山椒油의 利用에 關하여

呂壽東 慶北工業專門大學 1967 論文集 Vol.4 No.-

The "Sanchho oil" is contained in the fruits of "Fagara mandhaurica Honda Ver. inermis Nakai" which belong to the "Rutaceae". and its contents is 10.5 percent or so. the sanchho trees bloom in early summer and ripen their fiuits in october, which are dark brown globular form, their diameter is 0.5cm or so. Their distrbuting zone in Korea ranges throughout the country. The sanchho oil has too offensive ador for edibles, and therefore I have come to following conclusions through the research for its industirial utility. 1. Qualities: S.V: 197.3 I.V: 125.9 resemble to soybean oil as semidrying oil 2. About 310℃ of reaction heat is needed for Heat polymerization and it has increased the acid value owing to the decomposition. 3. The Oxidation polymerization of the oil by catalyst is easily proceeded at 150℃, but its color will be condensed, whoch is its the only drawback. 4. The addition of maleic anhydride is most adequate by acting around 7.5% at 230℃ 5. The esterification of the maleinized pil has been produced some A.V15.60 of esterified oil by acting around 4.7% of glycerin at 230℃ for an hour and fifteen. such processings as shown in No3,4,5 are Satisfactory method for obtaining paint Vehicle.

Benzyl Arenesulfonate와 N,N-디메틸아닐린과의 反應 (第3報). Benzyl Arenesulfonate의 難脫基의 置換基 效果

여수동,Soo-Dong Yoh 대한화학회 1975 대한화학회지 Vol.19 No.6

Benzyl arenesulfonate와 디메틸아닐린을 아세톤 중에서 $35^{\circ}C$로 반응시켜 離脫基의 置換基效果를 硏究한 結果 다음과 같은 結論을 얻었다. (1) 親核試藥이 피리딘에서 N,N-디메틸아닐린으로 바뀌어도 離脫基의 치환기效果는 변화가 없다. (2) p-MeO의 치환기정수는 아세톤에서 -0.35가 적당했다. (3) 치환 디메틸아닐린의 ) 親核力이 弱할 수록 전이상태에서는 N에서 C로 電子移動이 보다 크며 C${\ldots}$O結合 開裂은 보다 진행된 상태라고 생각된다. Substituent effect of the leaving groups of the reaction of benzyl arenesulfonate with dimethylanilines in acetone at $35^{\circ}C$ was obtained with the following results. 1. Substituent effect of the leaving groups was not variable when changed from pyridine to N,N-dimethylaniline in nucleophile 2.In acetone, the Hammett ${\sigma}$ constant of p-MeO of the leaving group was -0.35. 3. The weaker the nucleophilicity in dimethylaniline, the stronger the movement of electron from N to C, and the cleavage of the C${\ldots}$0 bond in transition state proceeds.

