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.

Polychloroanisidine 및 Fluorochloroanisole 유도체의 간편한 합성

김유선,김태영,김윤희,Kim, Yu Seon,Kim, Tae Yeong,Kim, Yun Hui 대한화학회 1974 대한화학회지 Vol.18 No.4

P-dichlorobenzene을 출발물질로하여 니트로화 반응, 메톡시화 반응 및 환원반응을 거쳐서 2-amino-4-chloroanisole을 얻은 다음 이것에 연속적인 염소화반응을 시켜 2-amino-3,4,5-trichloroanisole 만을 순수하게 얻을 수 있었다. 한편 4-chloro-2-nitroanisole 을 촉매 존재하에서 염소화반응시켜 2,4-dichloro-6-nitroanisole을 간편하게 얻었으나 이 이상의 염소화 반응은 보통 압력에서는 성공되지 못하였다. 2-amino-4,6-dichloranisole의 연속적인 염소화 반응으로 2-amino-3,4,5,6,-tetrachloroanosole을 간편하게 얻을수 있었다. 한편 2-amino-4-chloranisole 및 2-amino4,6-dichloranisole의 Schiemann반응으로 2-fluoro-4-chloranisole 및 2-fluoro-4,6-dichloroanisole을 각각 얻은 다음 이들의 연속적인 염소화 반응으로 2-fluoro-3,4,5,6-tetrachloroanisole을 간편하게 합성할 수 있었다. 염소화반응생성물들의 확인에 NMR 분석방식을 사용하여 생성물을 분리하지 않고 연속 합성하는 방식을 택하였으며 이러한 방식의 간편성을 논의 하였다. 높은 합성수득률 및 반응조건의 간이성에 따르는 실용성에 관하여서도 각각 제언 하였다. Starting from p-dichlorobenzene, 2-amino-4-chloroanisole could be prepared via a nitration, a methoxylation, and subsequent reduction. The repeated chlorination of 2-amino-4-chloroanisole resulted 2-amino-3,4,5-trichloroanisole without any isomeric products. The chlorination of 4-chloro-2-nitroanisole could easily give 2,4-dichloro-6-nitroanisole but polychlorination of the product could not be achieved at the atmospherical pressure. The repeated chlorination of 2-amino-4,6-dichloroanisole could give 2-amino-3,4,5,6-tetrachloroanisole, The Schiemann reaction of 2-amino-4-chloroanisole and 2-amino-4,6-dichloroanisole could give 2-fluoro-4-chloroanisole and 2-fluoro-4,6-dichloroanisole, respectively. The repeated chlorination of these fluorochloroanisoles could give 2-fluoro-3,4,5,6-tetrachloroanisole. In each chlorination process, the components of products were examined by means of NMR spectrometry and the chlorination reaction was repeated without isolating each isomeric product. The feasibility of the present routes of preparations was discussed in respects to the conveniency of reaction conditions and respective overall yields of the processes.

放射性 요오드化 反應 (第 II 報) 有機容媒 中에서의 各種 芳香誘導體의 低溫 요오드化 反應

김유선,김종두,Kim, You-Sun,Kim, Chong-Doo 대한화학회 1968 대한화학회지 Vol.12 No.1

Radio iodination of various aromatic derivatives (aniline, toluene, iodobenzene, acetanilide, benzene, benzoic acid) were achieved at low temperature by a chloroamine-T procedures in presence of polar solvent(dioxane). Organic base (piperidine) was used as the catalyst. Iodine replacement reaction had occured on the aromatic or alicyclic ring by this reaction, and the kind and ratio of iodinated products were proved to be different from those of usual iodide reaction in organic solvent at low temperature. The reactivity of various aromatic or alicyclic compounds towards the present iodination system was evaluated and the scope and limitation of the present procedures in the preparation of radio pharmaceuticals were discussed.

아민과 有機할로겐 化合物間의 Charge Transfer Complex 形成에 關한 硏究 (I)

