• Bulletin of the Korean Chemical Society
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• 제7권4호
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• pp.314-316
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• 1986

Methods for the preparation of p-nitrocalix[4]-arene via the direct substitution reaction of the p-tert-butylcalix[4]arene which is readily available with high yield from the base-induced direct condensation reaction procedure are described.

• Bulletin of the Korean Chemical Society
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• 제20권3호
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• pp.325-328
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• 1999

In the reactions of the enolates of various 2-piperidineacetates with iodomethane or trisyl azide, the anti isomer was always predominant over the syn one, independent of the stereochemistry of the piperidineacetates. The piperidineacetates having OTBDMS moiety at C5 proceeded more diastereoselectively than the compounds without the substituent. The diastereoselectivity could be explained by perpendicular model for the electrophilic substitution reaction.

• 대한화학회지
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• 제41권1호
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• pp.22-46
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• 1997

25℃와 35℃에서 메탄올-아세토니트릴 혼합용매계에 대한 할로겐화 펜아실과 피리딘 치환체와의 친핵성치환반응을 속도론적으로 연구하였다. 전이상태 파라미터인 ΔH≠와 ΔS≠ 및 Brosted β값으로 보아 $S_N2$반응 메카니즘을 예상할 수 있었고, 이탈기 변화에 따른 QM모형의 적용으로 이들 반응의 전이상태 역시 생성물 닮은 구조임을 알 수 있었다.

• 청정기술
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• 제11권2호
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• pp.105-116
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• 2005

본 연구는 NaOH 용액에 의한 머서화(mercerization) 반응과 모노클로로아세트산에 의한 에테르화 반응에 의해 carboxymethylcellulose(CMC)를 제조하고 각 제조단계에서의 반응시간, 시약 농도, 온도 등을 변수로 설정하여 결과물에 대한 영향을 고찰하였다. 제조된 샘플을 용해도와 카르복실기의 치환도를 통해 분석하였으며 부직포로서의 응용을 위해 제조된 수용성 섬유의 인장강도를 알아보았다. 섬유의 표면 변화는 SEM(scanning electron microscope) 사진을 통해 알아보았다. 제조된 섬유는 30분 이내에 80% 이상 용해되었으며 반응시간이나 반응 온도보다 시약의 농도에 의한 영향이 더욱 컸다. 또한 용해도가 80% 이상이었던 시편은 0.6 ~ 0.7의 치환도를 보였으며 모노클로로아세트산의 농도의 영향이 가장 크며 용해도가 증가할수록 치환도가 증가하는 경향을 보였다.

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2343-2353
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• 2007

We report the application of time-dependent density functional theory (TDDFT) to the calculation of potential energy profile relevant to the excited state intramolecular proton transfer (ESIPT) processes in title molecules. The TDDFT single point energy calculations along the reaction path have been performed using the CIS optimized structure in the excited state. In addition to the Stokes shifts, the transition energies including absorption, fluorescence, and 0-0 transition are estimated from the TDDFT potential energy profiles along the proton transfer coordinate. The excited state TDDFT potential energy profile of SA and 3ASA resulted in very flat function of the OH distance in the range ROH = 1.0-1.6 A, in contrast to the relatively deep single minimum function in the ground state. Furthermore, we obtained very shallow double minima in the excited state potential energy profile of SA and 3ASA in contrast to the single minimum observed in the previous work. The change of potential energy profile along the reaction path induced by the substitution of electron donating groups (-NH2 and -OCH3) at different sites has been investigated. Substitution at para position with respect to the phenolic OH group showed strong suppression of excited state proton dislocation compared with unsubstitued SA, while substitution at ortho position hardly affected the shape of the ESIPT curve. The TDDFT results are discussed in comparison with those of CASPT2 method.

• Bulletin of the Korean Chemical Society
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• 제18권8호
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• pp.868-873
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• 1997

Nucleophilic substitution reactions of 1-phenylethyl chlorides (1-PEC; YC6H4CH(CH3)Cl) with phenoxides (XC6H4O-) and thiophenoxides (XC6H4S-) are investigated theoretically using the PM3 method. The Bronsted α and β values are greater for the phenoxides indicating a more advanced reaction in the transition state (TS) than for the thiophenoxides. This is supported by a greater magnitude of ρX (- 6.4 ∼ - 7.4) and ρXY (- 0.76) for the phenoxides than for the thiophenoxides (ρX = - 3.6 ∼ - 4.4 and ρXY = - 0.60). The percentage bond order changes, %Δn≠, suggest that the extents of bond making and breaking are similar for the phenoxides and hence the TS is symmetrical, but bond making is somewhat greater than bond cleavage for the thiophenoxides indicating an unsymmetrical TS. The reactions in the gas phase for both nucleophile series proceed by a SN2 mechanism with a tight TS and negative charge development on the reaction center carbon, Cα. The reactions in water investigated with model systems of benzyl and 1-phenylethyl chlorides using the Cramer-Truhlar solvation model (PM3-SM3) indicate that the reactions of 1-PEC are far more complex due to enhanced stabilization of the carbocation by the methyl substitution for a benzylic hydrogen.

