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.

Reaction of Potassium Fluoride with Orgarnic Halogen Compound-II. Dimerization, Fluorination, and Decarboxylation of Organic Iodo acids, Iodides, and Polychlorinated Acid Ester

김유선,Kim, You-Sun Korean Chemical Society 1964 대한화학회지 Vol.8 No.4

아밀아이오다이드를 디메칠홀움아마이드 存在下에서 弗化加里와 低溫反應시켜 본 結果 弗化物과 데칸을 生成하였음. ${\alpha}$, ${\beta}$-디크로로-${\beta}$-페닐-푸로피온酸과 같은 多鹽素化物은 ${\alpha}$-크로로스타이렌, 弗化스타이렌 及 弗化酸을 生成하였음. 이 酸의 에칠에스텔은 弗化物을 生成하지 않고 各種 쌍合物의 混合物을 얻었음. 디부롬스타이렌은 부롬스타이렌과 弗化物을 生成하고 沃度를 含有한 有機酸, 메-타요드벤젠익酸은 有機酸의 鹽과 微量의 쌍合物을 生成하였음. 메타요드토류엔 及 1-아미노-4-요-드-2-메칠벤젠과 같은 沃化物은 弗化物은 弗化加里에 對하여 反應을 나타내지 않었음. 本報에는 各 反應條件과 弗化反應, 脫炭酸反應 及 쌍合反應에 關하여 論義하였음. The reaction of potassium fluoride with amyl iodide in presence of dimethylformamide at low temperature gave a fluorination product together with decane. Polyhalogenated acid such as ${\alpha}$, ${\beta}$,-dichloro-${\beta}$-phenyl-propionic acid gave ${\alpha}$-chlorostyrene, fluorinated styrene, and fluorinated acid. The same reaction with the ethyl ester did not give the fluorination product and gave a mixture of various dimerized product. Dibromostyrene gave bromostyrene together with fluorination product. Iodo acid such as m-iodo acid gave the salt and a trace quantity of dimerized product. Iodides such as m-iodotoluene and 1-amino-4-iodo-2-methyl benzene did not show any appreciable reactivity towards potassim fluoride. The reaction condition was described, and fluorination, ${\alpa}$-dehydrofluorination, decarboxylation, and dimerization were discussed.

Reaction of Organic Halogen Compounds with Metals (Part II) A Formation of Organic Chlorine Zinc Complex in Various Solvents

김유선,Kim, You-Sun Korean Chemical Society 1965 대한화학회지 Vol.9 No.1

토루엔, 디메틸폴움아마이드, 디메틸슬포옥사이드, 테트라하이드로퓨란, 아세토나이트라일 및 디옥센 等 溶媒存在下에서 모노클로로醋酸과 亞鉛을 反應시켜 본 結果, 溶媒효果를 나타내었다. 反應試藥의 反應度가 溶媒의 極性 및 親水性에 따라 增加하였다. 같은 溶媒系를 使用하여 에틸모노클로로醋酸을 反應시켜 본 結果, 溶媒효果를 나타냈으나 酸의 境遇보다 그 差가 크지 못하였다. 酸, 에스타, 亞鉛 및 카보닐化合物(벤즈알데히드 및 4-헤프타논)의 反應에 있어서는 알데하이드의 境遇에 있어서는 Reformatsky 反應生成物을 주었으나, 4-헤프타논과의 反應度는 없었다. 反應生成物의 收率은 試藥添加方法에 따라 變化되었다. 最高收率은 酸의 하이드로옥시酸(38.5%), 0.8g의 salt(아세트나이트라일溶媒)이며, 에스타의 境遇에는 에틸신나메이트(19.3%), 폴리머(21.6%)이였다. 카보닐化合物의 境遇에 있어서는 反應溫度에 따라 試藥의 反應度의 變化가 있었다. 硏究結果를 溶媒效果에 關聯시켜 論議하였으며, 硏究方法에 關하여 記述하였다. Reaction of monochloroacetic acid with zinc in presence of toluene, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, and dioxane solvents showed the solvent effect in order of dimethylformamide, dioxane, dimethyl sulfoxide, toluene, acetonitrile, and tetrahydrofuran. The increasing reactivity of the reagents was observed in order of the polarity and hydrophilicity of the solvent. The same reaction of ethyl monochloroacetate in the same series of solvents showed also the solvent effect, but the difference was not large as compared to that of the acid. The reaction of the acid, ester, zinc, and carbonyl precursors such as benzaldehyde and 4-heptanone gave the Reformatsky reaction product in the case of the aldehyde, but the reactivity with 4-heptanone was slight. The yield of the product was varied by the method of addition of reagents. The best yield observed in case of the acid reaction was 38.5% of the hydroxy acid and 0.8g of the salt in presence of acetonitrile and in case of the ester reaction 19.3% of ethyl cinnamate and 21.6% of polymer. The variation of the reactivity of reagents due to the reaction temperature was observed in case of carbonyl reaction. The result was discussed in terms of the solvent effect and the procedures were described.

