• 폴리머
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• 제25권6호
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• pp.796-802
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• 2001

나프탈렌을 측쇄로 갖는 새로운 폴리벤즈이미다졸 단량체을 합성하고, 이 단량체를 친핵치환반응에 의해 중합하였다. 4-Methoxy-N-naphthyl-1,2-phenylenediamine과 4-fluoro-benzoyl chloride의 반응으로 N-(4-fluorobenzoyl)-4-methoxy-N'-naphthyl-1,2-phenyl-enediamine이 합성되었고 이로부터 고리화반응 및 demethylation에 의해 단량체인 2-(4-fluoro-benzoyl)-5-hydroxy-1-naphthylbenzimidazole이 얻어졌다. 중합반응은 potassium carbonate를 함유하는 N-cyclohexyl-2-pyrrolidinone (CHP)에서 행해졌다. 생성된 폴리벤즈이미다졸은 N-methyl-2-pyrrolidinone (NMP)에 용해되었고 0.38 dL/g (NMP at $30^{\circ}C$)의 대수 점도를 가졌다. 유리전이온도($T_g$)는 $270^{\circ}C$였고 열중량분석에서 5% 중량감소를 보이는 온도는 질소분위기에서는 $550^{\circ}C$, 공기중에서는 $540^{\circ}C$였다.

• 한국세라믹학회지
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• 제37권5호
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• pp.466-472
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• 2000

As cathode materials of LiMn2O4-based lithium-ion secondary batteries, Li(Mn1-$\delta$M$\delta$)2O4 (M=Ni and Co, $\delta$=0, 0.05, 0.1 and 0.2) materials which Co and Ni are substituted for Mn, were syntehsized by the solid state reaction at 80$0^{\circ}C$ for 48 hours. No second phases were formed in Li(Mn1-$\delta$M$\delta$)2O4 system with substitution of Co. However, substitution of Ni caued to form a second phase of NiO when its composition exceeded over 0.2 of $\delta$ in Li(Mn1-$\delta$M$\delta$)2O4. As the results of charging-discharging test, the maximum capacity of Li(Mn1-$\delta$M$\delta$)2O4 appeared in $\delta$=0.1 for both Co and Ni. Also, Li(Mn1-$\delta$M$\delta$)2O4 electrode showed higher capacity and better cycle performance than LiMn2O4.

• 대한화학회지
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• 제41권12호
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• pp.666-671
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• 1997

Pseudosaccharin pyridinemethyl ether들의 광화학반응을 검토하였다. Pseudosaccharin 2-pyridinemethyl ether, pseudosaccharin 4-pyridinemethyl ether, pseudosaccharin 3-pyridinemethyl ether 모두 빛조사에 의해 신속히 반응하였으며 반응은 pseudosaccharyl 산소원자와 pyridinemethyl 탄소원자 사이의 결합 균형분해과정과 용매로 사용한 메탄올에 의한 pyridinemethoxy기의 들뜬상태 친핵성 치환과정을 거쳐 진행됨을 관찰하였다. 이들 두 과정은 반응용액 중에 존재하는 산소분자에 의해 소멸되지 않았다. 광생성물 수율로 볼 때 결합균형분해과정이 들뜬상태 친핵성 치환과정 보다 우세함을 알았다.

• 대한화학회지
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• 제51권3호
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• pp.244-250
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• 2007

항암작용이 기대되는 일련의 새로운 6-allylthio-3-aminopyridazine 유도체를 allylthiolation, amination을 이용하여 합성하였다. 피리다진 핵은 hydrazine monohydrate와 maleic anhydride의 축합반응으로 제조하였다. 3,6- Dichloropyridazine은 3,6-dihydroxypyridazine을 POCl3에 가하여 합성하였다. 6-Allythio-3-chloropyridazine은 3,6- dichloropyridazine에 allylmercaptan과 sodium hydroxide을 이용하여 얻었다. Morpholine, piperazine, pyrazole, imidazole, pyrrolidine, piperidine, perhydroazepine 및 perhydroazocine와 같은 질소 친핵체를 갖는 hetero환을 피리 다진 환의 3번 위치에 도입시켜 6-allylthio-3-aminopyridazine 합성하였다. 이 과정은 아민 친핵체의 친핵성 치환반응 으로 n-buthanol에서 NH4Cl를 가하고 24~48시간 동안 환류시켜 진행하였다.

• 대한화학회지
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• 제31권2호
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• pp.123-132
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• 1987

반경험적 분자궤도함수법인 MNDO방법을 사용하여 $SH^-,\;CN^-$ 그리고 $OH^-$와 메틸티오시아네이트(MTC)의 친핵성치환반응을 연구하였다. 각 친핵체에 대해 MTC세반응중심의 계산된 포텐샬에너지곡면(Intrinsic term)과 전이상태에서의 친핵체의 음전하크기(Solvent term)을 고려하여 가스상과 용액상에 대한 선택성을 논의하였다. 결과로써$SH^-$에 대해서는 선택성의 두 성분 모두 4-methylbenzylthiocyanate (4-MBTC)에 대해 얻어진 실험결과와 일치한반면 $CN^-$의 경우에는 고유항(Intrinsic term)의 선택성만이 일치하였고 $OH^-$의 경우에는 두 항중 어느것도 실험결과로 얻은 선택성과 일치하지 않았다. 정류점에서 모든 종에 대한 MNDO최적화된 구조들을 밝혔다.