김유선,오정희,Kim, Yoo-Sun,Oh, Jung-Hee 대한화학회 1967 대한화학회지 Vol.11 No.4

The formation of a charge transfer complex between various amines and organic halogen compounds was closely investigated. A mixture of amine (piperidine, pyridine, diethylamine, ethylamine, triethylamine and triethanolamine) and organic halides(carbon tetrachloride and chloroform) was checked for its UV absorption spectrum in presence of n-hexane solvent. A red shift was observed. The formation of charge transfer complex was observed in the case of triethylamine and diethylamine, whereas the formation of contact complex was distinct in case of piperidine. The relation between the nucleophilicity of amines and their tendency of forming charge transfer complex was discussed. 各種 아민과 할로겐化合物間의 Charge Transfer Complex 形成與否를 檢討하여 보았다. Pyridine Tridthylamine, Piperidine Ethanolamine Triethanolamine, Aniline, Diethylamine 等의 아민類와 四鹽化炭素 또는 클로로폼의 混合溶液을 n-Hexane 溶媒存在下에서 紫外線吸收 스펙트라를 檢査한 結果 장파장쪽의 Shift가 있었으며 特히 Diethylamine과 Triethylamine은 클로로폼 또는 四鹽化炭素와 1:1 Charge Transfer Complex를 形成하였고, Piperidine은 接觸的 Complex를 形成하는 것이 確認되었다. Complex의 形成경향과 아민의 Nucleophilicity와의 關係를 論議하였다.

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.

1977년도 국내외 한국과학기술자 종합학술대회 발표문-기초과학1부 방사성동위원소 이용연구

김유선,Kim, Yu-Seon 한국과학기술단체총연합회 1977 과학과 기술 Vol.10 No.4

본 발표문은 1,2,3,4로 이어지고 있는 것인바 여기서는 지면관계로 제 2부터 다루었기 양해를 구합니다. 제 1은 방사성 동위원소의 이용추세 입니다.

有機할로겐化合物과 金屬과의 反應 (第 3 報) 有機클로로酸 및 에스터와 各種金屬과의 反應生成物 및 反應系中의 金屬分布에 關하여

김유선,Kim, You-Sun 대한화학회 1965 대한화학회지 Vol.9 No.1

有機클로로酸, 또는 에스타와 各種金屬(亞鉛, 硅素, 마그네슘, 錫)과의 여러 溶媒存在下(아세트나이트라일, 디옥센 및 토루엔)의 反應에서 얻은 反應生成物, 또는 反應系中의 金屬分布狀態를 (n,${\gamma}$)反應으로 製造한 各種放射性 金屬트레이서를 使用하여 決定하였다. 有機클로로 金屬 콤푸렉스의 溶解度는 親水性溶媒에서는 顯著하게 增加하였으며, 無極性溶媒에는 減少하였다. 이 事實은 回收된 金屬, 또는 回收된 金屬混合物의 水洗液中의 金屬分布狀態의 增加로서 確認되었다. 카보닐化合物 存在下에서 反應시켰 때에도 같은 事實을 나타내었다. 親水性溶媒中의 金屬콤푸렉스의 溶解度는 亞鉛, 硅素, 錫 및 마그네슘이 順序로 減少되었으며 無極性溶媒下에서는 硅素, 錫, 마그네슘 및 亞鉛의 順으로 減少되었다. 有機할로겐化合物과 金屬과의 反應生成物로 普通 豫期되는 有機金屬化合物은 全反應을 通하여 거의 없었다. 反應結果를 論議하였으며, 本反應過程에서 觀察한 溶媒의 影響에 關하여 論及하였다. Metal distribution in the reaction products and system of reactions between organo chloro acid or ester and zinc, silicon, magnesium, and tin under acetonitrile, dioxane, and toluene solvent were determined by means of radioactive tracer prepared by means of a (n, ${\gamma}$) reaction. It was found that the solubility of the organo halogen metal complex was markedly increased in a hydrophilic solvent and was decreased in a nonpolar solvent which resulted in an increased metal distribution in the recovered metal or water washing of the recovered metal mixture. This was also true in the case of the reaction conducted in the presence of a carbonyl compound. The relative increase of the solubility of the metal complex in a hydrophilic solvent was in order of zinc, silicon, tin and magnesium, and in a nonpolar solvent, it was in order of silicon, tin, magnesium, and zinc. There was no formation of organo metallics throughout the reaction sequence. The result was discussed and the observed solvent influence on the present reaction path was criticized.

Study on the Facile Preparation of S-2-(${\omega}$-aminoalkylamino) ethyl Dihydrogen Phosphorothioates

