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Direct Conversion Reaction of Toluenes to Conjugated-Trienes and Their Applications

Research Project

Project/Area Number 01571160
Research Category

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

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionNagoya City University

Principal Investigator

SATO Yoshiro  Nagoya City University Pharmaceutical Sciences Professor, 薬学部, 教授 (80080183)

Project Period (FY) 1989 – 1990
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1990: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1989: ¥1,600,000 (Direct Cost: ¥1,600,000)
KeywordsYlide / Ammonium Salt / Sigmatropic Rearrangement / Sommelet-Hauser Rearrangement / Stevens Rearrangement / Conjugated-Triene / Organosilicon Compound / Amine / 有機ケイ素化合物 / ベンジルアミン / N-イリド / Sommelet-Hauser転位 / 環拡大
Research Abstract

When trialkylbenzylammonium salts were treated with a strong base such as sodium amide in liquid ammonia, benzylammonium N-ylides intermediates are initially formed which subsequently rearrange to 6-aminomethyl-5-methylene-1,3-cyclohexadenes (conjugated trienes) via a [2,3] sigmatropic pathway. However, isolation of the trienes was difficult because they were quickly aromatized to 2-methylbenzylamines (Sommelet-Hauser rearrangement).
N-Methylide formation reaction in non-basic mediums was revealed as a result of fluoride-ion induced desilylation reaction of N- (trimethylsilyl) methylammonium salts with cesium fluoride in dimethylformamide or hexamethylphosphoramide at room temperature in our laboratory. In this reaction condition, some conjugated triene compounds which were rearrangement products of benzylammonium N-methylides, were stable enough to isolate at room temperature and applied for DielsーAlder reaction to give polycyclic amines.

Report

(3 results)
  • 1990 Annual Research Report   Final Research Report Summary
  • 1989 Annual Research Report
  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] Naohiro Shorai: "Rearrangement of 1ーMethylー2ー(substituted phenyl)piperidinium 1ーMethylides in a Neutral Medium" The Journal of Organic Chemistry. 54. 836-840 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Seiji Okazaki: "Synthesis of 1ー(Trimethylsilyl)alkylamines" Synthesis. 36-38 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Seiji Okazaki: "Chemical Behavior of NーAlkylーNーmethylbenzylammonium NーAlkylide" The Journal of Organic Chemistry. 55. 334-337 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Naohiro Shirai: "Intermediate in SommeletーHauser Rearrangement og N,NーDimethylbenzylammonium NーMethylides" The Journal of Organic Chemistry. 55. 2767-2770 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Fumihiko Sumiya: "ConjugatedーTriene Intermadiates in the SommeletーHauser Rearraangement of 1ーMethylー2ーphenylcycloammonium 1ーMethylides" Chemical and Pharmaceutical Bulletin. 39. 36-40 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yoshio Machida: "Synthesis of 5ーAlkylideneー6ー(dimethylamino)methylー1,3ーcyclohexadienes from(αーSubstituted benzyl)ammonium NーMethylide" Synthesis. (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Fumihiko Sumiya: "ConjugatedーTriene Intermediates in the SommeletーHauser Rearrangement of 1ーMethy1ー2ーphenylcycloammonium 1ーMethylides" Chemical and Pharmaceutical Bulletin. 39. 36-40 (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] Yoshio Machida: "Synthesis of 5ーAlkylideneー6ー(dimethylamino)methy1ー1,3ーcyclohexadienes from(αーSubstituted benzyl)ammonium NーMethylide" Synthesis. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] Naohiro Shirai: "Rearrangement of 1-Methy1-2-(substituted-phenyl)piperidinium 1-Methylides in a Neutral Medium" The Journal of Organic Chemistry. 54. 836-840 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] Seiji Okazaki: "Chemical Behavior of N-Alkyl-N-methylbenzylammonium N-Alkylide" The Journal of Organic Chemistry. 55. 334-337 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] Naohiro Shirai: "Intermediate in Sommelet-Hauser Rearrangement of N,N-Dimethylbenzylammonium N-Methylides" The Journal of Organic Chemistry. 55. (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] Fumihiko Sumiya: "Conjugated-Triene Intermediates in the Sommelet-Hauser Rearrangement of 1-Methy-2-phenylcycloammonium 1-Methylides" Journal of Heterocylic Chemistry.

    • Related Report
      1989 Annual Research Report

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Published: 1989-04-01   Modified: 2016-04-21  

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