found to be added not only to carbon-carbon double bond but also to carbon-nitrogen triple bond and those adducts were cyclized to V.

• Journal of the Korean Chemical Society
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• v.28 no.2
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• pp.135-142
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• 1984

New type dioxygen bridged complexes of palladium were prepared by using $KO_2$ as a source of superoxide ion $(O_2^-)$. The method is completely different from the traditional one which has adopted the oxidative addition of molecular oxygen to transition metal complexes in low valency. It was suggested that the reaction to prepare the dioxygen complexes proceeded via nucleophilic displacement followed by electron transfer reaction. Five new type dioxygen complexes having ${\pi}$-allyl ligand were prepared and characterized by the application of the reaction of $O_2^-$.

• Applied Chemistry for Engineering
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• v.3 no.1
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• pp.64-71
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• 1992

New type dioxygen bridged complexes of palladium were prepared by using $KO_2$ as a source of superoxide ion($O_2{^-}$). The method is completely different from the traditional one which has adopted the oxidative addition of molecular oxygen to prepare the dioxygen complexes. This reaction proceeds via nucleophilic displacement followed by electron transfer reaction. Three new type dioxygen complexes of palladium having amine ligands were prepared and characterized by the application of the reaction of $O_2{^-}$.

• Bulletin of the Korean Chemical Society
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• v.12 no.3
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• pp.301-303
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• 1991

The rate constants for the nucleophilic addition of thiophenol to $\alpha$, N-diphenylnitrone and it's derivatives (p-$OCH_3$, p-Cl, p-$NO_2$) were determined from pH 3.0 to 13.0 by UV spectrophotometry and rate equations which can be applied over a wide pH range were obtained. On the basis of rate equation, general base and substituent effect a plausible addition mechanism of thiophenol to ${\alpha}$, N-diphenylnitrone was proposed: At high pH, the addition of sulfide ion to carbon-nitrogen double bond was rate controlling, however, in acidic solution, reaction was proceeded by the addition of thiophenol molecule to carbon-nitrogen double bond after protonation at oxygen of ${\alpha}$, N-diphenylnitrone.

• Journal of the Korean Chemical Society
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• v.17 no.5
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• pp.363-370
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• 1973

The rate constants of the nucleophilic addition of n-propyl-mercaptan to $\alpha$-cyano-$\beta$-piperonylacrylic acid were determined at various pH and a rate equation which can be applied over wide pH range is obtained. The rate equation reveals that below pH 4.5 the reaction is initiated by the attack of n-propylmercaptan to $\alpha$-cyano-$\beta$-piperonylacrylic acid. At pH 4.5~6.5, however, n-propylmercaptan is added to $\alpha$-cyano-$\beta$-piperonylacrylate ion; at pH 7.04~9.5 the competitive reaction between n-propylmercaptan and n-propylmercaptide ion is anticipated to occur. Above pH 10 the addendum is n-propylmercaptide ion and the acceptor is $\alpha$-cyano-$\beta$-piperonylacrylate ion.

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3543-3548
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• 2010

A kinetic study on nucleophilic displacement reactions of 2-pyridyl X-substituted benzoates 1a-e with potassium ethoxide (EtOK) in anhydrous ethanol is reported. Plots of pseudo-first-order rate constants ($k_{obsd}$) vs. $[EtOK]_o$ exhibit upward curvature. The $k_{obsd}$ value at a fixed $[EtOK]_o$ decreases steeply upon addition of 18-crown-6-ether (18C6) to the reaction mixture up to [18C6]/$[EtOK]_o$ = 1 and then remains nearly constant thereafter. In contrast, $k_{obsd}$ increases sharply upon addition of LiSCN or KSCN. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ has revealed that ion-paired EtOK is more reactive than dissociated $EtO^-$, indicating that $K^+$ ion acts as a Lewis acid catalyst. Hammett plots for the reactions of 1a-e with dissociated $EtO^-$ and ion-paired EtOK result in excellent linear correlation with $\rho$ values of 3.01 and 2.67, respectively. The $k_{EtOK}/k_{EtO^-}$ ratio increases as the substituent X in the benzoyl moiety becomes a stronger electron-donating group. $K^+$ ion has been concluded to catalyze the current reaction by stabilizing the transition state through formation of a 6-membered cyclic complex.