서지주요정보
1,3-옥사티올란술폭시드의 디히드로-1,4-옥사티인 유도체로의 전위에 관한 연구 = Studies on the rearrangement of 1,3-oxathiolane sulfoxides to dihydro-1,4-oxathiins
서명 / 저자 1,3-옥사티올란술폭시드의 디히드로-1,4-옥사티인 유도체로의 전위에 관한 연구 = Studies on the rearrangement of 1,3-oxathiolane sulfoxides to dihydro-1,4-oxathiins / 한호규.
저자명 한호규 ; Hahn, Ho-Gyu
발행사항 [서울 : 한국과학기술원, 1985].
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등록번호

4103457

소장위치/청구기호

학술문화관(문화관) 보존서고

MAC 8544

SMS전송

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초록정보

A new synthesis of 5,6-dihydro-$\underline{N}$-phenyl-1,4-oxathiin-2-acetic acid derivatives $\underline{13}$ by ring expansion of the corresponding 1,3-oxathiolane-3-oxide $\underline{6}$ is described. In DMF at 100℃ the sulfoxide $\underline{6}$, in which S→O bond and 2-methyl group are cis to each other rearranged to sulfenic acid $\underline{10}$ involving the unactivated 2-methyl group, followed by cyclisation to dihydro-1,4-oxathiin $\underline{13}$. The ring opening of the sulfoxide $\underline{6}$ to form $\underline{10}$ occurs probably by [2,3] sigmatropic process at 50℃, but its conversion to the dihydrooxathiin $\underline{13}$ requried more elevated temperature, 100℃. Recyclisation of the sulfonic acid $\underline{10}$ under natural conditions took place stereospecifically to give parent sulfoxide $\underline{6}$. This was explained by considering a probable conformation of $\underline{10}$ and its transition state maintaining hydrogen bonding between S-OH and amide or ester group. Due to carbonyl inductive effect, the conversion of sulfoxide ester $\underline{6b}$ to sulfenic acid $\underline{10b}$ was faster than that of sulfoxide amide $\underline{6a}$, but the cyclisation of sulfenic acid $\underline{10b}$ to oxonium ion $\underline{11}$ (or carbonium ion $\underline{12}$) was slower than that of $\underline{10}$a. The structure of dihydrooxathiin $\underline{13}$ was also discussed in detail. Thus, structure $\underline{13}$ was distinguished from the alternative structure $\underline{14}$ by spectroscopic data, independent synthesis and isotope labelling experiment.

서지기타정보

서지기타정보
청구기호 {MAC 8544
형태사항 [ii], 68 p. : 삽도 ; 26 cm
언어 한국어
일반주기 부록 : 수소핵자기공명스펙트럼
저자명의 영문표기 : Ho-Gyu Hahn
지도교수의 한글표기 : 이화석
지도교수의 영문표기 : Wha-Suk Lee
학위논문 학위논문(석사) - 한국과학기술원 : 화학과,
서지주기 참고문헌 : p. 48-50
주제 Organic compounds --Synthesis.
Rearrangements (Chemistry)
Organosulphur compounds.
화학 합성. --과학기술용어시소러스
자리 옮김 반응. --과학기술용어시소러스
옥사티인 유도체. --과학기술용어시소러스
옥사티올란 유도체. --과학기술용어시소러스
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