2-Phenylethyl Arenesulfonates와 피리딘과의 고압반응에 관한 연구

여수동,박종환,Yoh Soo Dong,Park, Jong Hwan 대한화학회 1986 대한화학회지 Vol.30 No.4

Kinetics of the reaction of 2-phenylethylarenesulfonates with pyridine in acetonitrile were investigated by an electric conductivity method under 1 to 2,000 bars and at 40∼60${\circ}C$. The rates of these reactions were increased with raising temperatures and pressures, but less than those of the reactions of benzyl benzenesulfonate with pyridine in acetoneitrile were investigated by an electric conductivity method under 1 to 2,000 bars and at 40~60${\circ}C$ .The rates of these reactions were increased with raising temperatures and pressures, but less than those of the reaction of benzyl benzenesulfonate with pyridine in acetone. The activation volumes and activation entropies of 2-phenylethyl m-nosylate were more negatively large than those of benzyl benzenesulfonate. From these phenomena it can be deduced that 2-phenylethyl system has more firmly $S_N2$ character in tranistion state. The Hammett reaction constants are also estimated from the second-order reaction constants. With increasing pressures the reaction parameters $({\rho})$ were decreased, but the $S_N2$ characters were increased. From these results, the reaction mechanism can be adequately described as typical $S_N2$ process under high pressure. 2-phenylethylarenesulfonates와 피리딘과의 아세토니트릴 용매중에서의 반응속도를 40∼60${\circ}C$, 1 ~ 2,000 bar에서 전기 전도도법으로 측정하였다. 반응속도는 온도가 높아지고 압력이 커짐에 따라 증가하였으며 아세톤 용매내에서 benzyl benzenesulfonate와 파라딘과의 반응속도보다 느렸다. 2-phenylethyl m-nosylate의 활성화 부피${\Delta}V^{\neq}$와 활성화 엔트로피 ${\Delta}S^{\neq}$는 benzenesuflonate보다 음의 값으로 컸다. 따라서 본 반응의 2-phenylethyl계가 전이 상태에서 벤질계보다 $S_N2$성이 크다고 추정된다. Hammett도시한 결과는 압력의 증가에 따라 값이 감소하여 $S_N2$성이 증가하였다. 이들의 모든 결과로 부터 고압하에서의 본 반응은 $S_N2$메카니즘으로 진행되며 압력의 증가는 $S_N2$반응성을 더욱 조장하였다.

아세톤 溶媒속에서 N,N^´-디메칠아닐린의 벤조일레이숀 親核置換反應에 관한 연구

呂壽東,郭永佑 慶北大學校 1975 論文集 Vol.20 No.-

The rate of the reaction of N, N'-dimethylaniline with various substituted benzoylchlorides has been measured by using spectrophotometer in acetone at 580㎚ and three different temperatures. The reaction was second order overall and pseudo first order with respect to each reactant. The rate constants were increased by electron-donating substituents, while they were decreased by electron-withdrawing groups. However, reaction of p-bromo and p-chloro benzoylchloride with N, N'-dimethylaniline had an abnormality in comparison with m-nitro and p-nitro benzoylchloride. Kinetic investigation carried out on this reaction showed that C-Cl bond breaking reaction predominates in the case of electron-releasing substituent but C-C bond making reaction becomes increasingly in the case of electron-withdrawing substituent. Activation parameters for the benzoylation were calculated.

Benzyl bromide 類의 溶媒分解에 關한 硏究 (I)

呂壽東 慶北工業專門大學 1969 論文集 Vol.6 No.-

The solvolysis of substituted benzyl bromides in methanol has been determined by the conductivity method. A plot of the Hammett substituent constants of benzyl bromides against logki gave a noonlinea curve and a mechanism was proposed to account for the non-linear behavior observed. Some activation parameters were also obtained.

置換 Benzyl Arenesulfonate 와 N,N-Dimethylanilines와의 反應 (第2報). 核置換 Benzyl Arenesulfonate의 置換基效果

여수동,Yoh Soo Dong 대한화학회 1975 대한화학회지 Vol.19 No.4

置換 benzyl (X)arensulfornate (Z)와 置換디메틸아닐린(Y)을 아세톤 容媒中에서 Menschatkin型 反應에 對한 벤질核의 置換基 效果를 檢討하였다. Z의 置換基가 電子끄는基에서 주는 基로 變할때 ZY 間에 存在하던 相互作用項이 消失되었다. ZY間의 相互作用項의 유무는 Z의 置換基 變化에 依한 $S_N2{\longrightarrow}S_N1$에의 機構의 變化에 對應된다고 생각된다. Substituent effects of benzyl substrates for the reaction of substituted benzyl(Z) arenesulfonate(X) with dimethylanilines in (Y) acetone at $35^{circ}$ were studied. The interactions between Z and Y disappeared when changed from electron withdrawing group to releasing group in benzyl substrates. The disappearance of interactions between Z and Y infers change of mechanism from $S_N2 to S_N1$ in substituent Z.

