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.

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.

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.

含할로겐 異元素環化合物에 關한 硏究 (第1報) Furfurylacetate 의 Chlorination 반응

김유선,정진성,Kim, You-Sun,Chung, Jin-Sung 대한화학회 1965 대한화학회지 Vol.9 No.2

醋酸풀퍼릴을 合成하여 여러가지 反應條件下에서 鹽素化시킨 結果 低溫反應에서 安定한 trans 四鹽化物(平均收率 25∼30%)을 生成하였고, 三鹽化物의 生成은 거의 없었다. 高溫反應에서는 反應生成物의 分解가 甚하였다. 鹽素化反應條件, 生成物의 分離方式 및 安定度, 立體化學構造에 對하여 各各 論及하였다. Furfurylacetate was prepared and was chlorinated under various reaction conditions. At the low reaction temperature the chlorination product was composed of the stable trans-tetrachloride (yield, 25∼30%), decomposition product (low chlorine content), and unstable cis-tetrachloride. There were no appreciable quantity of the trichloride. At the high reaction temperature the chlorination products were exclusively decomposed. The reaction conditions, separation scheme, and the configurataion of the product were discussed.

함평사건희생자유족회의 소장 기록물 분류표 개발에 관한 연구

김유선,이명규,Kim, You-sun,Lee, Myounggyu 한국기록관리학회 2018 한국기록관리학회지 Vol.18 No.1

이 연구의 목적은 함평사건희생자유족회의 소장 기록물에 대한 분류체계를 마련하는 데에 있다. 이에 따라 기록물의 맥락을 기능적 출처주의를 통해 구현하며, 기록물을 효과적으로 활용할 수 있도록 유형별 특성과 생산시기별 특성을 반영한 분류표를 제시하였다. 기능분류체계 개발 방법론인 DIRKS를 사용하여 함평사건희생자유족회의 업무분석을 수행함으로써, 업무기능-업무활동-처리행위로 이어지는 업무분류표를 도출한다. 함평사건희생자유족회 소장 기록물을 유형과 생산시기별 특성을 고려하여 그 범주를 결정한다. 기록물 맵핑은 업무분류표에 해당하는 업무분류체계에 1차적으로 실행하고, 2차적으로는 업무분류에 유형분류와 시대분류를 접목한 다중분류체계에 맵핑한다. 업무주제-업무활동-처리행위-유형-시대의 형태로 이어지는 기록물 분류표를 도출한다. The purpose of this study is to establish a classification system for the records of the Association for the Bereaved Families of the Hampyeong Massacre Victims. The content of the records is accordingly implemented through a functional source principle, and a classification table is presented in such a way that it reflects the characteristics by type and by production period so that the records can be used effectively. DIRKS, a methodology for the development of the functional classification system, is used to conduct a functional analysis of Hampyeong massacre victims' families to derive a task classification table that leads to task function-work activity-handling actions. The category is determined by taking into consideration the type and nature of the time of the production of the records of the Hampyeong massacre victims' families. The records are mapped according to the function classification system, which corresponds to the task classification table, and the multicategory system that drafts the type and period, which is used to classify the functions. The medical institution introduces a system for classifying records into task subjects, task activities, handling actions, types, and period.

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.

含할로겐 異元素環化合物에 關한 硏究 (第2報) 풀퍼릴誘導體-마레인酸無水物 附加物의 할로겐化反應

김유선,김정희,Kim, You-Sun,Kim, Chung-Hee 대한화학회 1965 대한화학회지 Vol.9 No.2

퓨란, 醋酸풀퍼릴, 풀퍼릴알코올과 마레인酸無水物을 에틸 에테르 存在下에서 附加反應시켜 exo附加物을 만들고 이 化合物들에 對한 臭素化反應을 물 存在下에서 行한 바 各各 모노부롬化락톤 및 디브롬酸을 生成하였으며 락톤의 生成收率은 轉位된 carbonium ion에 對한 carboxylic acid의 反應기여(participation)에 依하여 決定되면 化合物 自體의 立體條件(steric requirement)이 그 기여에 영향을 준다는 것을 究明하였다. 퓨란附加物을 有機溶媒(四鹽化炭素, 메틸렌크로라이드)存在下에서 臭素化反應하면 二臭化物이 生成하고 光線 存在下에서 鹽素化反應하면 四鹽化反應物이 生成됨을 究明하였다. 各 化合物의 合成方式 및 反應過程에 關하여 論及하였다. The exo adduct between furfuryl derivatives (furan, furfuryl acetate and furfuryl alcohol) and maleic anhydride were prepared in the presence of ethyl ether. The bromination of the exo adduct of each derivatives gave a monobromolactone and dibromoacid when the reaction was done in the presence of water. The formation of the bromolactone was proved to be dependent to the carboxylic participation to the incipient rearranged carbonium ion of a classical type, and the participation was sterically hindered by the steric structure of the substituents. The bromination of the furan-maleic anhydride adduct in the presence of organic solvent $(CCl_4,\;CH_2Cl_2)$ gave the dibromide, whereas the photochlorination of the same adduct in the presence of carbon tetrachloride gave the tetrachloride. The procedure of the preparation and the reaction path of the halogenation were described.

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.

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.