서지주요정보
1,3-디티올란 술폭시드의 전위에 의한 디히드로-1,4 -디티인 유도체의 합성 = Synthesis of dihydro-1,4-dithiins by rearrangement of 1,3-dithiolane sulfoxides
서명 / 저자 1,3-디티올란 술폭시드의 전위에 의한 디히드로-1,4 -디티인 유도체의 합성 = Synthesis of dihydro-1,4-dithiins by rearrangement of 1,3-dithiolane sulfoxides / 이구.
저자명 이구 ; Lee, Koo
발행사항 [서울 : 한국과학기술원, 1986].
Online Access 제한공개(로그인 후 원문보기 가능)원문

소장정보

등록번호

4103563

소장위치/청구기호

학술문화관(문화관) 보존서고

MAC 8613

SMS전송

도서상태

이용가능

대출가능

반납예정일

초록정보

A new synthesis of 5,6-dihydro-2-methyl-1,4-dithiins-3-carboxylic acid derivative $\underline{11a}$ and 5,6-dihydro-1,4-dithiin-3-acetic acid derivatives $\underline{12}$ by ring expansion of the corresponding 1,3-dithiolane-1-oxides $\underline{7a}$, $\underline{8}$ has been achieved. Structural assignments of the cis and trans isomers were made by $^1H$ NMR spectroscopy including aromatic solvent induced shift (ASIS) data. Disulfoxides $\underline{18a}$, $\underline{19a}$, $\underline{20a}$ and $\underline{20b}$ as byproducts were also formed by oxidation of 1,3-dithiolanes. In refluxing toluene the cis sulfoxide $\underline{7a}$ rearranged to sulfenic acid $\underline{9a}$, followed by cyclization to dihydro-1,4-dithiin $\underline{11a}$ in a high yield. In refluxing 1:1 DMF-$C_6H_6$ the trans sulfoxides $\underline{8}$ were converted to isomeric dihydrodithiins $\underline{12}$ in good yields via sulfenic acids $\underline{10}$. The ring opening of cis and trans sulfoxides $\underline{7a}$ and $\underline{8}$ to form respective $\underline{9a}$ and $\underline{10}$ occurs probably by [2,3] sigmatropic process involving 2-methylene hydrogens in the cis isomer and 2-methyl hydrogens in the trans isomer. With PTSA as a catalyst in benzene at reflux the cis sulfoxide $\underline{7a}$ readily afforded dihydro-1,4-dithiin $\underline{11a}$ in quantitative yield, while the trans sulfoxides $\underline{8}$ gave dihydrodithiins $\underline{11}$ and isomeric dihydrodithiins $\underline{12}$ in the ratio of 4:1 for amides and 1:5 for esters. In the presence of acid catalyst, the ring opening of the cis sulfoxide $\underline{7a}$ takes place presumably by stepwise mechanism via protonated sulfoxide $\underline{13a}$. The acid catalysed ring opening of the trans sulfoxides may proceed by stepwise mechanism involving 2-methylene hydrogens and by [2,3] sigmatropic rearrangement with 2-methyl hydrogens. Due to carbonyl inductive effect, the conversion of sulfoxide ester $\underline{8b}$ to sulfenic acid $\underline{10b}$ was faster than that of sulfoxide amide $\underline{8a}$, but the cyclization of sulfenic acid $\underline{10b}$ to form dihydrodithiin $\underline{12b}$ was slower than that of $\underline{10a}$. The structures of dihydrodithiins $\underline{11a}$ and $\underline{12}$ were identified by $^1H$ NMR spectroscopy and by independent synthesis.

서지기타정보

서지기타정보
청구기호 {MAC 8613
형태사항 [iii], 72 p. : 삽도 ; 26 cm
언어 한국어
일반주기 부록 : $^1H$ NMR 및 IR spectra
저자명의 영문표기 : Koo Lee
지도교수의 한글표기 : 이화석
지도교수의 영문표기 : Wha-Suk Lee
학위논문 학위논문(석사) - 한국과학기술원 : 화학과,
서지주기 참고문헌 : p. 49-51
주제 Rearrangements (Chemistry)
Sulphoxides.
화학 합성. --과학기술용어시소러스
자리 옮김 반응. --과학기술용어시소러스
술폭시화물. --과학기술용어시소러스
Organic compounds --Synthesis.
QR CODE qr code