Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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A Synthesis of 1,4-Thiazine Carboxanilide: Neighboring Group Participation in Pummerer Reaction

1,4-Thiazine Carboxanilide의 합성: Pummerer 반응에서의 인접기 참여효과

  • Han, Ho-Gyu (Organic Chemistry Lab, Korea Institute of Science and Technology) ;
  • Nam, Gi-Dal (Organic Chemistry Lab, Korea Institute of Science and Technology) ;
  • Ma, Hye-Deok (Department of Chemistry, Kyonggi University)
  • 한호규 (한국과학기술연구원 생체과학연구부) ;
  • 남기달 (한국과학기술연구원 생체과학연구부) ;
  • 마혜덕 (경기대학교 화학과)
  • Published : 2002.08.20
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Abstract

For the purpose of development of new agrochemical fungicide of ${\alpha},{\beta}-unsaturated$ carboxanilide series a synthesis of 4-acetyl-3-methyl-N-phenyl-1,4-thiazine-2-carboxamide (6) is described. Pummerer reaction of sulfoxide 7 obtained by sulfoxidation of dihydro-1,4-thiazine methyl ester 11 gave ${\alpha}-acetoxy$ dihydro-1,4-thiazine 10a. Under the same reaction conditions, dihydro-1,4-thiazine carboxanilide sulfoxide 14 was converted to acetoxymethyl dihydro-1,4-thiazine 18 through vinylogous Pummerer reaction involving carboxanilide of sulfonium ion through intermediate 15.1,4-Thiazine carboxanilide 6 was synthesized from the treatment of ${\alpha}-acetoxy$ dihydro-1,4-thiazine 10a with acid cat-alyst followed by hydrolysis and then the reaction with aniline.

새로운 ${\alpha},{\beta}$-불포화Carboxanilide계열의 살균제를 개발을 목적으로 4-acetyl-3-methyl-N-phenyl-1,4-thiazine-2-Carboxamide(6)의 합성에 대하여 기술하였다. Dihydro-1,4-thiazine methyl ester 11을 산화하여 생성된 sulfoxide 7을 Pummerer 반응하여 $\alpha$-acetoxy dihydro-1,4-thiazine 10a를 얻었다. 반며에 Dihydro-1,4-thiazine Carboxanilide sulfoxide14는 동일한 반응조건 하에서 중간체 sulfonium ion의 carboxanilide기가 관여한 vinylogous Pummerer 반응의 전위에 의하여 중간체를 15를 통하여 acetoxymethyl dihydro-1,4-thiazine 18이 생성되었다. 1,4-Thiazine carboxanilide 6은 $\alpha$-acetoxy dihydro-1,4-thiazine 10a를 산촉매로 처리한 다음 생성된 21a를 가수분해하고 아닐린과 결합하여 합성하였다

Keywords

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  3. 1,4-티아진 설폭사이드의 위치선택적 Pummerer 반응(II) vol.48, pp.4, 2004, https://doi.org/10.5012/jkcs.2004.48.4.443