有機할로겐化合物의 放射化 Thin Layer Chromatography

김유선,김순옥,김기수,YOU SUN KIM,SOON KO KIM,KI SOO KIM 대한화학회 1967 대한화학회지 Vol.11 No.2

有機할로겐化合物의 分離方法으로써 試料의 中性子照射에 依한 放射化 Thin Layer Chromatography를 Methanol을 展開溶媒로 하여 硏究한 結果 各種 할라이드, 할로겐酸, 할로겐알데하이드 等에서 銳敏한 展開 peak를 얻었으며 混合物의 展開에서도 定性確認에 充分한 分離 peak를 얻었다. 多 할로겐化合物, 芳香核鹽化物에 있어서는 試料의 中性子線 照射에 依하여 한 個 以上의 放射化할로겐化合物이 生成되어 確認이 困難하였으며 其他 할로겐 化合物에서는 再現性있는 Rf値를 얻을 수 있었다. 그리고 實驗方法을 記述하고 本 方法의 有用性에 關하여 論議하였다. Radio thin layer chromatography of organic halogen compounds by neutron irradiation technique was investigated for the purpose of identifying and separating the mixture of halogen compounds. It was found that various halides, organic acids, and aldehyde gave a distinct developing peak both in cases of individual compound and a mixture of two or three components when the samples were developed by solvent methanol. But poly chlorinated compounds and aromatic or alicyclic chlorides gave more than one component peak when the sample was developed after neutron irradiation. Rf value of each compound was distinct and reproducible. The procedures were described and validity of the present method is discussed.

Radiprotective Effects of S-2-($\omega$-aminoalkylamino) ethyl Derivatives and Their Drug Toxicities

김유선,김석원,Kim, You-Sun,Kim, Suc-Won Korean Association for Radiation Protection 1983 방사선방어학회지 Vol.8 No.2

S-2-($\omega-aminoethylamino) ethyl dihydrogen phosphorothioate, S-2-($\omega-aminopropylamino) ethyl dihydrogen phosphorothioate를 입수하기 용이한 출발화합물로부터 간편한 방식으로 합성하였다. 이들의 Isothiuronium 유도체들도 합성하였다. Isothiuroniu, 유도체들은 AET보다도 극심한 약독을 나타냈으며 이 약독은 분자내전위반응에 따른 고리화합물 생성에 기인하는 것으로 해석하였다. phosphorothioate 유도체들은 propyl의 경우 AET나 WR-638보다도우수한 방사성방호효과를 나타내주었으나 해당되는 ethyl유도체는 동일한 약량에서 훨씬 뒤떨어진 방호효과를 보여주었다. 이들 유도체들의 방사성방호효과, 약독 및 화학구조들 사이의 상호관계를 적외선 분광분석결과를 중심으로 하여 논의하였다. S-2-($\omega-aminoalkylamino) ethyl dihydrogen phosphorothioates and S-2-($\omega$-aminoalkylamino) ethyl isothiuronium bromides were prepared from easily available starting compounds via convenient synthetic processes. The isothiuronium derivatives showed extreme drug toxicities as compared to that of AET, which seemed to be due to an intramolecular rearrangement of these compounds. The propyl derivative of the phosphorothioate could show better radioprotective effect than those of AET and WR-638, whereas the ethyl derivative of the equivalent drug dose revealed far less protective effect. The correlation between radioprotective effects, drug toxicities, and chemical structures were discussed through infrared spectroscopy.

