1,3-Oxathiolane-3-oxide로 부터 유도되는 술펜산

Sulfenic Acid Derived from 1,3-Oxathiolane-3-oxide

  • 이화석 (한국과학기술원 유기화학연구실) ;
  • 박외숙 (충북대학교 자연대학 화학과)
  • Wha Suk Lee (Organic Chemistry Research Laboratory, Korea Advanced Institute of Science ant Technology) ;
  • Oee Sook Park (Department of Chemistry, Chungbuk University)
  • 발행 : 1987.04.20

초록

cis 및 trans 2-methyl-N-phenyl-1,3-oxathiolane-2-acetamide (b) 및 (c)의 sigmatropic rearrangement에 의하여 생성되는 각각의 sulfenic acid (d) 및 (f)는 deuterium exchange reaction에 의하여 확인되었다. cis와 sulfoxide (b)와 (c)의 이성질화가 중성조건하에서는 일어나지 않으나, 산성촉매 존재하에서는 일어난다는 것이 발견되었다. 중성조건하에서 이성질화가 일어나지 않는 것은 sulfenic acid의 SOH 산소원자와 NH proton 사이의 수소결합이 관여하는 stereospecific recyclization에 기인하거나 기하학적 요구에 기인한다고 설명된다. 한편 cis sulfoxide (b)와 trans sulfoxide (c)의 혼합물을 주는 전구물질 1, 3-oxathiolane의 산화반응에서 benzene seleninic acid를 촉매로 하는 $H_2O_2$의 산화에 의하여 cis sulfoxide (b)가 높은 수율로 선택적으로 얻어졌다.

Sigmatropic rearrangement of cis and trans-2-methyl-N-phenyl-1,3-oxathiolane-2-acetamide (b) and (c) gave unisolable sulfenic acids (d) and (f), respectively. These sulfenic acids were confirmed by deuterium exchange reactions involving 2-methylene and 2-methyl groups. The reactions also showed that no isomerization between the cis and trans sulfoxides (b) and (c) occurred under neutral conditions. However, the isomerization took place in the presence of acid catalyst. Stereospecific recyclization of sulfenic acids to the sulfoxides is attributable to possible hydrogen bonding between sulfenyl oxygen and NH proton or it arises from the geometrical requirements of the reacting bond and atoms in the reverse sigmatropic rearrangement. In the oxidation of 1, 3-oxathiolane, cis sulfoxide (b) could be obtained selectively in high yield by using $H_2O_2$-benzene seleninic acid.

키워드

참고문헌

  1. Systemic Fungicides R. W. Marsh(ed.)
  2. U.S. patent 3393202 M. Kulka;D. H. Thiara;W. S. Harrison
  3. J. Org. Chem. v.51 W. S. Lee;H. G. Hahn;K. D. Nam
  4. Synthesis J. Hans Reich Chow Flora;L. Steven Peake
  5. J. Amer. Chem. Soc. v.72 D. H. R. Barton;E. Miller
  6. Heterocycles v.11 Uyeo Shoichiro;Tsutomu Aoki;Wataru Nagata
  7. J. Amr. Chem. Soc. v.96 T. S. Chou;J. R. Burgtorf;A. L. Ellis;S. R. Lammert;S. Kukolja
  8. J. Amer. Chem. Soc. v.92 R. D. G. Cooper
  9. J. Chem. Soc. Chem. Commun. D. H. R. Barton;F. Comer;D. G. T. Greig;G. Lucente;P. G. Sammer