The Korean Journal of Pesticide Science (농약과학회지)

The Korean Society of Pesticide Science (한국농약과학회)
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Attempted Synthesis of Carboxin Derivative through Ring Expansion Reaction on Solid Phase

고체상에서 환팽창 반응에 의한 카르복신 유도체의 합성시도

  • Hahn, Hoh-Gyu (Organic Chemistry Lab, Korea Institute of Science and Technology) ;
  • Bae, Su-Yeal (Organic Chemistry Lab, Korea Institute of Science and Technology) ;
  • Nam, Kee-Dal (Organic Chemistry Lab, Korea Institute of Science and Technology)
  • 한호규 (한국과학기술연구원, 생체과학연구부, 유기화학연구실) ;
  • 배수열 (한국과학기술연구원, 생체과학연구부, 유기화학연구실) ;
  • 남기달 (한국과학기술연구원, 생체과학연구부, 유기화학연구실)
  • Published : 2005.09.30
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Abstract

Solid phase synthesis of 16, which is a derivative of the first systemic fungicide, carboxin 1 was described. Reaction of 1,3-oxathiolane derivative with solid resin of 4-hydroxy-3-nitrobenzophenone 6 gave 9 in 82% yield. Oxidation of sulfur in the solid 1,3-oxathiolane 9 by MCPBA followed by a ring expansion reaction under the acid catalyst afforded the corresponding dihydro-1,4-oxathiin derivative 12. Treatment of the solid 1,3-oxathiolane 9 with p-methoxyaniline resulted in 1,3-oxathiolane 14, 1,3-oxathiolane sulfoxide 15, dihydro-1,4-oxathiin 16, and acetoacetanilide derivative 17 in 41%, 35%, 14%, 10% yields, respectively.

최초의 침투이행성 농약 살균제, 카르복신 1의 유도체인 16을 고체상에서 합성하였다. 1,3-옥사티올란 유도체를 아실화 반응성을 갖고 있는 4-하이드록시-3-나이트로벤조페논 고체상 6에 연결하여 9를 82%의 수율로 합성하였다. 고체상의 1,3-옥사티올란 9의 황원자를 MCPBA로 산화한 다음 생성된 설폭사이드 10을 산촉매 존재하에서 환팽창하여 상응하는 고체상에 연결된 다이하이드로-1,4-옥사티인 유도체 12를 합성하였다. 고체상의 1,3-옥사티올란 9의 산화물을 p-메톡시아닐린과 반응시켜 1,3-옥사티올란 14, 1,3-옥사티올란 설폰 15, 다이하이드로-1,4-옥사티인 16, 그리고 아세토아세트아닐라이드 유도체 17을 각각 41%, 35%, 14%, 10% 수율로 얻었다.

Keywords

References

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