Syntheses of Substituted tert.-Butyl(o-tolyl)-perpropionates

한치선,Hahn, Chi-Sun,Martin, Michael M. Korean Chemical Society 1964 대한화학회지 Vol.8 No.4

The syntheses of substituted tert.-butyl ${\beta}$-(o-tolyl)- perpropionates via intermediates obtained by chloromethylation, malonic syntheses and decarboxylation is described. The intermediates substituted with a group possessing moderate substituent effect such as bromo, chloro, and methyl group were obtained in good yields. The nitro-substituted intermediat was obtained in poor yield. The chloromethylation of toluenes containing electron donating groups resulted in polymerization. Chloromethylation, malonic ester 합성법 및 decarboxylation에 의한 중간체들을 거친 tert.-butyl ${\beta}$-(o-tolyl)-perpropionate 치환체들의 합성을 기술하였다. 심하지 않은 치환기효과를 나타내는 bromo-, chloro- 및 methyl- 기를 가진 중간체들은 좋은 수율로 얻어져서 목적한 바 과산화 ester들을 얻었으나 nitro기를 가진 중간체는 극히 적은 수율로 얻어졌고 한편 센 electron donating effect를 나타내는 group로 치환된 toluene들의 chloromethylation은 polymerize하는 결과를 가져왔다.

Ring-Opening Reaction of 2,2-gem-Diphenylaziridine

한치선,남궁하일,강용익,Hahn, Chi-Sun,Nam-Goong, Ha-Il,Kang, Yong-Ik Korean Chemical Society 1969 대한화학회지 Vol.13 No.3

2,2-gem-dephenylaziridine의 醋酸에 의한 開環反應에서 反應生成物은1,1-diphenyl-2-amino-ethyl acetate 임을 알았다. 또한 이 開環反應은 aziridine環 안에 있는 窒素原子와 tertiary炭素原子사이의 結合이 切斷되어 中間體로서 carbonium이온이 形成되는 過程을 거쳐서 進行됨을 알았다. A study of the ring-opening reaction of 2,2-gem-diphenylaziridine by treating with acetic acid has been undertaken. The structure of the ring-opened product was confirmed as 1,1-diphenyl-2-aminoethyl acetate. It is most likely that the reaction proceeds through the cleavage of a bond between nitrogen and tertiary carbon atoms in the aziridine ring, followed by the formation of a carbonium ion intermediate.

科學的 精神과 韓國 科學敎育의 課題

韓治善 연세대학교 교육대학원 1970 교육논집 Vol.3 No.1

The Synthesis of 2-Methyl-5,5'-gem-Disubstituted-${\Delta}^2$-Thiazolines

한치선,Chi Sun Hahn Korean Chemical Society 1963 대한화학회지 Vol.7 No.4

The synthesis of 2-methyl-5,5'-gem-disubstituted-$\Delta^2$-thiazolines has been undertaken by two methods. The first involves the preparation of gem-disubstituted N-or S-acetylamino mercaptan intermediates by ring opening of the corresponding thiiranes with ammonia. The second consists of the ring opening of gem-disubstituted ethylene imines using thiolacetic acid. The thiirane rings have never been opened under conditions as vigorous as that of using sodium amide in liquid ammonia. This is probably due to retardation by the gem-disubstituents. In contrast to this, the corresponding ethylene imine ring opens easily, in spite of the same stereochemical situation. The stabilization of gem-disubstituted cyclic compounds has been discussed from a stereochemical point of view. It has been concluded from the results of this work that the compression effect of gem-disubstitution is not due to bond angle deformation, which was observed by Thorpe and Ingold, but mostly to an electronic bond interaction of the gem-disubstituents and to the hetero atom(s), if any. 2-Methyl-5,5'-gem-disubstituted-$\Delta^2$-thiazoline系 化合物의 合成을 1,1'-gem-dusubstituted thiiranes의 三員環을 ammonis로 開環하여 骸當하는 N-또는 S-acetyl-amino mercaptan을 얻고 그것을 다시 閉環하는 方法과 또 하나는 같은 三員環인 gem-disubstitutes imines을 thiolacetic acid 로 開環하고 그것을 直接 다시 閉環하여 얻은 두가지 方法에 의하여 硏究하엿다. 前者는 thiirane ring은 gem-disubtitution의 compression 效果에 의하여 極히 安定化되어 여러가지 强力한 反應條件下에서의 sodium amide를 利用한 ammonia nuclephile에 頑强한 抵抗을 나타냈으며 反對로 後者의 三員環 imine은 같은 gem-disubstitution 效果를 받음에도 不拘하고 容易하게 開環하였다. 이 gem-disubstitution 效果에 의한 環狀化合物의 開環阻止性과 閉環促進性을 立體化學的인 見地에서 考察하였으며 本硏究로서 環狀化合物의 安定性에 미치는 gem-disubstitution의 compression 效果는 所謂 Thorpe-Ingold bond angle deformation에 緣由하는 것이 아니고 오히려 gem-dusubstituents와 異節環狀化物內의 hetero atom(s)이 미치는 bond interaction에 起因하다는 結論을 얻었다.

