Updated on 2025/07/03

写真b

 
KOBAYASHI JUNJI
 
*Items subject to periodic update by Rikkyo University (The rest are reprinted from information registered on researchmap.)
Affiliation*
Preparatory Office for College of Environmental Studies
Graduate School of Science Doctoral Program in Chemistry
Graduate School of Science Master's Program in Chemistry
Title*
Professor
Degree
Ph.D. ( 4 2001   The University of Tokyo )
Courses in charge*
Campus Career*
  • 4 2025 - Present 
    Preparatory Office for College of Environmental Studies   Professor
  • 4 2024 - Present 
    Graduate School of Science   Master's Program in Chemistry   Professor
  • 4 2024 - Present 
    Graduate School of Science   Doctoral Program in Chemistry   Professor
  • 4 2024 - 3 2025 
    Preparatory Office for College of Environmental Studies   Professor
 

Research Areas

  • Environmental Science/Agriculture Science / Chemical substance influence on environment

  • Environmental Science/Agriculture Science / Environmental materials and recycle technology

  • Nanotechnology/Materials / Structural organic chemistry and physical organic chemistry

  • Nanotechnology/Materials / Functional solid state chemistry

Research History

  • 4 2024 - Present 
    Rikkyo University   Preparatory Office for College of Environmental Studies   Professor

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    Country:Japan

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  • 4 2020 - 3 2024 
    International Christian University   College of Liberal Arts Major: Chemistry   Associate Dean, College of Liberal Arts

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  • 4 2015 - 3 2024 
    International Christian University   College of Liberal Arts Major: Chemistry   Senior Associate Professor

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  • 4 2015 - 3 2017 
    International Christian University   Center for Teaching and Learning   Associate Director

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  • 9 2014 - 3 2017 
    International Christian University   Academic Planning Center   Director

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  • 4 2012 - 3 2016 
    International Christian University   Chemistry Major   Major Adviser

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  • 9 2010 - 3 2015 
    International Christian University   College of Liberal Arts   Associate Professor

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  • 4 2007 - 8 2010 
    The University of Tokyo   Department of Chemistry, Graduate School of Science   Assistant Professor

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  • 1 2001 - 3 2007 
    The University of Tokyo   Department of Chemistry, Graduate School of Science   Research Associate

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Education

  • 4 1998 - 12 2000 
    The University of Tokyo   Graduate School of Science   Department of Chemistry

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  • 4 1996 - 3 1998 
    The University of Tokyo   Graduate School of Science   Department of Chemistry

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  • 4 1992 - 3 1996 
    The University of Tokyo   Faculty of Science   Department of Chemistry

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Papers

  • Synthesis, structures and properties of novel tricyclic tetraalkylphosphoranes with hydrogen and chlorine atoms at the apical position Peer-reviewed

    Takayuki Kawashima, Atsushi Yatabe, Shin-ya Nakafuji, Junji Kobayashi, Yosuke Uchiyama

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS197 ( 5-6 ) 414 - 419   6 2022

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1080/10426507.2021.2013844

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  • In-beam Mossbauer spectra for Mn-57 implanted sulfur hexafluoride Peer-reviewed

    Yasuhiro Yamada, Yukiko Sato, Yoshio Kobayashi, Takatoshi Ando, Noriko Takahama, Kanako Some, Masami Sato, Mototugu Mihara, M. Kenya Kubo, Wataru Sato, Jun Miyazaki, Takashi Nagatomo, Junji Kobayashi, Atsushi Okazawa, Shinji Sato, Atsushi Kitagawa

    HYPERFINE INTERACTIONS241 ( 1 )   2 2020

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    Language:English   Publishing type:Research paper (international conference proceedings)  

    DOI: 10.1007/s10751-019-1655-y

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  • Triphosphasumanene Trisulfide: High Out-of-Plane Anisotropy and Janus-Type pi-Surfaces Peer-reviewed

    Shunsuke Furukawa, Yuki Suda, Junji Kobayashi, Takayuki Kawashima, Tomofumi Tada, Shintaro Fujii, Manabu Kiguchi, Masaichi Saito

