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Study on Synthesis and Properties of Novel pi System Compounds

Research Project

Project/Area Number 07640709
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionSaitama University

Principal Investigator

MACHIGUCHI Takahisa  Saitama University, Faculty of Science Professor, 理学部, 教授 (00008864)

Co-Investigator(Kenkyū-buntansha) YAMADA Shinichi  Nara University of Education, Educational Technology Center, Professor, 教育学部, 教授 (00109117)
HASEGAWA Toshio  Saitama University, Faculty of Science Research Assistant, 理学部, 助手 (00237976)
Project Period (FY) 1995 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1997: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1996: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1995: ¥1,000,000 (Direct Cost: ¥1,000,000)
KeywordsRing Opening Reaction / Triene / Tropothione / Tropothione S-sulfide / Metal Complex / Ketene / Diene / [4+2] Cycloaddition / トロポン / 赤外スペクトル / 水銀錯体 / トリポチオン / π電子系化合物 / チオスルフィン / 双極子モーメント
Research Abstract

We have found the following results,
1.A novel and supriginly facilc nucleophilic ring opening of tropone oxime tosylate to produce all-cisoid trienes stereoselectively. The reaction is usuful method to obtain conjugated trienes.
2.Tropothione S-sulfife is synthesized from tropone hydrazone with S_2Cl_2. The S-sulfide is detected as an unprecedented [10pi+2pi] -type cycloadduct with DMAD.
3.We have suceeded in synthesis, isolation, and spectral characterization of tropothione, the sulfur analogue of tropone. The physical properties of tropothione are in sharp contrast to those of tropone. The electric dipole moment of tropothione and tropone hase been compared. The charge separation of tropothione and tropone is evaluated on the basis of the dipole moment and ab initio calculations.
4.HgCl_2 complexes of tropothione and tropone are studied both experimentally and theoritically. IR spectroscopic data of these complexes are compared with theoritical ones derived from vidrational analyzes. Tropone is linked with HgCl_2 in the form of a sigmacomplex. But, tropothione give pi complex.
5.Non-recognition for dienes in ketene reactions has long been an important problem in organic chemistry since the diphenylkefene-cyclopentadiene reaction was found by Staudinger in 1920. We have discoverd that the ketene recognizes conjugated dienes. The ketene is a dienophile not for well-known [2+2] cycloadditions but [4+2] (Diels-Alder) reactions across its C=O bond.

Report

(4 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • 1995 Annual Research Report
  • Research Products

    (38 results)

All Other

All Publications (38 results)