4-Nitroazoxybenzene에 關한 硏究 (第2報) 强酸 溶液中에서의 $\alpha$- 및 $\beta$-4-Nitroazoxybenzene의 性質

한치선,Chi Sun Hahn 대한화학회 1963 대한화학회지 Vol.7 No.4

The nature of the two isomers of 4-nitroazoxybenzenes in strongly acidic solution have been analyzed by U.V. spectrophotometry. Oxygen atom in the azoxy-group of $\alpha$-and $\beta$-4-nitroazoxybenzene in strong acid solution migrates neither to para position nor ortho position of the unsubstituted benzene ring of the compound in contrast with the cases of methyl-and bromo-substituted azoxybenzene, and shown no Wallach rearrangement. Since the $^1A{\rightarrow}^1H$ bands of the spectra shown hyperchromic effect whereas the ${\pi}{\rightarrow}{\pi}^*$ bands of them exhibit extream hypochromic effect, it appears most likely that trans ${\rightarrow}$cis isomerization take place in the media. A mechanism of a triangular transition state by which the transformation might be proceeded, is proposed.

Syntheses of Metallic Monoazo Complexes

한치선,박대철,남궁하일,강용익,Hahn, Chi-Sun,Park, Dae-Chul,Nam-Goong, Ha-Il,Kang, Yong-Ik Korean Chemical Society 1968 대한화학회지 Vol.12 No.3

몇가지 ortho-hydroxy monoazo 化合物들을 合成하여 이것들을 遷移元素로 金屬化시켰다. 三酸化크롬, 酢酸銅 및 酢酸코발드를 이 金屬錯鹽生成反應에 使用하였다. 이 硏究에서 다음과 같은 事實들을 알 수 있었다. (1) 이 金屬錯鹽生成反應에서의 溶媒는 다른 여러가지 有機溶媒보다는 물이 가장 좋고, (2) 金屬錯鹽生成反應 混合液의 가장 適當한 液性은 pH=4.5~5.5程度 이었으며, (3) 이들 monoazo 金屬錯鹽의 물에 대한 溶解性은 主로 그 錯鹽의 組成에 달렸으나 어느 程度는 分子內의 黃酸基의 存在에 의하여서도 影響을 받는다. 그리고 (4) 分子當 두개의 ortho-hydroxy基를 가진 金屬錯鹽이 더 强한 結合能을 가지고 있다. Some ortho-hydroxy monoazo-compounds have been synthesized and these were metallized with transition elements. Chromium trioxide, cupric acetate and cobalt acetate were used for the metallization. The following facts have been found in this investigation: (1) water is the best solvent, when compared to various organic solvents, for the metallization, (2) the optimum pH for the metallizing mixture ranges from 4.5 to 5.5, (3) the solubility of these metallic monoazo-compounds in water depends mainly on the composition of the complexes and to some extent on the presence of sulfonic acid groups in the molecules, and (4) metallized compounds having two ortho-hydroxy groups per molecule have stronger binding characteristics.