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY139 ( 16 ) 5787 - 5792   4 2017

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/jacs.6b12119

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  • The Chemistry of Heterasumanenes

    Masaichi Saito, Shunsuke Furukawa, Junji Kobayashi, Takayuki Kawashima

    CHEMICAL RECORD16 ( 1 ) 64 - 72   2 2016

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/tcr.201500211

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  • Synthesis of π-Extended Dibenzophospholes by Intramolecular Radical Cyclization and Their Properties

    Shunsuke Furukawa, Shunsuke Haga, Junji Kobayashi, Takayuki Kawashima

    Organic Letters16 ( 12 ) 3228 - 3231   3 6 2014

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/ol501189u

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  • Low-Coordinate Germanium(II) Centers Within Distorted Axially Chiral Seven-Membered Chelates: Stereo- and Enantioselective Cycloadditions

    Hidekazu Arii, Taiyo Amari, Junji Kobayashi, Kunio Mochida, Takayuki Kawashima

    Angewandte Chemie International Edition51 ( 27 ) 6738 - 6741   5 6 2012

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/anie.201201566

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  • Synthesis and Structure of a Heptacoordinate Trichlorostannane Bearing a Triarylmethyl-Type Tetradentate Ligand

    Junji Kobayashi, Kohei Iwanaga, Takayuki Kawashima

    ORGANOMETALLICS29 ( 21 ) 5725 - 5727   11 2010

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/om100386v

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  • Chemistry of pentacoordinated anti-apicophilic phosphorus compounds

    Junji Kobayashi, Takayuki Kawashima

    COMPTES RENDUS CHIMIE13 ( 8-9 ) 1249 - 1259   8 2010

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1016/j.crci.2010.06.010

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  • Synthesis of a C-3 Symmetric Host Molecule for C-60 Bearing a Bicyclic Triarylphosphate Framework

    Junji Kobayashi, Yuya Domoto, Takayuki Kawashima

    CHEMISTRY LETTERS39 ( 2 ) 134 - 135   2 2010

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1246/cl.2010.134

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  • Synthesis and Optical Properties of a Bis(Benzothiaborino)Carbazole, a Thiaborin-Carbazole Mixed Ladder-Type -Conjugated Molecule

    Tomohiro Agou, Junji Kobayashi, Takayuki Kawashima

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS185 ( 5-6 ) 947 - 951   2010

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1080/10426501003769736

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  • Application of the sila-Friedel–Crafts reaction to the synthesis of π-extended silole derivatives and their properties

    Shunsuke Furukawa, Junji Kobayashi, Takayuki Kawashima

    Dalton Transactions39 ( 39 ) 9329 - 9329   2010

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/c0dt00136h

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  • Multi-step detection of cyanide ion by a bis(dimesitylboryl)dibenzoazaborine

    Tomohiro Agou, Masaki Sekine, Junji Kobayashi, Takayuki Kawashima

    JOURNAL OF ORGANOMETALLIC CHEMISTRY694 ( 23 ) 3833 - 3836   11 2009

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1016/j.jorganchem.2009.07.046

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  • Development of a Sila-Friedel-Crafts Reaction and Its Application to the Synthesis of Dibenzosilole Derivatives

    Shunsuke Furukawa, Junji Kobayashi, Takayuki Kawashima

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY131 ( 40 ) 14192 - +   10 2009

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/ja906566r

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  • Synthesis of pi-Conjugated Dendrimers Based on Azaborines

    Tomohiro Agou, Tatsuo Kojima, Junji Kobayashi, Takayuki Kawashima

    ORGANIC LETTERS11 ( 16 ) 3534 - 3537   8 2009

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/ol901035d

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  • Synthesis and Reversible Control of the Fluorescent Properties of a Divalent Tin Dipyrromethene

    Junji Kobayashi, Tomokatsu Kushida, Takayuki Kawashima

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY131 ( 31 ) 10836 - +   8 2009

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/ja904470m

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  • Synthesis and Properties of Pentacoordinated Phosphorus Compounds with Anti-apicophilic Arrangement