• Bulletin of the Korean Chemical Society
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• 제25권2호
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• pp.203-206
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• 2004

The kinetics of reactions between Z-aryl thiophene-2-carbodithioates and X-pyridines in acetonitrile at 60.0 $^{\circ}C$ have been investigated. The Bronsted plots obtained for the pyridinolysis of aryl thiophene-2-carbodithioates are curved, with the center of curvature at $pK_a$ ~ 5.2 ($pK_a^{\circ}$). The Bronsted plots for these nucleophilic reactions show a change in slope from a large ( ${\beta}_X{\cong}$0.78-0.87) to a small ( ${\beta}_X{\cong}$0.33-0.35) value, which can be attributed to a change in the rate-determining step from breakdown to formation of a zwitterionic tetrahedral intermediate in the reaction path as the basicity of the pyridine nucleophile increases. A clear-cut change in the crossinteraction constants, ${\rho}_{XZ}$, from +0.92 to -0.23 supports the proposed mechanistic change. The breakpoint at $pK_a$ = 5.2 for R = thiophene ring in the present work is in agreement with those for the pyridinolysis of R = Me and 2-furyl, and attests to the insignificant effects of acyl group, R, on the breakpoint.

• 대한화학회지
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• 제27권1호
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• pp.1-8
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• 1983

단일양성자성용매(메탄올, 에탄올, 1-프로판올)와 단일반양성자성용매(아세톤, 아세토니트릴, 아세토페논, 니트로벤젠) 및 이성분혼합용매계(메탄올-아세톤, 메탄올-아세토니트릴, 메탄올-벤젠)에서 염화나프탈렌술포닐과 피리딘의 친핵성치환반응에 미치는 용매효과를 전기전도도법으로 연구하였다. 단일양성자성용매의 반응속도상수는 유전상수가 큰 쪽에서 크게 관측되었고 반양성자성 용매의 반응속도상수는 유전상수가 큰 쪽에서 작게 나타났다. 아세토니트릴은 유전상수가 큰 반양성자성용매인데도 다른 반양성자성용매들보다 속도상수가 크게 관측되었다. 본 친핵성치환반응에서 용매효과는 ${\pi}^{\ast}$가 중요하고 염소이온의 이탈효과보다 수소결합형성이 전이상태를 안정화시키는데 기여함을 알 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제15권2호
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• pp.161-167
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• 1994

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates (3) with alkali metal ethoxides ($EtO^-M^+$) and butane-2,3-dione monoximates ($Ox^-M^+$) in ethanol at $25^{\circ}C$. The reactivity of the alkali metal ethoxides decreases in the order $EtO^-K^+> EtO^- > EtO^-Li^+$, indicating that $K^+$ ion behaves as a catalyst and $Li^+$ ion acts as an inhibitor for all the substrates studied. For the corresponding reactions of 3 with Ox^-M^+$, $Li^+$ ion also exhibits inhibitory effect for all the substrates, while, $K^+$ ion shows catalytic or inhibitory effects depending on the nature of substituents on the acyl and phenyl moieties. A study of substituent effect on rate has revealed that both EtO^- $and Ox^-$ systems have the same reaction mechanism. The different behavior shown by $K^+$ ion for the reaction of 3 with $EtO^-$ and $Ox^-$ would be attributed to a difference in charge polarization of S=O bond in the transition state between the two systems and/or a change in conformation of Ox^-K^+$.

• 한국산업융합학회 논문집
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• 제3권1호
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• pp.77-82
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• 2000

The stereoselective ligand exchange reaction of trans-$[Co(SS-epm)Cl_2]^+$ and racemic propane-1,2-diamine (rac-pn) produces the complex that is identified as $[CO(N)_6]^{3+}$ type of $[Co(SS-epm)(pn)]^{3+}$ by absorption spectrum. It is conceivable that the reaction mechanism involves substitution and isomerization. The calculated and experimentally determined ratios of the complexed enantiomeric substrates at equilibrium were as follows: $[Co(SS-epm)(pn)]^{3+}$,calcd 32 % / 68 %, exptl 19 % / 81 % R-pn / S-pn. It has been shown that the employment of molecular mechanics calculations as a predictive tool may lead to the design of chiral complexes that may be applied to the separation of racemic mixtures of simple bidentate ligands.

• 한국식품영양학회지
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• 제16권4호
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• pp.321-327
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• 2003

The reaction rates of 4-ethyl pyridine with p-methyl benzylbromide have been measured by conductometry in acetonitrile, and the rate constants of these reactions are determined in accordance with various temperatures (20, 25, 30$^{\circ}C$) and pressures (1, 200, 500, 1000 bar). The rate constants increased with the higher pressure and temperature. The activation energies and activation parameter values of these reactions are calculated by determination of the rate constants the same. The activation volume, activation compressibility coefficient and the activation entropy are all negative. The result of kinetic studies for the pressure show that this reaction proceeds in typical bimolecular nucleophilic substitution reaction.