• Bulletin of the Korean Chemical Society
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• 제32권4호
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• pp.1268-1272
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• 2011

The specific rates of solvolysis of phenyl fluorothionoformate (PhOCSF, 1) have been determined in 22 pure and binary solvents at $10.0^{\circ}C$. The extended Grunwald-Winstein equation has been applied to the specific rates of solvolysis of 1 over the full range of solvents. The sensitivities (l = $1.32{\pm}0.13$ and m = $0.39{\pm}0.08$) toward the changes in solvent nucleophilicity and solvent ionizing power, and the $k_F/k_{Cl}$ values are similar to those previously observed for solvolyses of acyl haloformate esters, consistent with the addition step of an additionelimination pathway being rate-determining. The large negative values for the entropies of activation are consistent with the bimolecular nature of the proposed rate-determining step. The results are compared with those reported earlier for phenyl chloroformate and chlorothionoformate esters and mechanistic conclusions are drawn.

• 한국수소및신에너지학회논문집
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• 제19권1호
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• pp.56-63
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• 2008

In this study, thermochemical degradation of hemicellulose by Acetone-Solvolysis, the effects of reaction temperature, conversion yield, degradation properties and degradation products were investigated. Experiments were performed in a tube reactor by varying reaction temperature from $200{\circ}C$ to $400{\circ}C$ at 40 min of reaction time. The liquid products from pyrolysis-liquefaction of hemicellulose contained various kinds of ketones. ketones, as 4-methyl-3-penten-2-one, 3-methylene-2-pentanone, 22,6-dimethyl-2, 5-heptadien-4-one, 4-methyl-2-pentanone, 5-methyl-2-hexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, and bezenes. as 1,4-dimethylbenzene, 1-methyl-2-(1-methylethyl)-benzene, 1,4-dimethyl-2-(2-methylpropyl)benzene, 4-secbutyl-ethyl benzene, could be used as high-octane-value fuels and fuel additives. Combustion heating value of liquid products from thermochemical conversion processes of hemicellulose was in the range of $6,680{\sim}7,170cal/g$. After 40min of reaction at $400{\circ}C$ in Acetone-Solvolysis of hemicellulose, the energy yield and mass yield was as high as 72.2% and 41.2g oil/100g raw material, respectively.

• 대한화학회지
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• 제7권4호
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• pp.264-270
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• 1963

前報에서 誘導한 置換基效果 一般關係式은 溶媒組成에 따르는 常數, Y를 potential energy 項에 代置함으로서 solvolysis 反應에 適用할 수가 있다. 新方程式, $\Delta{\Delta}H^\neq=a'Y+b\Delta{\Delta}S^\neq$, 의 適用性은 文獻에 報告된 35個反應에 對한 直線關係를 調査해 봄으로서 檢討하였다. 結果로 平均 相關係數 0.977을 얻었고, 따라서 이 方程式이 solvolysis反應에 一般的으로 適用됨을 밝혔고, 또 Grunwald-Winstein의 式이 지니는 몇몇 難點을 解決할 수가 있음을 알 수 있었다. enthalypy-entopy 直線效果는 外部 enthalpy와 外部 entropy에 限한 것이며, 嚴格히 말해서 外部 enthalpy entropy 直線效果임을 强調하였다.

• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2413-2417
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• 2011

The specific rates of solvolysis of 1- naphthyl chloroformate (1-NaphOCOCl, 1) and 2-naphthyl chloroformate (2-NaphOCOCl, 2) have been determined in a wide range of solvents at 2.0 and 10.0$^{\circ}C$. These give a satisfactory correlation over the full range of solvents when the extended (two-term) Grunwald-Winstein equation is applied. The sensitivities (l and m-values) to changes in solvent nucleophilicity ($N_T$) and solvent ionizing power ($Y_{Cl}$) are similar to those reported previously for solvolysis of phenyl chloroformate, which has been suggested to proceed through an addition-elimination mechanism with the addition step being rate determining. For four representative solvents, studies were made at several temperatures and activation parameters determined. These observations were also compared with those previously reported for phenyl chloroformates and naphthoyl chlorides.

