• 대한화학회지
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• 제10권1호
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• pp.15-17
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• 1966

Phenol과 각 종 Dimethylaniline(DMA)간의 수소결합을 Infrared Spectrophotometer로 연구하였다. 일반으로 DMA는 n-donor 및 ${\pi}$-donor의 2중 역활을 하나 주로 n-donor로 작용하며 phenol의 O-H stretching frequency의 shift(${\Delta}{\nu}$)는 DMA의 basicity에 비례하였고 (${\Delta}{\nu}$) 와 Hammett의 σcontant사이에는 linearity가 성립함을 알았다.

• Bulletin of the Korean Chemical Society
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• 제18권4호
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• pp.395-401
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• 1997

The substituent effects in the gas-phase rearrangement of carbenes to ketenes involved in the Wolff reaction have been investigated theoretically using the AM1 method. In the initial state, carbene, there is a relatively strong vicinal n-σ* interaction between the lone pair (n) and carbonyl group (σ*). In the bridged transition state (TS), electronic charge is transferred from the migrating ring (Z-ring) toward the nonmigrating ring (Y-ring). The carbenes are stabilized by an electron donor Y (δσY < 0) whereas the TS is stabilized by an electron acceptor Y (δσY > 0). Multiple regression analysis of log (kYZ/kHH)(=-δΔG≠/2.3RT) leads to a relatively large negative cross-interaction constant, ρYZ=-0.53, log (kYZ/kHH)=2.96 σY--1.40 σZ-0.53 σY-σZ reflecting an extensive structural change in the transition state due to the stabilization of the initial state by the vicinal n-σ* overlap. When the solvent (water) effects are accounted for by the SM2.1 model of the Cramer and Truhlar method, the magnitude of all the selectivity parameters, ρY-, ρZ and ρYZ (=-0.66) are increased.

• Bulletin of the Korean Chemical Society
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• 제9권3호
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• pp.157-160
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• 1988

The rates of hydrolysis of N-(benzenesulfonyl) benzimidoyl chlorides (p-H, $p-CH_3,\;p-CH_3,\;p-NO_2\;and m-NO_2$) have been measured by UV spectrometry in 60% methanol-water at $25^{\circ}C$ and a rate equation which can be applied over wide pH range was obtained. Below pH 7.00, the substituent effect on the hydrolysis rate of N-(benzenesulfonyl) benzimidoyl chloride was found to conform to the Hammett ${\sigma}$ constant with ${\rho}$ = -0.91, whereas above pH 9.00, with ${\rho}$ = 0.94. On the basis of the rate equation obtained and the effect of solvent, substituents and salt, the following reaction mechanism were proposed; below pH 7.00, the hydrolysis of N-(benzenesulfonyl) benzimidoyl chloride proceeds by $S_N1$ mechanism, however, above pH 9.00, the hydrolysis is initiated by the attack of the hydroxide ion and in the range of pH 7.00-9.00, these two reactions occur competitively.

• 공업화학
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• 제26권6호
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• pp.698-705
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• 2015

유연격자로써 부틸렌 또는 1-메틸부틸렌기를 갖는 두 시리즈의 대칭성 이메소젠 액정 화합물을 합성하였으며, 이 화합물들의 메소젠 그룹은 말단에 치환기를 포함하고 있는 아조벤젠기로 되어 있다. 합성된 화합물의 화학구조와 열적 성질, 액정성 및 광화학 성질은 FT-IR, $^1H-NMR$, 시차주사열량측정(DSC), 편광현미경(POM), 그리고 UV-visible 분광분석법에 의하여 조사되었다. 화합물 P-H, P-F, $P-OC_6H_{13}$는 단방성 액정성을, 나머지 화합물들은 양방성 액정성을 나타내었고, 유연격자로써 부틸렌기를 갖는 화합물이 1-메틸부틸렌기를 갖는 화합물들보다 넓은 액정상 온도구간과 높은 열전이온도를 나타내었으며, Hammett 치환기 상수의 절댓값이 큰 화합물이 높은 열전이 온도와 액정안정성을 나타내었다. 또한, UV 광 조사 시, 아조 메소젠 그룹의 말단 치환기가 최대흡수파장(${\lambda}_{max}$) 및 광이성화 속도(K)를 결정하는 중요한 요인임을 알 수 있다.

