• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4403-4407
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• 2011

The nucleophilic substitution reactions of dipropyl chlorothiophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are primary normal ($k_H/k_D$ = 1.11-1.35). A concerted mechanism involving predominant frontside nucleophilic attack is proposed on the basis of the primary normal DKIEs and selectivity parameters. Hydrogen bonded, four-center-type transition state is proposed. The steric effects of the two ligands on the anilinolysis rates of various substrates are discussed.

• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4179-4184
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• 2011

The nucleophilic substitution reactions of bis(2,6-dimethylphenyl) chlorophosphate (5), containing the four ortho-methyl substituents, with X-pyridines are investigated kinetically in MeCN at $65.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a breakpoint at a X = 3-Cl. Unusual positive ${\rho}_X$ (= +5.40) and negative ${\beta}_X$ (= -0.83) values are obtained with the weakly basic pyridines. The pyridinolysis rate of 5 is hundreds times slower compared to that of bis(phenyl) chlorophosphate because of the steric hindrance of the four ortho-methyl substituents in the two phenyl rings. Ion-pair mechanism is proposed and positive ${\rho}_X$ and negative ${\beta}_X$ values are substantiated by an imbalance of the transition state.

• Bulletin of the Korean Chemical Society
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• 제31권9호
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• pp.2571-2574
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• 2010

We investigate the mechanism of $S_NAr$ fluorination reactions under the influence of protic solvents and ions. We find that counterion or protic solvent alone retards the $S_NAr$ reactions, but together they may promote the reaction. In this mechanism, the protic solvent acts on the counterion as a Lewis base, and the nucleophile reacts as an ion pair. We also show that an anion (mesylate) may exhibit catalytic effects, suggesting the role of ionic liquids for accelerating the $S_NAr$ reactions.

• Bulletin of the Korean Chemical Society
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• 제35권7호
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• pp.2077-2080
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• 2014

Cobalt-immobilized SBA-15 6a-c was synthesized from alkyne-attached SBA 5a-c by the reaction with $Co_2(CO)_8$ in toluene. Alkyne group was introduced into amino SBA-15 (4) by imine-linkage or substitution with propargyl bromide to afford iminoalkyne 5a and aminoalkyne 5b, respectively. Meanwhile, alkyne 5c was prepared in one-step by reacting triethoxysilyl hexyne with SBA-15. Dicobalt-complexes 6a-c were characterized by means of FT-IR, solid-state NMR and elemental analysis.

• 환경위생공학
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• 제20권4호통권58호
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• pp.38-44
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• 2005

Cryptand resins were synthesized with 1-aza-15-crown-5 macrocyclic ligand attached to styrene divinylbenzene (DVB) copolymer with crosslink of $1\%,\;2\%,\;5\%\;and\;10\%$ by substitution reaction. The synthesis of these resins was confirmed by content of chlorine, element analysis, and IR-spectrum. The effects of pH, time, dielectric constant of solvent and crosslink on adsorption of uranium$(UO_2^{2+})$ ion were investigated. The uranium ion was showed fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in increasing order uranium$(UO_2^{2+})$ > zinc$(Zn^{2+})$ > samarium$(Sm^{3+})$ ion. The adsorption was in order of $1\%>2\%>5\%>10\%$ crosslink resin and adsorption of resin decreased in proportion to order of dielectric constant of solvents.

• 한국재료학회지
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• 제26권1호
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• pp.1-7
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• 2016

The graphene oxides (GOs) were tested as a fluorescent quencher in the field of DNA-diagnostics. The various suspensions of GO nanoplates were prepared by changing the synthesis conditions. The suspensions were stable for at least 6 weeks by differing degrees of functionalization of various oxygen-containing groups of atoms. Depending on the properties of GO nanoplates, their fluorescent quenching abilities, which were determined by the amount of the tagged immobilized oligonucleotide, were also changed. GO suspension synthesized at $75^{\circ}C$ of reaction mixture showed the fluorescent quenching of 16.39 nmol/mg, which would be a potential substitution of molecular fluorescent quencher in test-systems for DNA-diagnostics.

• Macromolecular Research
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• 제13권3호
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• pp.229-235
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• 2005

Various alkoxyamine initiators for nitroxide mediated radical polymerization (NMRP) were prepared in high yields by a simple substitution reaction of nitroxide anions with benzyl bromide. The required nitroxide anions were easily generated by treating either nitroxide free radicals or hydroxy amine with an alkali metal such as sodium or potassium in THF. This method is both practical and efficient, since the ionic conditions prevent other side reactions from occurring, such as the self-coupling or oligomerization reactions that are observed in the case of radical trapping conditions. To demonstrate the utility of the resulting alkoxyamine initiators, end- and telechelic-alkoxyamine PEG macroinitiators derived from the alkoxyamines were synthesized by a simple chemical modification, and used for the preparation of PEG-b-PS and PS-b-PEG-b-PS block copolymers by NMRP.

• 환경위생공학
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• 제23권1호
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• pp.57-65
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• 2008

Resins were synthesized with 1-aza-15-crown-5 macrocyclic ligand attached to styrene(dangerous matter) divinylbenzene(DVB) copolymer with crosslink of 1, 2, 6 and 15% by substitution reaction. The synthesis of these resins was confirmed by content of chlorine, element analysis, and IR-spectrum. The effects of pH, time and crosslink on adsorption of metal ion　from water fire extinguishing agent by the synthetic resin adsorbent were investigated. The metal ion was showed fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in water was in increasing order of $Mg^{2+}>Al^{3+}>Pb^{2+}$. The adsorption was in the order of 1, 2, 6, and 15% crosslink resin.

• 대한화학회지
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• 제24권5호
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• pp.337-341
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• 1980

페놀계 산화방지제들의 라디칼 생성반응을 분자궤도론적으로 고찰하였다. 결과로 페놀계 산화방지제는 전자공여성인 알킬기의 치환으로 phenoxy 라디칼 생성이 용이해지며, 따라서 산화방지 능력이 증가함을 알았다. 이것은 electrophilic 라디칼의 작용으로 형성되는 양이온을 안정화시켜 주기 때문임을 밝혔다

• Carbon letters
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• 제4권4호
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• pp.175-179
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• 2003

It is well established that halogenated fullerene derivatives act as synthetic intermediates for further substitution via replacement with nucleophlies. In the present work, systematic studies were carried out on the synthesis of bromofullerenes under different experimental conditions. The effect of reaction time on the product formed was observed. We observed the formation of new compound of bromofullerenes in a different stoichiometric ratio i.e., $C_{60}Br_{14}$; in addition to previous reported bromofullerenes in the stoichiometric ratio of $C_{60}Br_6$, $C_{60}Br_8$, and $C_{60}Br_{24}$. The new derivative of bromofullerene was isolated and well characterized by various analytical techniques like FT-IR, TGA, DSC, and elemental analysis. In this paper, detail of the synthesis and characterization of the bromofullerene prepared are described. The yields obtained were better than those reported previously.