• Bulletin of the Korean Chemical Society
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• 제19권3호
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• pp.349-353
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• 1998

Solvolysis rates of substituted 2-aryl-1,1-dimethylethyl bromides (1) were determined in a variety of solvents such as aqueous mixtures of ethanol, acetone, 2,2,2-trifluoroethanol, and also mixtures of ethanol and TFE at 25 ℃, 35 ℃, and 45 ℃. The solvent effects were analyzed in terms of Winstein-Grunwald equation. The solvent effects of 1-4-MeO failed to give a single linear correlation against either Y or YCl (YBr), but exhibited a wide split pattern which could not be related to the solvent nucleophilicity. On the other hand 1-4-CH3 and 1-H gave a fairly good linearity. In the case of 1-4-MeO, a fairly good linearity was observed against YΔ defined from the solvolysis of 4-methoxyneophyl tosylate. It is assumed that resonance interaction between reaction site and aryl-π-system operates to give charge delocalization regardless of the different solvolysis mechanisms. The Hammett-Brown treatment of the solvolytic rate constant of compounds 1 was obtained non-linear two separated lines of - 1.06 to - 1.46, suggesting of mechanistic changeover from kc-ks to kΔ on going from electron-withdrawing to electron-donating substituents as a basis of 4-CH3 group.

• 대한화학회지
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• 제30권1호
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• pp.3-8
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• 1986

물-글리세롤, 물-에틸렌 글리콜, 물-이소프로필 알코올 및 물-t-부틸 알코올의 2성분 혼합용매 중에서 cis-$[Co(en)_2ClNO_2]^+$착이온의 가용매 분해반응을 분광광도법으로 연구하였다. 용매의 극성이 커짐에 따라 반응속도도 커지는 경향이 있었으며 반응속도의 대수값과 $\frac{D-1}{2D+1}$값을 도시한 결과 비직선적인 관계를 나타내는 것으로 보아서 용매의 수소결합이나 분산력등의 비정전기적인 상호작용이 지배적으로 작용함을 알 수 있었다. log k와 Grundwald-Winstein의 Y값을 도시한 직선의 기울기와 Kivinen식에서 구한 전이상태에 관여하는 물분자의 수 n값으로부터 실험에 사용한 착물의 가용매 분해반응은 Id메카니즘으로 진행됨을 알았다. 한편 자유에너지 사이클의 결과는 초기상태에서 보다 전이상태에서 용매구조의 효과가 더 큼을 알 수 있었다.

• 대한화학회지
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• 제24권5호
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• pp.342-346
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• 1980

염화디메틸술파모일의 가용매분해반응속도와 활성화파라미터를 메탄올-물, 에탄올-물, 아세톤-물 및 아세토니트릴-물, 혼합용액에서 결정하였따. 각종 용매효과 상관관계에 따르면 이 가용매 분해반응은 전이상태에서 이탈기의 절단이 진전된 $S_n2(dissociative S_n2)$ 메카니즘으로 진행됨을 보여주었다

• 대한화학회지
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• 제15권4호
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• pp.205-209
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• 1971

The thermodynamic parameters for the solvolysis of the p-chlorobenzyl chloride taking place in the various aqueous mixtures were determined. From the application of these data to the formula ${\delta}_M{\Delta}H^{\neq}=a'Y+b{\delta}_M{\Delta}S^{\neq}$ the following conclusion was obtained: That the substrate constant a' differs in different aqueous solvent was found, and using each a' value the solvolysis mechanism of p-chlorobenzyl chloride in each aqueous mixture can be determined.

• 대한화학회지
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• 제10권1호
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• pp.11-14
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• 1966

Ethanol-water mixture 內에서 일어나는 p-nitrobenzyl chloride의 solvolysis反應에 대한 熱力學的 parameter를 구하고 이 data를 ${\delta}_M{\Delta}H^{\neq} = a'Y + b{\delta}_M{\Delta}S^{\leq}$에 適用함으로써 反應常數 a'가 50% 이하의 alcohol solvent에서나 50% 이상의 solvent에서 같다는 것을 알 수 있었다. 즉 water-rich solvent에서나 alcohol-rich solvent에서나 solvolysis反應의 mechanism은 변함이 없다는 것을 알았다.

• 대한화학회지
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• 제17권4호
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• pp.235-239
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• 1973

아세톤-물 혼합용매속에서의 benzoyl chloride치환체들의 solvolysis반응을 속도론적으로 연구하였다. 결과로 물함량이 적은 부분에서는 2분자과정으로 반응이 진행되고 물함량이 큰 부분에서는 1분자과정이 점점 큰 비율을 차지하게됨을 알았다.