• Bulletin of the Korean Chemical Society
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• 제14권6호
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• pp.669-673
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• 1993

The CO substitution reactions of the complex, $Cp(S-2,4-Me_2C_5H_5)CrCo$ with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. From the reaction rates, it was suggested that the CO substitution reaction took place by first-order (dissociative) pathway. Activation parameters in decaline were ${\Delta}H^{\neq}\;=\;22.0\;kcal{\cdot}mol^{-1}$, ${\Delta}S^{\neq}=\;-3.8cal{\cdot}mol^{-1}{\cdot}K^{-1}$. Unusually low value of ${\Delta}S{\neq}$ suggests an ${\eta}^5-S{\to}{\eta}^5-U$ conversion of the pentadienyl ligand. This suggestion was confirmed by the Extended-Huckel molecular orbital (EHMO) calculations, which revealed that the total energy of $Cp(S-2,4-Me_2C_5H_5$)CrCO is about 0.42 kcal/mol more lower than that of $Cp(U-2,4-Me_2C_5H_5)CrCO$ and the energy of $[Cp(U-2,4-Me_2C_5H_5)Cr{\cdots}CO]^{\neq} $ transition state is about 2.43 kcal/mol lower than that of $[Cp(S-2,4-Me_2C_5H_5)Cr{\cdots}CO]^{\neq}$ transition state.

• Bulletin of the Korean Chemical Society
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• 제14권2호
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• pp.207-211
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• 1993

The CO substitution reactions in the complex, $Cp(S-C_5H_7)CrCO$ with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. From the reaction rates, it was suggested that the CO substitution reaction takes place by first-order (dissociative) pathway. Activation parameters in decaline are ${\Delta}H^{\neq}\;=\;24.58\;kcal\;{\cdot}\;mol^{-1},\;{\Delta}S^{\neq}\;=\;3.05 cal\;{\cdot}\;mol^{-1}{\cdot}K^{-1}$. Unusually low value of ${\Delta}S^{\neq}$ suggests an ${\eta}^5-S\;{\to}\;{\eta}^5-U$ conversion of the pentadienyl ligand. This was confirmed by the extended-Huckel molecular orbital (EHMO) calculations, which revealed that the total energy Of $Cp(S-C_5H_7)CrCO$ is about 6.84 kcal/mol more stable than that of $Cp(U-C_5H_7)CrCO$ and the energy of $[Cp(U-C_5H_7)CrCO^{\neq}$ transition state is about 4.25 kcal/mol lower than that of $[Cp(S-C_5H_7)Cr]^{\neq}$ transition state.

• 대한화학회지
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• 제29권5호
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• pp.478-481
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• 1985

염화 알칸술포닐과 파라 치환된 아닐린간의 친핵성 치환반응을 메탄올-아세토니트릴 혼합용매하에서 연구하였다. 기질의 반응성, 친핵체의 치환기효과 및 용매효과로 부터 반응 메카니즘이 $S_N2$임을 알았다. i-PSC의 경우 메탄올 조성이 커짐에 따라 전이상태가 더 loose해 짐을 알았다.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 춘계학술발표대회
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• pp.9.2-9.2
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• 2011

Ultrathin polyelectrolyte (PE) multilayer films prepared by the versatile layer-by layer (LbL) assembly method have been utilized for the preparation of light-emitting diodes, electrochromic, membrane, and drug delivery system, as well as for selective area patterning and particle surface modification because the various materials with specific properties can be inserted into the film with nano-level thickness irrespective of the size or the shape of substrate. Since the introduction of the LbL technique in 1991 by Decher and Hong, various hydrophilic materials can be inserted within LbL films through complementary interactions (i.e., electrostatic, hydrogen-bonding or covalent interaction). In this study, it is demonstrated that LbL SA multilayer films based on nucleophilic substitution reaction can allow the preparation of the highly efficient magnetic and/or optical films and nonvolatile memory devices.