放射性 沃化反應 (第 1 報) 低溫沃化反應

김유선,김종두,YOU SUN KIM,CHONG DOO KIM 대한화학회 1967 대한화학회지 Vol.11 No.2

放射性 沃化反應 中 分解하기 쉬운 化合物의 沃化反應으로 有用한 低溫沃化反應에 關하여 硏究하였다. Chloroamine-T를 利用한 沃化反應은 低溫에서 높은 收率로 放射性 沃化反應을 進行시킬 수 있었으며, 活性化된 芳香核이 있는 또는 이에 類似한 아미노酸, 蛋白質化合物, 各 種 Phenol類의 沃化가 不可能하였으나 二重結合化合物 및 一般化合物엔 큰 效果가 없었다. 反應收率은 $100{\sim}60%$이었으며, 各 化合物의 試藥에 對한 反應度는 親電子反應에 對한 芳香核의 反應度와 比例하는 것이었다. 反應操作을 記述하였으며 反應過程을 考察하였다. A procedure, which is effective enough to label various compounds at low temperature by radioactive iodine, was investigated. The chloramine-T procedure was mostly effective for labelling various protein, amino acids, hormones, and organic compounds by iodine, and the procedure was able to afford both high specific activity and high radiochemical yield. However, the procedure was ineffective for labelling unsaturated compounds or other organic compounds which has not active aromatic nucleus of reactive character. The radiochemical yield of the procedure was generally averaged from 100% to 60%. The reactivity of the aromatic part of the organic compound towards this reagent was correspond to that of an electrophillic reagent. The procedures were described and the reaction path was considered.

含弗素有機 Carbonyl化合物의 Knoevenagel反應에 關한 硏究

김유선,You Sun Kim 대한화학회 1963 대한화학회지 Vol.7 No.1

The Knoevenagel reaction of fluorinated carbonyl compounds, 1,1,1-trifluoro-propanone-2-heptafluoro-butyraldehyde, 1,3-dichloro-1,1,3,3-tetrafluoro-acetone, tetradecafluoro-heptanone-4 and 2,2,2-trifluoro-acetophenone yielded fluorinated ${\beta},{\beta}$-dialkyl-${\beta}$-hydroxy acids. Dehydration of the acids do not give the olefinic acid in the case of the perfluorinated system and gave a lactone. From the consideration of electronic and steric effects a mechanismic path of the reaction via a carbanion intermediate was proposed for the reaction. Preparation of related derivatives are also described.

Reaction of Potassium Fluoride with Organic Halogen Compounds. (Part I) Reactions of Potassium Fluoride with Organic Halides, Acids, and Esters in presence of Dimethyl Formamide and their Pyrolytic Decaboxylation in presence of Potassium Fluoride

김유선,You Sun Kim Korean Chemical Society 1963 대한화학회지 Vol.7 No.3

Reactions between potassium fluoride with organic halogen-containing carboxylic acids in dimethyl formamide solvent gave a decarboxylation reaction for the case of fluoro carboxylic acids of the type of $CF_3\;COOH,\;C_3F_7COOH,\;and\;C_2F_5COOH,$ whereas an additional partial fluorination together with dimerization reaction occurred for the chlorine containing acids of the type of $CH_2ClCOOH,\;CH_3CHClCOOH, \;CHCl_2COOH\;and\;o-Cl-C_6H_4-COOH.$ The phenyl halides showed no reactivity, but the halides with two electron attracting substituents on the benzene ring gave mainly dimerization reaction. The esters and alcohols gave an usual fluorination reaction. The same reactions in absence of the solvent at the elevated temperature increase the yield of the dimerized product and gave the cyclized product, fluorenone, in case of ο-chlorobenzoic acid. It was found that the fluorination usually precede the decarboxylation reaction by checking the stiochemical sequence of reaction. Catalytic influence of potassium fluoride were discussed and the mechanism of the reaction was considered. <디메칠호롬아마이드> 溶媒系에서 有機含할로겐化合物을 弗化加里와 反應시켜 본 結果 $CF_3COOH,\;C_3F_7COOH,\;C_2F_5COOH$와 같은 含弗素有機酸에서는 脫炭酸反應이 일어나며, 含鹽素有機酸, $CH_2ClCOOH,\; CH_3CHClCOOH,\;CHCl_2COOH $및 $o-Cl-C_6H_4COOH$은 一部 弗化反應이 일어나고 雙合(dimerization) 反應이 隨伴된다는 것을 究明하였다. 芳香族할라이드類에서는 反應度를 나타내지 않았으나 芳香環에 誘電子置換基가 두個있는 試藥에서는 主로 雙合反應을 일으켰다. 알콜 및 에스테르類는 通常的인 弗化反應을 잘 일으켰다. 같은 反應을 溶媒 使用치 않고 高溫에서 進行시켜 본 結果 雙合反應物의 收率을 增加시켰고 $o-ClC_6H_4COOH$에서는 環化物(fluorenone)을 少量生成하였다. 反應段階中의 各 試藥의 消耗및 生成에 對한 化學量的關系를 比較檢討한 結果 酸의 反應에서는 普通 脫炭酸反應보다 弗化反應이 優先 進行됨을 究明하였다. 弗化加里의 反應觸發作用및 反應機構에 關하여서는 論議하였다.