• Applied Biological Chemistry
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• 제42권1호
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• pp.68-72
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• 1999

비스 방향족 ${\alpha},{\beta}$-불포화 케톤 유도체들중 비교적 양호한 farnesyl protein transferase(FPTase) 저해활성을 나타낸 1,3-diphenylpropenone 유도체들에 대하여 in vitro에서 사람의 종양세포주인 A549(폐암)를 비롯하여 SKMEL-2(피부암), HCT-15(결장암), SKOV-3(자궁암) 및 XF-498(뇌암)등 5종의 종양 세포주에 대한 세포독성을 측정하고 기질분자의 치환기 변화에 따른 구조-활성관계(SAR)를 Free-Wilson방법과 Hansch방법으로 검토하였다. 전체적으로 styryl group중의 Y-치환기보다 benzoyl group중의 X-치환기가 세포독성에 큰 영향(X>Y)을 미쳤으며, 2,4-dichloro 치환체, 15와 2,4-dimethyl 치환체, 16이 모든 종양 세포주에 대하여 가장 높은 세포독성을 나타내었다. 또한, X-치환기는 주로 적정값$({\sigma}_{opt}=0.22{\sim}0.29})$의 약한 전자끌게$({\sigma}>0)$에 의한 전자전달 효과$({\sigma})$에 의존적으로 세포독성이 증가하는 반면에 Y-치환기는 logP, $B_1$ 및 R상수 등 다양한 요소로 영향을 미치고 있음을 알았다.

• Reproductive and Developmental Biology
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• 제31권1호
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• pp.15-20
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• 2007

가축의 번식과 수요를 조절할 수 있는 생물학적 자극 통제 수단으로 새로운 돼지 페르몬성 냄새 물질를 탐색하고자, 기질 분자로서 2-cyclohexyloxytetrahydrofurane (A), 2-phenoxytetrahydrofurane (B) 유도체들의 설명인자인 물리화학 파라미터와 돼지 페로몬의 수용체 (pOBP)에 대한 결합 친화력 상수($p[Od.]_{50}$) 간의 2D-QSAR 모델을 유도하고 검토하였다. 2D-QSAR 모델은 결합 친화력 상수를 약 96.4% 설명하는 매우 양호한 모델($r^{2}=0.964$)로서 분자내 치환기의 소수성 (SL) 상수에 관한 적정값이 $(SL)_{opt.}=1.418$일 때 가장 높은 결합 친화력을 나타냄을 알았다. 그러므로 분자내 치환기의 소수성 인자가 결합 친화력 상수에 가장 큰 영향을 미치는 중요한 요소이었다.

• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1579-1582
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• 2009

The reaction rates of 4-X-2,6-dinitrochlorobenzenes (X = $NO_2,\;CN,\;CF_3$) with Y-substituted pyridines (Y = 3-$OCH_3,\;H,\;3-CH_3,\;4-CH_3$) in methanol-acetonitrile mixtures were measured by conductometry at 25 ${^{\circ}C}$. It was observed that the rate constant increased in the order of X = 4-$NO_2\;>\;4-CN\;>\;4-CF_3$ and the rate constant also increased in the order of Y = 4-$CH_3\;>\;3-CH_3\;>\;H\;>\;3-OCH_3$. When the solvent composition was varied, the rate constant increased in order of MeCN > 50% MeOH > MeOH. The electrophilic catalysis by methanol may be ascribed to the formation of hydrogen bonds between alcoholic hydrogen and nitrogen of pyridines in ground state. Based on the transition parameters, ${\rho}_S,\;{\rho}_N,\;{\beta}_Y,\;{\rho}_{XY}$ and solvent effects, the reaction seems to proceed via $S_N$Ar-Ad.E mechanism. We also estimated the isokinetic solvent mixtures (${\rho}_{XY}$ = 0) based on cross-interaction constants, where the substituent effects of the substrate and nucleophile are compensated.

