DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | Kim, Yong-Hae | - |
dc.contributor.advisor | 김용해 | - |
dc.contributor.author | Chung, Bong-Chul | - |
dc.contributor.author | 정봉철 | - |
dc.date.accessioned | 2011-12-13T04:54:56Z | - |
dc.date.available | 2011-12-13T04:54:56Z | - |
dc.date.issued | 1982 | - |
dc.identifier.uri | http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=63282&flag=dissertation | - |
dc.identifier.uri | http://hdl.handle.net/10203/32332 | - |
dc.description | 학위논문(석사) - 한국과학기술원 : 화학과, 1982.2, [ [iv], 59 p. ] | - |
dc.description.abstract | The reactions of 2,4-dinitrobenzenesulfonyl chloride, and o-nitrobenzenesulfonyl chloride with potassium superoxide ($KO_2$) were carried out at -35$^\circ$C -0$^\circ$C in various solvents such as dimethyl sulfoxide, tetrahydrofuran, and acetonitrile in order to study on the peroxy-intermediates such as peroxy-sulfenate and sulfonate which have been postulate to be unstable intermediate. The treatment of two arylsulfonyl chlorides with $KO_2$ gave only one product, i.e., the corresponding potassium sulfonate in good yields. The reactions appear to be initiated by a nucleophilic attack of superoxide ion ($O_2^{\bar{\cdot}}$) on the sulfur atom to form peroxy-sulfonate intermediates, which convert to the corresponding sulfonates. When dimethyl sulfoxide was used as a trapping agent for the peroxy oxygen of peroxy-sulfonate intermediate, actually dimethyl sulfone of oxidation product along with the sulfonate was obtained in good yield. Thus, the reaction of arylsulfonyl chloride with $O_2^{\bar{\cdot}}$ undoubtedly is initiated by forming peroxy-sulfonates, which are available as a new oxidizing reagent under mild condition in aprotic organic solvents. While, the reactions of 2,4-dinitrobenzenesulfenyl chloride, and o-nitrobenzenesulfenyl chloride with $KO_2$ in THF or $CH_3CN$ gave the corresponding sulfonates and interestingly the corresponding disulfide were also obtained. In the case of 2,4-dinitrobenzenesulfenyl chloride, only bis (2,4-dinitrophenyl) disylfide was obtained as main product. From the observation of these facts the reactions appear to be initiated by a nucleophilic attack of $O_2^{\bar{\cdot}}$ on the sulfenyl sulfur atom to form a peroxy-sulfenate intermediate, which may compete two pathways: one is proceeded via cleavage of peroxy-sulfenate intermediate to form thiyl radical yielding the disulfide, and the other is converted to peroxy-sulfenate intermediate yielding the sulfonate. The reactions of 1,3-disubstituted thioureas with $O_2^{\bar{\... | eng |
dc.language | eng | - |
dc.publisher | 한국과학기술원 | - |
dc.title | Reactions of organo sulfur compounds with superoxide ion | - |
dc.title.alternative | 유기황화합물과 슈퍼옥사이드와의 반응에 대한 연구 : 아릴술포닐클로라이드, 아릴술페닐클로라이드, 그리고 티오우레아 유도체의 산화반응 | - |
dc.type | Thesis(Master) | - |
dc.identifier.CNRN | 63282/325007 | - |
dc.description.department | 한국과학기술원 : 화학과, | - |
dc.identifier.uid | 000801243 | - |
dc.contributor.localauthor | Kim, Yong-Hae | - |
dc.contributor.localauthor | 김용해 | - |
dc.title.subtitle | oxidations of arylsulfonyl chlorides, arylsulfenyl chlorides and thiourea derivatives | - |
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