Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

Reactions of Thianthrene Cation Radical Perchlorate with N-Arylbenzene- and N-Aryl-p-toluenesulfonamides. Synthesis of 5-(p-N-Arylbenzenesulfonamidephenyl)- and 5-(p-N-Aryl-p-toluenesulfonamidophenyl)thianthrenium Perchlorate

티안트렌 양이온 자유라디칼 과염소산염과 N-아릴벤젠술폰아미드 및 N-아릴-p-톨루엔술폰아미드의 반응. 5-(p-N-아릴술폰아미드페닐)티안트렌이움 과염소산염과 5-(p-N-아릴-p-톨루엔술폰아미드페닐)티안트렌이움 과염소산염의 합성

  • Sung Hoon Kim (Department of Chemistry, College of Natural Science, Seoul National University) ;
  • Kyongtae Kim (Department of Chemistry, College of Natural Science, Seoul National University)
  • 김성훈 (서울대학교 자연과학대학 화학과) ;
  • 김경태 (서울대학교 자연과학대학 화학과)
  • Published : 1981.12.30
Download PDF
⟨ Previous Next ⟩

Abstract

Thianthrene cation radical perchlorate reacts with N-arylsulfonamides such as p-toluenesulfonanilide, benzenesulfonanilide, N-(2-methylphenyl)benzenesulfonamide, and N-phenyl-p-toluenesulfonanilide to give 5-(p-N-p-toluenesulfonamidophenyl)-(1a), 5-(p-N-benzenesulfonamidophenyl)-(1b), 5-(4-N-benzenesulfonamido-3-methylphenyl)-(1c), and 5-(p-N-phenyl-N-p-toluenesulfonamidophenyl thianthrenium perchlorate (1d), respectively. In the meantime, 1d reacts further with thiathrene cation ratical to form diperchlorate(1e). The structure of 1a~1e is very similar to 5-(p-acetamidophenyl) thianthrenium perchlorate which has been obtained from the reaction with acetanilide. However, the discrepancy in the stoichiometry between two reactions indicates that the reaction with sulfonamide appears not to proceed with a single mechanism.

티안트렌 양이온 자유라디칼 과염소산염은 p-톨루엔술포아니리드, 벤젠술폰아니리드, N-(2-메틸페닐)벤젠술폰아미드, N-페닐-p-톨루엔술폰아닐리드와 같은 N-아릴술폰아미드와 반응하여 각각 5-(p-N-p-톨루엔술폰아미도페닐)티안트렌이움 과염소산염(1a), 5-(p-N-벤젠술폰아미도페닐)티안트렌이움 과연소산염(1b), 5-(4-N-벤젠술폰아미도-3-메틸페닐)티안트렌이움 과염소산염(1c), 5-(p-N-페닐-N-p-톨루엔술폰아미도페닐)티안트렌이움 과염소산염(1d)을 준다. 한편 1d는 티안트렌 양이온 자유라디칼과 다시 반응하여 이과염소산염(1e)을 생성한다. 1a∼1e의 구조는 아세트아니리드와의 반응생성물인 5-(p-아세트아미도페닐)티안트렌이움 과염소산염과 매우 비슷하다. 그러나 두 반응의 양 관계에서 상이한 점은 술폰아미드와의 반응이 단일 메카니즘으로 진행되지 않음을 암시한다.

Keywords

References

  1. Adv. Phys. Org. Chem. v.13 A. J. Bard;A. Ledwith;H. J. Shine
  2. J. Org. Chem. v.39 K. Kim;H. J. Shine
  3. v.39 K. Kim;V. J. Hull;H. J. Shine
  4. J. Amer. Chem. Soc. v.57 G. Dougherty;P. D. Hammond
  5. M. S. thesis, S.N.U. N. C. Jeong
  6. Reagents for Organic Synthesis v.1 L. F. Fieser;M. Fieser
  7. Handbook of Chemistry and Physics R. C. Weast(ed.)
  8. J. Amer. Chem. Soc. v.57 L. C. Raiford
  9. Ber. v.55B J. Halberkann
  10. J. Org. Chem. v.34 Y. Murata;H. J. Shine
  11. J. Amer. Chem. Soc. v.97 U. Svanholm;O. Hammerich;V. D. Parker