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1992 Fiscal Year Final Research Report Summary

Studies on the Development for New Synthetic Reagents of Organic Sulfur and Selenium Compounds and their Organization

Research Project

Project/Area Number 02453018
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionUniversity of Tsukuba

Principal Investigator

FURUKAWA Naomichi  TSUKUBA UNIV.,DEPT.OF CHEM.,PROFESSOR, 化学系, 教授 (80015966)

Project Period (FY) 1990 – 1992
KeywordsCoupling Reaction / PyridylSulfoxide / Optically Active Compound / Carbanion / Thianthrene / Pentalene / Thiophene / Ring Contraction and Enlargement
Research Abstract

1.It was found that phenyl 3- and 4-pyridyl sulfoxides underwent Grignard exchange reactions to afford readily 3-and 4-pyridyl magnesium bromide which reacted with various aldehydes and ketones to give the corresponding addition products. By using this exchange reactions, optically active 3-and 4-pyridylphenyl sulfoxides were prepared. On the other hand, 2-pyridyl phenyl sulfoxide gave under similar condition to provide the ligand coupling products.i.e., 2-pyridyl derivatives in high yields. The reaction of 2-PyS(O) Ph with LDA (lithium diisopropylamide) gave highly regioselectively the 3-lithiated sulfoxide which then reacts with electrophiles to result in the formation of the 3-substituted 2-phenylsulfinyl pyridines. These pyridyl derivatives gave finally optically active 2-phenyl pyridines on treatment with Grignard reagents. Also first synthesis of optically active 2-p-tolyl pyridyl sulfoxide was performed by employing the above mentioned procedure.
2. On treatment with LDA and then with ArCHO,optically pure 2-PyCH_2S(O)-Tol-p gave a-phenyl alkoxyl substituted sulfoxides by asymmetric induction. After desulfinylation, optically active 1-aryl-2-(2-pyridyl)ethanols were synthesized.
3. Monooxides of thianthrene and selenanthrene were converted to 4,6-disubstituted derivatives by treatment with LDA and electrophiles such as (PhS)_2. Furthermore,4,6-disubstituted thianthrene and selenanthrene 1-oxides were found to react with n-BuLito give the ring contracted 1,9-disubstituted dibenzothiophenes and dibenzoselenophenes. These 1,9-disubstituted dibenzothiophenes and dibenzoselenophenes provide [3.4, bc]thienothiophene and selenophene on pyrolysis and photolysis.

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] T.Kimura: "First Preparation and Structures of Dibenzo[bc,fg][1,4]- diselenapentalene and -selenathiapentalene." Chem.Lett.(1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Kimura: "Simple Preparation of Sterically Congested 1,9-Disubstituted Dibenzothiophenes and Formation of Their Dithia Dications via Transannular S-S Interaction." Heteroatom Chemistry. (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Kimura: "First Preparation of Dibenzo[bc,fg][1,4]dithiapentalene and Determination of the Structure by X-Ray Analysis." Tetrahedron Lett.33. 6355-6358 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Furukawa: "Preparation of 2,5-Disilylated Thiophene Derivatives and Their Conversion to 2,5-Dihalo Derivatives." Heterocycles. 34. 1085-1088 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Kimura: "Structures of Sterically Encumbered 1,9-Bis(arylthio)- dibenzothiophenes and Detection of Their Dithia Dications in Concentrated Sulfuric Acid by ^1H-NMR." Heterocycles. 33. 101-104 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Furukawa: "Generation of New Dithia Dications from Sterically Congested 1,9- Dithiodibenzothiophenes and Their Monooxides in Concentrated Sulfuric Acid." Tetrahedron Letters. 33. 1489-1490 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Kimura,Y.Ishikawa,and N.Furukawa.: "First Preparation and Structures of Dibenzo[bc,fg][1,4]-diselenapentalene and -selenathiapentalene." Chem.Lett.(1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Kimura,Y.Horie,S.Ogawa,and N.Furukawa F.Iwasaki.: "Simple Preparation of Sterically Congested 1,9-Disubstituted Dibenzothiophenes and Formation of Their Dithia Dications via Transannular S-S Interaction." Heteroatom Chemistry. (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Kimura,Y.Ishikawa,S.Ogawa,T.Nishio,I.Iida,and N.Furukawa.: "First Preparation of Dibenzo[bc,fg][1,4]dithiapentalene and Determination of the Structure by X-Ray Analysis." Tetrahedron Lett.33,No.42. 6355-6358 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N.Furukawa,H.Hoshiai,T.Shibutani,M.Higaki,F.Iwasaki,and H.Fujihara.: "Preparation of 2,5-Disilylated Thiophene Derivatives and Their Conversion to 2,5-Dihalo Derivatives." Heterocycles. 34. 1085-1088 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Kimura,Y.Horie,S.Ogawa,H. Fujihara,F.Iwasaki,and N.Furukawa.: "Structures of Sterically Encumbered 1,9-Bis(arylthio)-dibenzothiophenes and Detection of Their Dithia Dications in Concentrated Sulfuric Acid by ^1H-NMR." Heterocycles. 33. 101-104 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N.Furukawa,T.Kimura,Y.Horie,S.Ogawa,and H.Fujihara.: "Generation of New Dithia Dications from Sterically Congested 1,9-Dithiodibenzothiophenes and Their Monooxides in Concentrated Sulfuric Acid." Tetrahedron Letters. 33. 1489-1490 (1992)

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

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Published: 1994-03-24  

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