Reaction of Organic Halogen Compounds with Potassium Fluoride. (Ⅲ) Fluorination of Aromatic vic-dihalides

김유선,김기수,You Sun Kim,Ki Soo Kim Korean Chemical Society 1969 대한화학회지 Vol.13 No.1

${\alpha},{\beta$}-dichloro-${\beta$}-phenyl propionate, Ethyl ${\alpha},{\beta$}-dibromo-${\beta$}-phenyl propionate, Etyyl ${\alpha},{\beta$}-dichloro-${\beta$}-(p-chlorophenyl)propionate, 및 dibromo-styrene 等의 化合物을 各種溶媒(dimethly formamide, diethylene glycol, 및 diethylene glyco monomethyl ether 等) 存在下에서 弗化反應을 시켜 보았으며 放射性弗素-18을 追跡子로 使用하여서 위의 化合物들의 弗化카리에 對한 反應度를 檢査하여 보았다. 一般的으로 弗化反應 生成物은 모노弗化物과 脫할로겐된 二重結合物을 生成하였다. diethylglycol 存在下에서 高溫反應시킨 條件下에서는 二重結合生成物이 많았고 diethylene glyco-monoethyl ether 存在下에서 低溫反應시킨 條件下에서는 弗化物이 多量生成하였다. 모노弗化物의 合成方式 및 確認方法에 關하여 說明하였으며 本反應의 合成上의 用途($F^{18}$ 標識化合物包含)에 言及하였다. Flourination of Ethyl, ${\alpha},{\beta$}-dichloro-${\beta$}-phenyl propionate, Ethyl ${\alpha},{\beta$}-dibromo ${\beta$}-phenyl propionate, Ethyl ${\alpha},{\beta$}-dichloro ${\beta$}-(p-chloro-phenyl) propionate, and dibromostyrene by potassium fluoride were investigated in presence of dimethyl formamide, diethylene glycol, and diethylene glycol monomethyl-ether. The reactivity of these organic halogen esters and hydrocarbons towards potassium fluoride was checked further by means of radioactive fluorine-18. tracer. Generally, the reaction gave monofluoride together with dehalogenated olefin. The formation of olefine was increased when the reaction was done at high reaction temperature in presence of diethylene glycol, whereas the lower reaction temperature in presence of diethyleneglycol monomethyl ether favored the formation of mono fluoride in a good yield. The procedures and methods of the identification of monofluorides were described and the feasibility of this reaction of fluorine containing ester including the F-18 labelled compounds was discussed.

Study on a Ridio Paper Partition Chromatography of Organic Halogen Compounds by a Neutron Irradiation. A Qualitative Approach

김유선,최송자,Kim, You-Sun,Chae, Song-Cha Korean Chemical Society 1964 대한화학회지 Vol.8 No.2

展開한 페이퍼크로마토그램을 韓國 Triga-Mark-Ⅱ 硏究用 原子爐의 뉴마딕튜부施設(中性子線束; 1.5{\times}$10^{12}n/cm^2$, sec)을 利用하여 照射하여 본 結果 크로마토그램上에 展開된 스폿트(spot)를 定性的으로 確認할 수 있었다. 有機하로겐 化合物(크로로酸, 크로로에스테르, 沃化物, 及 弗化物)에 있어서 一般發色法으로서는 明確한 着色스폿트(spot)를 나타내지 못한 것에 있어서도, 이 方法으로서 展開된 스폿트를 明確히 區別할 수 있었다. 濾紙成分의 放射化에 依한 誤差를 減少시키기 爲하여 濾紙두께 補正 及 放射化度 補正을 硏究한 結果, 濾紙두께 補正 及 放射能崩壞 補正法을 究明하였으며, 이 方法으로 스폿트를 放射化하여 定性分析하는데 좋은 結果를 얻을 수 있었다. 有機하로겐化合物의 分析 及 確認에 있어서의 이 方法의 效用性에 關하여 論議하였다. 濾紙相으로는 正常相 及 逆相을 함께 使用하였다. When a developed paper partition chromatogram was irradiated by means of the pneumatic tube system of the Korean research reactor (neutron flux: 1.5 ${\times}10^{12}n/cm^2$sec.) the qualitative confirmation of the developed spot on the chromatogram was possible. In the case of an organic halogen compounds (chloro-acid, chloro-ester, iodide, and fluoride) the spot analysis was possible by the present method whereas the same spot could not give the distinct coloring with a common coloring reagents. Filterpaper thickness calibration and activity calibration induced by irradiation of the components of the filter paper, which were a source of erraneous interpretation of the spot, were searched and an average filterpaper calibration method and filter paper activity were improvised to obtain a good qualitative analysis of the spot. Finally the use and applicability of this method for the analysis identification of an organic halogen compound were evaluated. As the filter paper phase an ordinary phase (Whatmann #1, filter paper) and reversed phase (liquid paraffin impregnated) were used.

