Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Studies on the Desulfurization of 1,3,4-Oxathiazol-2-one and 1,2,4-Dithiazol-3-one with Trivalent Phosphorus Compounds

1,3,4-옥사티아졸-2-온과 1,2,4-디티아졸-3-온의 3가인 화합물과의 탈황반응에 관한 연구

  • Dong Young Oh (Department of Chemistry, Korea Advanced Institute of Science and Technology) ;
  • Chung Ryeol Kim (Department of Chemistry, Korea Advanced Institute of Science and Technology)
  • 오동영 (한국과학기술원 화학과) ;
  • 김충렬 (한국과학기술원 화학과)
  • Published : 1983.10.20
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Abstract

The reactions of various 5-aryl-1,3,4-oxathiazol-2-ones with triethylphosphite resulted in the formation of the corresponding benzonitriles and ethylphosphorothioate by desulfurization reaction in 66∼94% yields. 5-(4-Nitrophenyl)-1,3,4-oxathiazol-2-one was also reacted with trimethylphosphite, triethylphosphine, and triphenylphosphine to give 4-nitrobenzonitrile. But it did not react with triphenylphosphate. The reactions of 5-(4-bromophenyl)-1,2,4-dithiazol-3-one with triphenylphosphine resulted in the formation of 4-bromothiobenzoyl isocyanate and triphenylphosphine thioxide. The thioacyl isocyanate was fragmented into nitrile in ether but was stable in chloroform. This desulfurization reaction observed in each reaction may proceed by the intramolecular rearrangement after insertion of the phosphorus compound into the ring. The stable thioacyl isocyanate in chloroform reacted with imine to give 1,3,5-thiadiazin-4-one via 1,4-cycloaddition reaction.

5-아릴-1,3,4-옥시티아졸-2-온을 트리에틸포스파이트와 반응시키면 탈황반응에 의해 벤조니트릴과 에틸포스포로티오에이트가 66~94% 수득율로 얻어졌다. 다른 3가의 인화합물 즉, 트리메틸포스파이트, 트리에틸포스핀, 그리고 트리페닐포스핀들과도 같은 탈황반응이 관찰되었다. 그러나 트리페닐포스파이트와는 전혀 반응하지 않았다. 5-아릴-1,3,4-디티아졸-2-온을 트리페닐포스핀과 반응시키면 티오아실 이소시아네이트가 얻어졌다. 이것은 에테르에서 자체적으로 분해되어 벤조니트릴로 변하게 되나 클로로포름에서는 안정하다. 이 두 반응에서 관찰되는 탈황반응은 인이 고리속으로 들어가 고리를 늘인후 분자내에서의 자리옮김 반응에 의해 일어나는 것이라 생각된다. 클로로포름에서 안정한 티오아실 이소시아네이트는 이민과 1,4-고리화 첨가반응을 일으켜 티아다이아지논을 생성하였다.

Keywords

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