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.

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.

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.

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

2,4-디할로겐 또는 2,4,6-트리할로겐아니솔 유도체들과 요오드 또는 염화요오드 사이에 생성된 전하이동 착물에 관한 연구

김유선,박경배,Kim, You Sun,Park, Kyung Bae 대한화학회 1976 대한화학회지 Vol.20 No.5

전자 공여체로서 할로겐으로 치환되어 있는 아니솔 유도체들(아니솔, 4-클로로아니솔, 2,3-디클로로 아니솔, 2-플루오로-4-클로로아니솔, 2-브로모-4-클로로아니솔, 2-요도드-4-클로로아니솔, 2-브로모 4,6-디클로로아니솔, 2-요오드-4,6-디클로로 아니솔, 2-요오드-2,4,6-드리클로로아니솔)을 쓰고 전자를 받아들이는 화합물로서는 요오드 또는 염화 요오드를 사용하여 그 사이에 생성되는 전하이동 착물에 관하여서 사염화탄소 또는 헥산을 용매계로 하여 연구하여 보았다. 연구한 결과로서 착물의 생성량이 벤젠고리의 2-치환 할로겐 원자의 Van der Waals 반경에 따라서 영향을 받음이 확인 되었으며 더 나아가서 전자 공여 화합물 분자의 입체적 배치 환경에 의하여서도 역시 영향을 받고 있음을 알 수 있었다. 이와 같은 경향은 클로로포름과의 착물 생성에서도 핵자기 공명분석법으로 확인될 수 있었다. 분광 분석법으로 얻은 착물 생성에 관한 데이터를 제시하였으며 벤젠고리에 치환된 2-할로겐 원자의 입체구조와의 상호관계를 논의하였다. The trends of forming a charge transfer complex have been studied for electron donors such as anisole, 4-chloroanisole, 2,4-dichloroanisole, 2-fluoro-4-chloroanisole, 2-bromo-4-chloroanisole, 2-iodo-4-chloroanisole, 2-fluoro-4,6-dichloroanisole, 2,4,6-trichloroanisole, 2-bromo-4,6-dichloroanisole, 2-iodo-4,6-dichloroanisole, and 2-iodo-4,5,6-trichloroanisole, and electron acceptors such as iodine and iodine monochloride in the carbon tetrachloride or the hexane solvent system. It was found that the formation of a charge transfer complex was influenced by the Van der Waals Radii of the 2-halogen atoms on the benzene ring and further the overall steric moiety of the molecule of the electron donor. These trends were also experienced in a system of chloroform and one of the prementioned electron donor by means of a nuclear magnetic resonance spectrometry. The spectrophotometrical data on the formation of the charge transfer complex were presented and the results were discussed with views of the steric structure of the 2-halogen atom on the benzene ring.

할로겐을 소유한 이원소 고리 화합물에 관한 연구(제 3보) 유기산 또는 Lewis산 존재하에서 이루어진 초산 Furfuryl의 염소화반응

김유선,이수선,오명원,Kim, You-Sun,Lee, Soo-Sun,Oh, Myung-Won 대한화학회 1970 대한화학회지 Vol.14 No.3

Furfuryl acetate was chlorinated in presence of acetic acid using carbontetrachloride as the solvent. When the chlorination proceeded at the low concentration of acetic acid, the formation of the tetrachloride was more efficient than that of higher concentration. The chlorination done in presence of various Lewis acids such as aluminum chloride, hydrogen fluoride, and borontrifluoride could not give high yield of tetrachloride, but trichloride. In case of borontrifluoride and hydrogen fluoride, the decomposition of the reaction mixture was apparent. The results were discussed in terms of the stability of furfuryl nucleus towards an electron acceptor and the convenient procedure of preparing trichloro furfuryl acetate was described.