A New Gas-Chromatograghic Method of Organic Elemental Analysis

김유선,손연수,최규원,Kim, You-Sun,Son, Youn-Soo,Choi, Q.Won Korean Chemical Society 1964 대한화학회지 Vol.8 No.4

微量元素分析用 燃燒爐 內에서 內部酸化劑(酸化銀과 二酸化 망간의 混合物)와 함께 有機試料를 헤륨 氣流下에서 燃燒시키고 發生한 물은 칼슘카바이드管에 通하여 아세틸렌으로 變換시킨다. 二酸化炭素와 아세틸렌을 molecular sieve 5A 管에 室溫에서 吸着시킨 후 $340^{\circ}C$까지 溫度${\cdot}$프로그탬法으로 脫着시켜 실리카켈管을 通하여 分別流出시키고 熱傳導式 檢知器로 $CO_2$와 $C_2H_2$를 定量하는 方法을 發展시켰다. 벤조酸을 標準物質로 하여 作成한 檢量線을 使用하여 各種 有機試料中의 炭素 및 水素含量을 分析한 結果 平均誤差가 炭素의 경우 ${\pm}0.5%$, 水素인 경우${\pm}0.33%$ 이었다. A new gas-chromatographic method for determining carbon and hydrogen in organic compounds has been developed. After sample combustion was performed in a regular analytical combustion tube with an internal oxidant (a mixture of silver oxide and manganese dioxide) under a helium flow, the water produced was converted to acetylene by passing through a calcium carbide tube. The carbon dioxide and acetylene were trapped by a molecular sieve 5A column at room temperature. The trapped gases were released under programmed temperature raise up to $340^{\circ}C$ and the released gases were passed through a silica gel column. The adsorption of $CO_2$ and $C_2H_2$ in the molecular sieve 5A trapping column were found to be quantitative and the silica gel column showed an excellent resolution of $CO_2$ and $C_2H_2$ for analytical purpose. The analytical results for various known compounds based on the out-put of the thermal conductivity cell calibrated for the amounts of carbon and hydrogen contents in benzoic acid, showed average errors ${\pm}0.5%$ and ${\pm}0.33%$ for carbon and hydrogen, respectively.

有機 Halides 와 Amines 間의 光反應에 關한 硏究

김유선,박용자,Kim, You-Sun,Park, Yong-Ja 대한화학회 1962 대한화학회지 Vol.6 No.2

The reactions between organic halides$(CCl_4,\;C_6H_5Br,\;C_6H_5Cl,\;C_6H_5I)$ and amines $(C_6H_5NH_2,\;R_2NH,\;R_3N,\;(CH_2)_5NH,\;pyridine)$ were studied under mixed u.v. irradiation. The modes of reactions were examined by means of gas chromatography and product-reactant ratio determination. The reaction of $CCl_4$ with amines give chloroform and hexachloroethanes, and the reaction of aromatic halides with amines gave biphenyl and benzene. In each series of reaction there obtained mainly corresponding amine hydrohalides, but no amination products. The reactivity was in the order of the basicity of amines and of the reactivity of organic hahides, except in the case of cyclic tertiary amine. The result was interpreted as a non-chain photodecomposition process. A competitive proton abstraction reaction path via the formation of a change transfer complex was proposed as the reaction mechanism.

2,3,4,5,6-펜타클로로아니솔 및 그 브로모 또는 요오도 유도체들의 간편한 합성법

김유선,박경배,오옥두,You Sun Kim,Kyung Bae Park,Ok Doo Auh 대한화학회 1976 대한화학회지 Vol.20 No.3