• Bulletin of the Korean Chemical Society
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• 제26권12호
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• pp.1981-1985
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• 2005

Kinetic studies have been performed for alkaline hydrolysis of a series of [(methoxy)(p-substituted styryl)carbene]pentacarbonyl chromium(0) complexes ($(CO)_5$Cr=$C(OCH_3)CH=CHC_6H_4X$, X = p-$OCH_3$, p-$CH_3$, H, p-Cl, p-$NO_2$). Second-order rate constants $(k_{{OH}^-})$ for the alkaline hydrolysis in 50% acetonitrile-water(v/v) were determined spectrophotometrically at various temperatures. At a low pH region (pH < 7.5), the observed rate constant $(k_{obs})$ remained constant with a small value, while in a high pH region (pH > 9.5), $k_{obs}$ increases linearly with increasing the pH of the medium. The second-order rate constants $(k_{{OH}^-})$ increase as the substituent X changes from a strong electron donating group to a strong electron withdrawing group. The Hammett plot obtained for the alkaline hydrolysis is consisted of two intersecting straight lines. The nonlinear Hammett plot might be interpreted as a change in the rate-determining step. However, the fact that the corresponding Yukawa-Tsuno plot is linear with $\rho$ and r values of 0.71 and 1.14, respectively indicates that the nonlinear Hammett plot is not due to a change in the rate-determing step but is due to ground-state stabilization through resonance interaction. The positive $\rho$ value suggests that nucleophilic attack by $OH^-$ to form a tetrahedral addition intermediate is the rate-determining step. The large negative ${\Delta}S^\neq$ value determined in the present system is consistent with the proposed mechanism.

• 대한화학회지
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• 제23권1호
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• pp.37-41
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• 1979

Benzyl m-nitrobenzenesulfonate와 N,N-dimethylaniline類와의 反應速度를 아세톤 溶媒에서 電氣傳導度法으로 測定하였다. N,N-디메틸아닐린의 反應性에 關한 置換基效果와 直線 自由에너지 關係를 考察하였다. 反應速度常數 k는 2.55∼487 $10^{-4}l{\cdot}mol^{-l}{\cdot}sec^{-1} (35^{\circ}C)$였으며 置換基가 電子를 주는 能力이 클수록 反應은 빨랐다. Hammett 도시에서 置換基常數 ${\sigma}$와 ${\sigma}p$-MeO = -0.35의 새로운 값을 使用했을때 ${\rho}$ = -1.37의 좋은 直線이 얻어졌다. 本反應의 경우 r값은 브롬화벤질에 比해 큰 값을 가졌다. Bronsted 圖示에서 溶媒效果에 基因된 p-MeO基를 除外하고는 좋은 直線이 얻어졌으며 C${\cdot}{\cdot}{\cdot}$O 結合의 쪼개짐이 結合 形成보다 優先的인 $S_N2$ 轉移狀態를 갖는다고 推定된다.

• 상하수도학회지
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• 제32권1호
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• pp.27-35
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• 2018

The stability of liquid ferrate(VI) produced by an innovative method was confirmed and the degradation characteristics of cyclic compounds(Benzene, Aniline, Toluene, 1,4-Dioxane) by liquid ferrate(VI) were investigated under the same reaction conditions. When it was compared with the ferrate manufactured by the wet oxidation method, the liquid ferrate was more stable. And the stability of liquid ferrate was tested at the storage temperature. As a result, only 17.7% of liquid ferrate(VI) has decomposed at the storage temperature($4^{\circ}C$) for 28 days. Among the cyclic compounds, the aniline was rapidly degraded compare to other cyclic compounds, which seems to be due to the electron-donating ability of the substituent, $-NH_2$ group. Especially, when 1,4-dioxane was compared with benzene, the decomposition rate of 1,4-dioxane was lower than that of benzene, suggesting that oxygen atoms hinder the electrophilic reaction. Among 4 cyclic compounds, it was observed that aniline has the highest rate constant than those of other cyclic compounds.