서지주요정보
1,3-옥사티올란 유도체와 그의 술폭시드로부터 고리팽창 반응에 의한 새로운 디히드로-1,4-옥사티인 유도체의 합성에 관한 연구 = Synthesis of dihydro-1,4-oxathiins from 1,3-oxathiolanes and their sulfoxides by ring expansion
서명 / 저자 1,3-옥사티올란 유도체와 그의 술폭시드로부터 고리팽창 반응에 의한 새로운 디히드로-1,4-옥사티인 유도체의 합성에 관한 연구 = Synthesis of dihydro-1,4-oxathiins from 1,3-oxathiolanes and their sulfoxides by ring expansion / 강순방.
저자명 강순방 ; Kang, Soon-Bang
발행사항 [서울 : 한국과학기술원, 1988].
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소장정보

등록번호

4104788

소장위치/청구기호

학술문화관(문화관) 보존서고

MAC 8801

SMS전송

도서상태

이용가능

대출가능

반납예정일

초록정보

Synthesis of new 5,6-dihydro-1,4-oxathiin derivatives $\underline{22}$ and $\underline{23b}$ has been achieved by ring expansion of the corresponding 1,3-oxathiolane-3-oxides $\underline{16}$ and $\underline{17}$ and by chlorinolysis of the corresponding 1,3-oxathiolane $\underline{14b}$. Structural assignments of the cis and trans isomers were made by $^1H$ NMR spectroscopy including ASIS data. In DMF at $100^\circ{C}$ the cis sulfoxide 16a rearranged to sulfenic acid $\underline{18a}$, followed by cyclization to dihydro-1,4-oxathiin 22a in good yield, while the trans isomer $\underline{17a}$ gave $\underline{22a}$ in fair yield. The ring opening of cis and trans sulfoxides $\underline{16a}$ and $\underline{17a}$ occurs probably by [2,3]-sigmatropic process involving 2-methylene group in the cis isomer and 2-methyl group in the trans sulfoxide to give sulfenic acids $\underline{18a}$ and $\underline{19a}$, respectively. It was foudn that sulfenic acid $\underline{19a}$ was isomerized to $\underline{18a}$ to give only $\underline{22a}$. The maxiture of cis and trans sulfoxides $\underline{16b}$ and $\underline{17b}$ (47:53), which was not separated from each other, gave phthalimido oxathiins $\underline{22b}$ and $\underline{23b}$ in the ratio of 9:37 (\%) in DMF at $100^\circ{C}$. But with PTSA as a catalyst in benzene at reflux this mixture afforded only $\underline{23b}$ as minor product. The acid catalyzed ring opening of the sulfoxides $\underline{16b}$ and $\underline{17b}$ may proceed by B -elimination of a methyl proton which is effected by the amide nitrogen or carbonyl oxygen to give sulfenic acid $\underline{19b}$. By the action of chlorine on 1,3-oxathiolane $\underline{14b}$ in methylene chloridecarbon tetrachloride solution oxathiins $\underline{22b}$ and $\underline{23b}$ were produced in the ratio fo 10:80 (%). From the initially formed chlorosulfonium salt $\underline{39}$ unobserved transient sulfenyl chlorides $\underline{40}$ and $\underline{41}$ were generated, followed by cyclization to probable oxonium ions $\underline{42}$ and $\underline{43}$ to give dihydro-1,4-oxathiins $\underline{22b}$ and $\underline{23b}$. The structure of oxathiins $\underline{22a}$, $\underline{22b}$ and $\underline{23b}$ was elucidated by $^1H$ NMR spectroscopy and by independent synthesis.

서지기타정보

서지기타정보
청구기호 {MAC 8801
형태사항 iii, 83 p. : 삽도 ; 26 cm
언어 한국어
일반주기 부록 : $^1H$ NMR 및 IR spectra
저자명의 영문표기 : Soon-Bang Kang
지도교수의 한글표기 : 이화석
공동교수의 한글표기 : 김성각
지도교수의 영문표기 : Wha-Suk Lee
공동교수의 영문표기 : Sung-Gak Kim
학위논문 학위논문(석사) - 한국과학기술원 : 화학과,
서지주기 참고문헌 : p. 65-68
주제 Ring formation (Chemistry).
Organosulphur compounds.
화학 합성. --과학기술용어시소러스
고리 확대 반응. --과학기술용어시소러스
유기 황 화합물. --과학기술용어시소러스
Organic compounds --Synthesis.
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