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1987 Fiscal Year Final Research Report Summary

Reactivities of Nitrenium Ion Intermediates and the Application to Organic Syntheses

Research Project

Project/Area Number 60490007
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 広領域
Research InstitutionShinshu University

Principal Investigator

TAKEUCHI Hiroshi  Shinshu University, 工学部, 助教授 (00029258)

Co-Investigator(Kenkyū-buntansha) TSUCHIDA teruko  Shinshu University, 工学部, 教務員
MITANI Michiharu  Shunshu University, 工学部, 助教授 (20021016)
KOYOMA Kikuhiko  Shinshu University, 工学部, 教授 (40029012)
Project Period (FY) 1985 – 1987
KeywordsArylnitrenium ions / Aryl azides / Trifluoroacetic acid / Dearylamines / Alkyl thioanilines / Parent nitrenium ion / Vinylnirenium ions / イソオキサゾール誘導体
Research Abstract

The chemistry of nitrenium ions has been actively investigated in recent years since they are not only reactive metabolites of some carcinogens but also important intermediates for organic syntheses.
Arylnitrenium ions (ArN.^H or ArN^+-^-AlCl_3) are generated from aryl azides in the presence of trifluoroacetic acid (TFA), trifluoromethanesulfonic acid (TFSA), or aluminium chloride. The singlet arylnitrenium ions are capable of bringing about inter- and intra-molecular aromatic N-substitutions and stereospecific additions to olefins, whereas the triplet nitrenium ions lead only to hydrogen abstraction. The substitutions afforded diarylamines, carbazoles, and 9,10-dihydroacridine. The reaction of alkyl sulfides with phrnylnitrenium ion generated from phenyl azide in the presence of both TFA and TFSA gave a new synthetic method for alkyl thioaniline dirivatives (i.e. aminophenyl sulfides).
Phenylnitrenium ion, parent nitrenium ion, and alkylnitrenium ions are generated in the thermolysis or photolysis of 1-(phenylamino, amino, and alkylamino)-pyridinium salts in the presence of TFA. Direct aromatic N-substitutions are also allowed to occur by these ions in singlet states. The parent nitrenium ion is also formed in the photolysis of S-aminophenylsulfonium salts.
The reaction of <beta>-azidostyrene in the presence of TFA, difluoroacetic acid, trichloroacetic acid, dichloroacetic acid, or chloroacetic acid produced a novel compound 4-pheny1-5-halomethylisoxazole, respectively. On the contrary, the reaction of <alpha>-azidostyrene instead of <beta>-azidostyrene did not give isozazole but acetophenone imide. Mechanistic study suggests that the reactions proceed via vinylnitrenium ion intermediates.

  • Research Products

    (11 results)

All Other

All Publications (11 results)

  • [Publications] 竹内寛: J. Chem. Soc. , Perkin Trans. 1. 677-684 (1985)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 竹内寛: J. Chem. Soc. , Chem. Commun. 287-289 (1985)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 竹内寛: J. Chem. Soc. , Prekin Trans.1. 611-618 (1986)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 竹内寛: J. Chem. Soc. , Perkin Trans. 1. 57-60 (1987)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 竹内寛: J. Chem. Soc. , Chem. Commun. 961-963 (1987)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 竹内寛: J. Chem. Soc. , Parkin Trans.1. (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hiroshi,Takeuchi: "Addition of Phenylnitrenium Ion to Olefins. Reactions of Phenyl Azide with Some Olefins in the Presence of Trifluoroacetic Acid" J. Chem. Soc., Perkin Trans. 1. 677-684 (1985)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hiroshi,Takeuchi: "Cyclisation of 2-Azidodiphenylmethane and 2-Azidodiphenyls by Regiospecific N-Attack of Arylnitrenium-Aluminium Chloride Complexes" J. Chem. Sco., Chem. Commun.287-289 (1985)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hiroshi,Takeuchi: "N- and C-Attacks of Phenylnitrenium Ions Generated from Phenyl Azides in the Presence of Trifluoroacetic Acid and/or Trifluoromethanesuphonic Acid" J. Chem. Soc., Perkin Trans. 1. 611-618 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hiroshi,Takeuchi: "Inter- and Intra-moleculer Aromatic N-Substitution by Arylnitrenium- Aluminium Chloride Complexes" J. Chem. Soc., Perkin Trans. 1. 57-60 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hiroshi,Takeuchi: "Direct Amination of Aromatic Compounds by Nitrenium Ion and Alkylnitrenium Ions. Photolysis of 1-(Amino and alkylamino)-2-methy1-4,6-diphenylpyridinium Tetrafluoroborates in Aromatic Solvent-Trifluoroacetic Acid" J. Chem. Soc., Chem. Commun.961-963 (1987)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1989-03-30  

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