  • [Publications] T.Machiguchi: "A Novel Synthesisof Trienes Nucleophilic Ring Cleavage of Tropone Oxime Tosylate" J.Am.Chem.Soc.117. 1258-1264 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Machiguchi: "Tropothione S-Sulfide,A New Class of Thisulfine" Chem.Lett.1821-1822 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Machiguchi: "Synthsis and Isolation of Tropothione:A Comparative Study of Spectral Property withTropone" Tetrahedron. 51. 2507-2514 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Yamabe: "Ketene is a Dienophile for [4【double half arrows】2](Diels-Alder)Reactions across its C_〓O Bond." J.Am.Chem.Soc.118. 6518-6519 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Machiguchi: "The problem of non-recognition for dienes in ketene reactions(A big fault in ketene history and its sokution)" J.Synth.Org.Chem.Jpn.55. 56-64 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Yamabe: "Novel πHgCl_2 comblexes of tropothione" J.Mol.Struct,CHEOCHEM. 418. 197-207 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Machiguchi: "A Novel Synthesis of Trienes by Nucleophilic Ring Cleavage of Tropone Oxime Tosylate" J.Am.Chem.Soc.117. 1258-1264 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Machiguchi: "Tropothione S-Sulfide. A New Class of Thiosulfine" Chem.Lett.1821-1822 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Machiguchi: "Synthesis and Isolation of Tropothione : A Comparative Study of Spectral Property with Tropone" Tetrahedron. 51. 1133-1142 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Minato: "Tropothione versus Tropone : A Comparison of the Charge Separation in the Ground State" Tetrahedron. 51. 2507-2514 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Okuma: "Reaction of Vinylphosphonium Salts with Sulfoxonium Ylides. Synthesis of Cyclopropylphosphonium Salts" Bull.Chem.Soc.Jpn.68. 2313-2317 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Yamabe: "Ketene is a Dienophile for [4+2] (Diels-Alder) Reactions across its C==O Bond." J.Am.Chem.Soc.118. 6518-6519 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Minato: "WHY ARE THE TROPONOID RINGS OF THE MESYLATE AND TOSYLATE OF TROPONE OXIME CLEAVED EASILY BYNUCLEOPHILES?" Tetrahedron. 52. 8439-8450 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.MATSUMOTO: "Unusual formation and X-ray crystal structure of stable anti-Bredt compound by reaction of diazapentalene with dimethyl acetylene dicarboxylate" J.Chem.Soc. , Perkin Trans.1. 2333-2335 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.MATSUMOTO: "Formation of 1 : 2,3 : 4-dibenzocycl [2.2.3] azines by a novel consecutive 1,3-dipolar cycloaddition of pyridinium dicyanomethilides to benzyne" J.Chem.Soc. , Perkin Trans.1. 2599-2602 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Matsumoto: "Oxidation potentials and electron spin resonance spectra of 1 : 2,3 : 4-dibenzocycl [2.2.3] azines and their radical cations. A novel peripheral 18pi system" Bull.Chim.Soc.France. 891-896 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Machiguchi: "The problem of non-recognition for dienes in ketene reactions (A big fault in ketene history and its solution)" J.Synth.Org.Chem.Jpn.55. 56-64 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Yamabe: "Novel pi HgCl_2 complexes of tropothione" J.Mol.Struct.CHEOCHEM. 418. 197-207 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Hasegawa: "Infrared Spectroscopy of Tropothione" J.Mol.Struct.CHEOCHEM. 418. 221-229 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Matsumoto: "Correlation of ^<13>C-and ^<15>N-NMR Chemical Shifts of Ylidic Carbon and Nitrogen with Calculated Partial Charges in Pyridinium Dicyanomethylides" Heterocycles. 45. 2443-2448 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Matsumoto: "Correlation of ^<15>NNMR Chemical Shifts with Calculated Partial in Pyridine N-oxide" Heterocycles. 45. 645-650 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Matsumoto: "Synthesis and Properties of Porphyrin-linked Indolizine" Heterocycles. (in press). (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T. Machiquchi: "The Problem of Non-recognition for Dienes in Ketene Reactions (A Big Fault in Ketene History and its Solution)" J.Synth.org.Ohem. Jpn.55. 56-64 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] S. Yamabe: "Novel π HgCl^2Complexes of Tropothine" J. Mol. Struct. CHEOCHEM. 418. 197-207 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T. Hasegawa: "Infrared Spectroscopy of Tropothione" J. Mol. Struct. CHEOCHEM. 418. 221-229 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K. Matsumoto: "Correlation of 15N-NMR Chemical Shifts with Calculated Partizl in Pyridine N-Oxide" Heterocycles. 45. 645-650 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K. Matsumoto: "Correlation of 13C-and15N-NMR Chemical Shifts of Ylidic Carbon and Nitrogen with Calculataed Partial Charges in Pyridinium Dicyanomethylides" Heterocycles. 45.

    • Related Report
      1997 Annual Research Report
  • [Publications] K. Matsumoto: "Synthesis and Properties Prophyrin-linked Indolizine" Heterocycles. 46(in Press). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Shinichi Yamabe: "Ketene is a Dienophile for [4+2](Diels-Alder) Reactions Across its C=O Bond" J.Am.Chem.Soc.118. 6518-6519 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Tsutomu Minato: "Why are the Troponoid Rings of the Mesylate and Tosylate of Tropone Oxime Cleaved Easily by Nucleophiles?" Tetrahedron. 52. 8439-8450 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Shinichi Yamabe: "Novel πHgCl_2 Complexes of Tropothione" J.Mol.Struct.THEOCHEM. 387. 2864-2872 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Toshio Hasegawa: "Infrared Spectroscopy of Tropothione" J.Mol.Struct.THEOCHEM. 387. 2918-2926 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Takahisa Machiguchi: "The Problem of Non-Recognition for Dienes in Ketene Reactions (A Big Fault in Ketene Histry and Its Solution)" 有機合成化学協会誌. 55. 56-64 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Takahisa Machiguhi: "A Novel Synthesis of Trienes by Nucleophilic Ring Cleavagel of Tropone Oxime Tosylate" J. Am. Chem. Soc.117. 1258-1264 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Takahisa Machiguchi: "Tropothione S-Sulfide. A New Class of Thiosulfine" Chem. Lett.103-104 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Takahisa Machiguchi: "Synthesis and Isolation of Tropothione: A Comparative Study of Spectral Property with Tropone" Tetrahedron. 51. 1133-1142 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Tsutomu Minato: "Tropothione versus Tropone: A Comparison of the Carge Separation in the Ground State" Teterahedoran. 51. 2507-2514 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Shinichi Yamabe: "Fine Tuning [4+2] and [2+4]q Diels-Alder Reactions Catalyzed by Lewis Acids" J. Am. Chem. Soc.117. 10994-10997 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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