김유선,김석원,You Sun Kim,Suc Won Kim Korean Chemical Society 1983 대한화학회지 Vol.27 No.6

The facile route of preparing S-2-(${\omega}$-aminoalkylamino) ethyl dihydrogen phosphorothioates, potential chemical radioprotectants, have been studied. Intermediate 3-(2-phthalimidoethyl)-2-oxazolidinone was prepared by a reaction of potassium phthalimide and 3-(2-bromoethyl)-2-oxazolidinone, which was obtained through the alkaline ring closure of a mixture of carbonate and 2,2'-dibromo diethylamine prepared from diethanolamine. This was converted to N-[2-(2-bromoethylamino)ethyl] phthalimide hydrobromide by 30% HBr(gas) in acetic acid and N-(2-bromoethyl)-1,2-ethanediamine dihydrobromide was obtained by reacting the hydrobromide with a solution of HBr-HOAc. N-(2-bromoethyl)-1,3-propanediamine dihydrobromide could be prepared through the Cortese treatment of 2-(3-aminopropylamino) ethanol, which was prepared by a reaction of 1,3-diaminopropane and 2-chloroethanol. These dihydrobromides were treated by sodium thiophosphate in DMF to result S-2-(${\omega}$-aminoalkylamino) ethyl dihydrogen phosphorothioates. The characteristics of each reaction path were discussed in regards to reaction conditions and overall yields and a facile route of preparing each derivative was proposed. 방사선장해를 예방할 수 있는 특성을 지닌 티오인산 이수소 S-2-(${\omega}$-아미노알킬아미노)에틸들의 간편한 합성법을 연구하였다. 중간체인 3-(2-프탈이미도에틸)-2-옥사졸리디논을 프탈이미드 칼륨염과 3-(2-브로모에틸)-2-옥사졸리디논을 반응시켜 만들었으며, 이 브로모에틸의 옥사졸리디논 유도체는 디에탄올아민으로부터 만들어진 2,2-디브로모 디에틸아민과 탄산염 혼합물의 알카리성 고리닫기 반응으로 합성할 수 있었다. 이 중간체는 30% 브롬화수소(가스)-초산용액으로 반응시켜 브롬화수소 N-(2-(2-브로모에틸아미노)에틸)프탈이미드로 유도되었고 이것을 다시 브롬화수소-초산용액으로 반응시켜 이브롬화수소 N-(2-브롬화에틸)-1,2-에탄디아민을 얻을 수 있었다. 1,3-디아미노프로판과 2-클로로에탄올로부터 2-(3-아미노프로필아미노)에탄올을 합성하고 이것을 Cortese씨법으로 처리하여 이브롬화수소 N-(2-브로모에틸)-1,3-프로판아민을 얻었다. 이들 이브롬화수소들을 DMF 용매에서 티오인산 나트륨으로 처리하여 티오인산 이수소 S-2-(${\omega}$-아미노알킬아미노) 에틸들을 합성하였다. 각각의 합성과정의 특징을 반응조건 및 총수율과 관련시켜 논의하였으며 티오인산 유도체를 합성하는 각편한 방법을 제의하였다.

아민과 有機할로겐 化合物間의 Charge Transfer Complex 形成에 關한 硏究 (II) Electron Acceptor 에 따른 Charge Transfer Complex 形成能에 關한 硏究

김유선,오정희,Kim, Yoo-Sun,Oh, Jung-Hee 대한화학회 1967 대한화학회지 Vol.11 No.4

Various amines (Triethylamine, Diethylamine, Dimethylaniline, Pyridine and Diphenylamine) and electron acceptors (Carbontetrachloride, iodine monochloride and iodine) were reacted in the hexane solvent system to form a charge transfer complex in each case. The tendency of forming a charge transfer complex by these electron acceptors was proportional to the basicity of amines and the different type of complex was formed as the polarity of electron donor had markedly changed, which were identified by ultraviolet spectrophotometry. A correlation between the formation of complex and the basicity of amine and the polarity of electron acceptor was discussed. 各 種 아민(triethylamine, diethylamine, pyridine, diphenylamine, dimethylaniline)과 各種 Electron Acceptor($CCl_4,\;ICl,\;I_2$)를 Hexane 溶媒 存在下에서 作用시킨 結果 各各 Charge Transfer Complex를 形成하였으나 그 形成能은 아민의 Basicity에 比例하였고 Electron Donor의 Polarity의 差가 클 때에는 다른 形式의 Complex를 形成함을 紫外線 吸收 分光法으로 確認하였다. Complex 形成能과 아민의 Basicity 및 Electron Acceptor의 Polarity의 關係를 論하였다.

방사성요오드화반응-IV,V보-과산화수소를 이용한 요오드표지 합성법의 검토

김유선,김태영,You sun Kim,Tae young Kim 대한화학회 1970 대한화학회지 Vol.14 No.2

A study was made on the radioiodination of organic compounds in presence of hydrogen peroxide both in aqueous and organic solvent systems. In case of the reaction of rosebengal, Hippuran, and 5-iodo-uracil the aqueous reaction system could give high labelling yield within a relatively short reaction time. Labelling yield of average 50% could be obtained within 30 minutes of reaction sequence. In cases of organic solvent systems (D.M.S.O., D.M.F., and Dioxane) the solvent system of D.M.S.O. could give better yield for neutral organic compounds, where as D.M.F. and Dioxane gave better labelling result for acidic materials. Especially, o-iodobenzoic acid, o-iodotoluene, and pentachlorophenol could be labelled better in organic solvent system.