다핵환 유기화합물의 전기반도성에 관한 연구 : Cu-Pc의 전기적 성질 Electric Properties of Cu-Pc

韓治善,배선건,엄익환,정대일 연세대학교 자연과학연구소 1980 學術論文集 Vol.5 No.-

Copper-phthalocyanine의 정기적 성질, 특히 그 전기적 전도도와 capacitance의 진동수와 온도에 의한 의존도를 실험 조사하였다. 전기적 전도도와 capacitance에 미치는 진동수 의존도는 hopping 및 band 전도의 동시작용에 의하여 설명할 수 있었다. 흡수된 산소의 dc 전도도에 미치는 영향은 대단히 컸으나, ac 전도도에는 별로 이렇다할 영향이 없음을 알았다. Electric properties of copper-phthalocyanine, especially the dependence of frequency and temperature on its conductivity and capacitance has been examined. It has been found that the frequency dependence of the conductivity and capacitance can be postulated by concomitant hopping and band conduction. Oxygen absorbed has been affected on dc conductance in a great deal, but no effect has been detected on ac conductivity.

The Wallach Rearrangement The Behaviour of Monosubstituted Azoxybenzenes in Strongly Acidic Solution

한치선,Hahn, Chi-Sun Korean Chemical Society 1962 대한화학회지 Vol.6 No.2

The rearrangement reaction of azoxybenzenes into hydroxyazobenzenes in strongly acidic solution has been studied by an U. V. spectrophotometric method and by isolation of the rearranged compound. In all cases under investigation, it appeared that the oxygen atom in the azoxy group migrated to the unsubstituted ring, depending neither on the substituent already present in the other ring, nor on the distance between the oxygen atom and the eligible position; whereas, the position in the open ring, ortho or para, to which the oxygen migrates depends on the substituent already present in the other ring. In all compounds besides ${\alpha}$-and ${\beta}$-4-methyl azoxybenzene, the oxygen atom migrates to the para position. In the case of ${\alpha}$ and ${\beta}$-4-methylazoxybenzene, the oxygen atom migrates to the ortho position of the unsubstituted ring.

The Absorption Spectra of Substituted Azoxybenzenes and the Additivity of the their Absorption Maxima

한치선,Hahn, Chi-Sun Korean Chemical Society 1962 대한화학회지 Vol.6 No.2

The ultraviolet and visable absorption spectra of trans, cis-azoxybenzene, substituted azoxybenzenes and their conjugate acids have been studied. The 320-350$m{\mu}$ main bands of free-base of azoxybenzenes are due to ${\pi}{\to}{\pi}^{\ast}$ transition. These bands of their conjugate acids shown bathochromic shift into visible range. The following emperical relationship between absorption maxima of the main bands was found. ${\lambda}_{max}={\lambda}^{\circ}_{max}+{\Delta}{\lambda}_x+{\Delta}{\lambda}_y$ This relationship in terms of wave number is also hold in good agreement. ${\nu}={\nu}_{\circ}-({\Delta}{\nu}_x+{\Delta}{\nu}_y)$

Kinetics of the Rearrangement of $\beta$-4-Nitroazoxybenzene in Strongly Acidic Solution

한치선,이귀자,남궁하일,Han, Chi-Sun,Lee, Kwi-Ja,Nam Goong, Ha-Il Korean Chemical Society 1967 대한화학회지 Vol.11 No.4

The rearrangement of ${\beta}$-4-nitroazoxybenzene into 4-hydroxy-4'-nitroazobenzene in strongly acidic solutions has been as certained by UV spectrophotometry. The kinetics of the rearrangement in 20 vol. % ethanol and 80 vol. % of aqueous sulfuric acid-water solutions has been studied, and the rearrangement was found to be acid catalyzed pseudo-frst-order reaction. The mechanism of the rearrangement is also discussed. 强酸性溶液 中에서 ${\beta}$-4-Nitroazoxybenzene이 4-Hydroxy-4'-Nitroazobenzene으로 轉位하는 反應을 UV 分光光度法에 의하여 確認하였다. 20Vol%의 알코올과 80Vol.%의 여러가지 농도의 황산수용액에서의 이 轉位反應 反應速度을 究明하였으며, 그 結果 이 反應이 酸觸媒에 의한 擬1次反應임을 알았으며, 또한 이 轉位反應의 機構도 考察하였다.