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2001 Fiscal Year Final Research Report Summary

Investigation for Strategy on Preparation of New Accumulated Molecules by the Interaction of Chalcogen Elements

Research Project

Project/Area Number 11440186
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionFOUNDATION FOR ADVANCEMENT OF INTERNATIONAL SCIENCE (2000-2001)
University of Tsukuba (1999)

Principal Investigator

FURUKAWA Naomichi  FOUNDATION FOR ADVANCEMENT OF INTERNATIONAL SCIENCE, CHIEF RESEARCHER, 主席研究員 (80015966)

Co-Investigator(Kenkyū-buntansha) ERNST Horn  立教大学, 理学部・化学科, 教授
SATO Soichi  DEPARTMENT OF CHEMISTRY UNIVERSITY OF TSUKUBA, LECTURER, 化学系, 講師 (90280908)
KOBAYASHI Kenji  DEPARTMENT OF CHEMISTRY UNIVERSITY OF TSUKUBA, LECTURER, 化学系, 講師 (40225503)
HORN Ernst  DEPARTMENT OF CHEMISTRY RIKKYO UNIVERSITY, PROFESSOR
Project Period (FY) 1999 – 2000
KeywordsDication / Chalcogen Element / Interaction / Active Species / Accumulation Effect / Remote Reaction / Hypervalency / Benzothiete
Research Abstract

Both electronic and steric interaction work among the multiple chalcogen elements arranged appropriately in the molecules. In general, the repulsive forces predominantly work in the dicoordinated chalcogen elements. On the other hand, when one generates a cation at one of the chalcogen atoms in the molecule by oxidation, other dicoordinate chalcogen elements react with the cationic center by the attractive forces to form the stable dications between the two elements. Furthermore, this dication reacts cumulatively with other chalcogen elements to create a new chemical bonds having a hypervalent structure at the central chalcogen elements in the molecule. We have found that the dication species become a strong electron withdrawing property and activate the carbon atoms attached at the chalcogen elements of the dication.
In the present investigation, we report the following results : 1) by using the previous procedure, we succeeded to generate new active chemical species, i.e., carbocation … More s, ketenes, and carbens. We also succeeded to generate first organo-dicoordinated sulfur and selenium cations(R-S^+, R-Se^+). Furthermore, we could generate benzodithiete by the reaction of 2-benzylthiophenyl benzyl sulfoxide with Tf_2O. 2) 2, 6-Bisphenylchalcogenylmethylphenyl(or 2, 6-bisdimethylaminomethyl)phenyl telluride reacts with NOBF_4 to afford dication bearing a hypervalent tellurane structure at the central tellurium atom. By using this oxidation reaction we found a new remote oxidation reaction of the analogous molecules which have multi phenylenethio moiety as a spacer in the molecule. This reaction gave the oxidized product at the chalcogen atom at the separated position from that of the initial reaction site. We proposed that this new type of oxidation reaction should be called a remote oxidation and a new type of chemical reaction. 3) We identified the formation of the tetracation by following the 1^H-NMR spectorscopy on treatment of 1, 4-methylthiomethylsulfinylbenzene with CF_3CO_2H and as an extension of this reaction we could prepare various active polythiapoly cations from which cyclic polyphenylenepolysulfides were prepared. Less

  • Research Products

    (14 results)

All Other

All Publications (14 results)

  • [Publications] Naomichi Furukawa et al.: "Self-assembly of a Radially Functionalized Hexagonal Molecule : Hexakis(4-hydroxyphenyl)benzene"Angew.Chem., Int.Ed.. 38. 3483-3486 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Naomichi Furukawa et al.: "Two-Dimensional Hexagonal Hydrogen-Bonded Network with Triangle-Like Large Cavities : Hexakis(4-carboxyphenyl)benzene"Tetrahedron Lett.. 41. 89-93 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Naomichi Furukawa et al.: "Molecular Capsule Constructed by Multi Hydrogen Bonds : Self-Assembly of Cavitand Tetracarboxylic Acid with 2-Aminopyrimidine"Chem.Commun.. 41-428 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Naomichi Furukawa et al.: "Reduction of Sulfoxides to Sulfides Mediated by Ferrocene and Trifluoroacetic Anhydride"Chem.Let.. 400-401 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Naomichi Furukawa et al.: "Dealkylation of a 1,2-bis(benzylthio)benzene derivative : generation of benzothiete or its equivalent via a dithia dication"Chem.Commun.. 1667-1668 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Naomichi Furukawa et al.: "Synthesis and Properties of Ditelluroxanes and Oligochalcogenozxanes : Hypervalent Oligomers with Te-O Apical Linkages in the Main Chain"Chem.Eur.J.. 7. 4272-4279 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Naomichi Furukawa et al.: "Chemistry of Hypervalent Compounds"WILEY-VCH. 241 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Kobayashi, T. Shirasaka, A. Sato, E. Horn, and N. Furukawa: "Self-assembly of a Radially Functionalized Hexagonal Molecule"Angew. Chem., Int, Ed.. 38. 3483-3486 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Kobayashi, T. Shirasaka, E. Horn, and N. Furukawa: "Two-Dimensional Hexagonal Hydrogen-Bonded Network with Triangle-Like Large Cavities : Hexakis(4-caboxyphenyl) benzene"Tetrahedron Lett.. 41. 89-93 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Kobayashi, T. Shirasaka, K. Yamaguchi, S. Sakamoto, E. Horn, and N. Furukawa: "Molecular Capsule Constructed by Multi Hydrogen Bonds : Self-Assembly of Cavitand Tetracarboxylic Acid with 2-Aminopyrimidine"Chem. Commun.. 41-428 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Kobayashi, Y. Kubota, and N. Furukawa: "Reduction of Sulfoxides to Sulfides Mediated by Ferrocene and Trifluoroacetic Anhydride"Chem. Let.. 400-401 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Kobayashi, E. Koyama, M. Goto, C. Noda, and N. Furukawa: "Dealkylation of a 1, 2-bis (benzylthio) benzene derivative : beneration of benzothiete or its equivalent via a dithia dication"Chem. Commun.. 1667-1668 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Kobayashi, K. Tanaka, H. Izawa, Y. Arai, and N. Furukawa: "Synthesis and Properties of Ditelluroxanes and Oligochalcogenozxanes : Hypervalent Oligomers with Te-O Apical Linkages in the Main Chain"Chem. Eur. J. 7. 4272-4279 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Furukawa and S. Sato: "Structure and Reactivity of Hypervalent Chalcogen Compounds : Selenuran (Selane) and Tellurane (Tellane)"Chemistry of Hypervalent Compunds, Chapt. 8, Ed. By K. Akiba, Wiley-VCH. (2000)

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      「研究成果報告書概要(欧文)」より

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Published: 2003-09-17  

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