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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
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥15,100,000 (Direct Cost: ¥15,100,000)
Fiscal Year 2000: ¥4,800,000 (Direct Cost: ¥4,800,000)
Fiscal Year 1999: ¥10,300,000 (Direct Cost: ¥10,300,000)
KeywordsDication / Chalcogen Element / Interaction / Active Species / Accumulation Effect / Remote Reaction / Hypervalency / Benzothiete / カルコゲヌラン / テルラン / カルコゲニド / カルコゲナジカチオン / 情報伝達 / 渡環相互作用 / 分子内分子間相互作用 / 分子間相互作用 / ジカルコゲジカチオン / Pummerer反応 / テトラカチオン / 高配位テルル / 刺激の伝達
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

Report

(3 results)
  • 2001 Final Research Report Summary
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • Research Products

    (28 results)

All Other

All Publications (28 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
    • Related Report
      2001 Final Research Report Summary
  • [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
    • Related Report
      2001 Final Research Report Summary
  • [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
    • Related Report
      2001 Final Research Report Summary
  • [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
    • Related Report
      2001 Final Research Report Summary
  • [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
    • Related Report
      2001 Final Research Report Summary
  • [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
    • Related Report
      2001 Final Research Report Summary
  • [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
    • Related Report
      2001 Final Research Report Summary
  • [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
    • Related Report
      2001 Final Research Report Summary
  • [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
    • Related Report
      2001 Final Research Report Summary
  • [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
    • Related Report
      2001 Final Research Report Summary
  • [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
    • Related Report
      2001 Final Research Report Summary
  • [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
    • Related Report
      2001 Final Research Report Summary
  • [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
    • Related Report
      2001 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Naomichi Furukawa et al.: "Transannular and intermolecular interactions between chalcogen atoms : syntheses and properties of dichalcogena dications and trichalcogena hypervalent dications"Journal of Organometallic Chemistry. 611. 116-126 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Crystal structure of S-[4-(2,6-dimethylphenylselenide)-3,5-dimethyl-phenyl]-dibenzothiophenium bis (triflate) hydrate, [C_<20>H_<16>SSe_<0.5>]_2(CF_3O_3S)_22.78H_2O"Zeitschrift fYr Kristallographie-New Crystal Structures. 215. 555-556 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Crystal structure of 1-oxa-6-thia-7,10-bis (trimethylsilyl)-11-sulfoxide-spiro[4.4.5]undeca-3,8-dien-2-one,C_<14>H_<22>O_3S_2Si_2"Zeitschrift fYr Kristallographie-New Crystal Structures. 215. 359-360 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Crystal structure of bis[2,6-{bis (dimethylamino) methyl} phenyl]-di-moxoditellurium bis (hexafluorophosphate),[Te(C_<12>H_<19>N_2)Ol_2(PF_6)_2"Zeitschrift fYr Kristallographie-New Crystal Structures. 215. 21-22 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Crystal structure of 1,6-dibromo-2-phenyl-1,2-diselenaacenaphthylene, BrSe(C_<10>H_5Br)Se(C_6H_5)"Zeitschrift fYr Kristallographie-New Crystal Structures. 215. 23-24 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Ab initio molecular orbital study of dications of 1,5-Dichalcogenacyclooctanes"Heteroatom Chemistry. 11. 31-41 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Remote Pummerer Reaction via Intermolecular Through-Space Interaction between Sulfonium and Sulfenyl Sulfur Atmos"J. Org. Chem.. 64. 3190-3195 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Nucleophilic Addition of Telluroxides to a Cationic Ditelluroxane: Oilgotellurxanes"Angew. Chem. Int. Ed.. 38(11). 1638-1640 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Generation of Ketenes by Photolysis of Naphtho[1,8de]-1,3-dichalcogeninylidene 1-Oxides"Tertrahedron Letters. 40. 5211-5214 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Formation and Stability of New Hybrid Dichalcogena Dications(S-Se,S-Te and Se-Te) Bearing(2-Methychalcogenomethy1) phenyl Skeleton"Chemistry Letters. 723-724 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Through-bond interaction between sulfonium and sulfenyl sulfur atoms having anthracene and naphthalene spacers"Tetrahedron Letters. 40. 8833-8836 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Self-assembly of cavitand tetracarboxylic acid: highly porous packing structure of one-dimensional hydrogen-bonded network"Tetrahedron Letters. 40. 8883-8836 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Chemistry of Hypervalent Compounds"WILEY-VCH. 241 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "New Aspects of Hypervalent Organosulfur Compounds"Topics in Current Chemistry. 129 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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