2-Phenylethyl Arenesulfonates와 피리딘과의 고압반응에 관한 연구

呂壽東,朴鍾煥 慶北大學校 物理化學硏究所 1986 硏究論文集 Vol.7 No.-

2-Phenylethyl arenesulfonates와 피리딘과의 아세토니트릴 용매중에서의 반응속도를 40∼60℃, 1∼2,000 bar에서 전기 전도도법으로 측정하였다. 반응속도는 온도가 높아지고 압력이 커짐에 따라 증가하였으며 아세톤 용매내에서 benzyl benzenesulfonate와 피리딘과의 반응속도 보다느렸다. 2-phenylethyl m-nosylate의 활성화 부피(ΔV^≠)와 활성화 엔트로피(ΔS^≠)는 benzyl benzenesulfonate보다 음의 값으로 컸다. 따라서 본 반응의 2-phenylethyl계가 전이 상태에서 벤질계보다 S_N2성이 크다고 추정된다. Hammett 도시한 결과는 압력의 증가에 따라 값이 감소하여 S_N2성이 증가하였다. 이들의 모든 결과로 부터 고압하에서의 본 반응은 S_N2 메카니즘으로 진행되며 압력의 증가는 S_N2 반응성을 더욱 조장하였다. Kinetics of the reaction of 2-phenylethylarenesulfonates with pyridine in acetonitrile were investigated by an electric conductivity method under 1 to 2,000 bars and at 40∼60℃. The rates of these reactions were increased with raising temperatures and pressures, but less than those of the reaction of benzyl benzenesulfonate with pyridine in acetone. The activation volumes and activation entropies of 2-phenylethyl m-nosylate were more negatively large than those of benzyl benzenesulfonate. From these phenomena it can be deduced that 2-phenylethyl system has more firmly S_N2 character in transition state. The Hammett reaction constants are also estimated from the second-order reaction constants. With increasing pressures the reation parameters(ρ) were decreased, but the S_N2 characters were increased. From these results, the reaction mechanism can be adequately described as typical S_N2 process under high pressure.

β-phenylethyl P-Bromobenzenesulfonate와 피리딘과의 고압반응에 관한 반응속도론적 연구

呂壽東,朴鍾煥 慶北大學校 物理化學硏究所 1984 硏究論文集 Vol.5 No.-

Recently, Kinetic studies of the reaction of benzylbenzenesulfonate with pyridine in acetone were carried out by the electric conductivity method under 1 to 2,000 bars at 20 to 40℃. From the activation enthalpy, activation entropy and activation volume, it was found that this reaction precedes via the S_N2 reaction mechanism in which the rate of the reaction was determined by C…N bond formation at the transition state.

Dodecyl Monochloroacetate와 置換 Pyridine類와의 反應速度論的 硏究

呂壽東 慶北大學校 師範大學 1978 敎育硏究誌 Vol.20 No.-

The rates of quaternization of substituted pyridines with dodecyl monochloroacetate were measured in dimethylformamide. The effects of substituents and solvent on the reactivity of pyridines were discussed. The rates of the reaction were increased with increase of the electron donating power of substituents. The isokinetic relationship between E_α and ΔS≠ was seen except for 4-aminopyridine. The excellent linearity, given by the following equation, was observed between logk and pk_α of pyridines except for 4-aminopyridine. logk=0.214pk_α-5.1 in DMF at 65℃ The deviations from the Hammett σ polt were also noticed for pyridines substituted with amino and cyano groups at 4-position, but 4-aminopyridine was correlated with σ^+ value. These deviations were considered to be attributed to the localization of π-electron on pyridine ring induced by the nitrogen atom and solvent effect on the substituents. From the above results, this reaction was found a typical SN2.

Phenacylbromide와 3次아민의 反應에 對한 溶媒效果

呂壽東,趙舜煥,李五錫 慶北大學校 1982 論文集 Vol.33 No.-

The kinetics of the quarterization reaction of phenacylbromide with tertiary amines including pyridine 3.5-lutidine and triethylamine in the media of acetonitrile, dimethylformamide, methanol, acetone and tetratydrofuran have been measured at 25℃, 35℃ and 45℃. The results of experiments show that the rate of quarternization are greatly affected by polarity of solvent except methanol. Activation parameters obtained in this study have the values we can expect for usually S_N2 mechanism. A linear relationship has been obtained between pK_a and logk, though such relationship is not clear in triethylamine. The good linear relationship has also been obtained between activation entropy and enthalpy. The linear relationship between logk and solubility parameters has turned out to be better than that dielectric constants.