    Junji Kobayashi, Takayuki Kawashima

    JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN67 ( 8 ) 787 - 797   8 2009

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  • Detection of Biologically Important Anions in Aqueous Media by Dicationic Azaborines Bearing Ammonio or Phosphonio Groups

    Tomohiro Agou, Masaki Sekine, Junji Kobayashi, Takayuki Kawashima

    CHEMISTRY-A EUROPEAN JOURNAL15 ( 20 ) 5056 - 5062   2009

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/chem.200802159

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  • Synthesis and reactivity of a bis(dimesitylboryl)azaborine and its fluoride sensing ability

    Tomohiro Agou, Masaki Sekine, Junji Kobayashi, Takayuki Kawashima

    CHEMICAL COMMUNICATIONS ( 14 ) 1894 - 1896   2009

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/b818505k

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  • Synthesis of Dibenzochalcogenaborins and Systematic Comparisons of Their Optical Properties by Changing a Bridging Chalcogen Atom

    Junji Kobayashi, Keiko Kato, Tomohiro Agou, Takayuki Kawashima

    CHEMISTRY-AN ASIAN JOURNAL4 ( 1 ) 42 - 49   2009

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/asia.200800302

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  • Perfectly "Anti-Apicophilic" Phosphoranes: Conversion of a 1-Hydro-5-carbaphosphatrane into 1-Alkyl- and 1-Aryl-5-carbaphosphatranes

    Junji Kobayashi, Takayuki Kawashima

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS184 ( 4 ) 1028 - 1035   2009

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1080/10426500902748080

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  • Inclusion of C60 into the hexagonal columnar space formed by intra- and intermolecular CH⋯π interactions

    Junji Kobayashi, Yuya Domoto, Takayuki Kawashima

    Chemical Communications ( 41 ) 6186 - 6186   2009

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/b909881j

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  • Synthesis, optical properties, and reactivities of a dibenzophosphaborin and its derivatives

    Junji Kobayashi, Tomohiro Agou, Takayuki Kawashima

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS183 ( 2-3 ) 389 - 392   2 2008

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1080/10426500701735296

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  • Synthesis and complexations of a novel stable carbene bearing a phosphorus ylide

    Shin-ya Nakafuji, Junji Kobayashi, Takayuki Kawashima

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS183 ( 2-3 ) 642 - 643   2 2008

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1080/10426500701795167

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  • A novel ylide-stabilized carbene; formation and electron donating ability of an amino(sulfur-ylide)carbene

    Junji Kobayashi, Shin-ya Nakafuji, Atsushi Yatabe, Takayuki Kawashima

    CHEMICAL COMMUNICATIONS ( 46 ) 6233 - 6235   2008

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/b813454e

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  • Generation and coordinating properties of a carbene bearing a phosphorus ylide: An intensely electron-donating ligand

    Shin-ya Nakafuji, Junji Kobayashi, Takayuki Kawashima

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION47 ( 6 ) 1141 - 1144   2008

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/anie.200704746

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  • Steric stabilization of a monomeric proalumatrane: Experimental and theoretical studies

    Weiping Su, Junji Kobayashi, Arkady Ellern, Takayuki Kawashima, John G. Verkade

    INORGANIC CHEMISTRY46 ( 19 ) 7953 - 7959   9 2007

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/ic7010327

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  • Phase transfer of fluoride ion by phosphonioborins

    Tomohiro Agou, Junji Kobayashi, Youngmin Kim, Franqois P. Gabbai, Takayuki Kawashima

    CHEMISTRY LETTERS36 ( 8 ) 976 - 977   8 2007

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1246/cl.2007.976

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  • Development of a general route to periphery-functionalized azaborines and ladder-type azaborines by using common intermediates

    Tomohiro Agou, Junji Kobayashi, Takayuki Kawashima

    CHEMICAL COMMUNICATIONS ( 30 ) 3204 - 3206   2007

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/b706418g

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  • Electronic and optical properties of ladder-type heteraborins

    Tomohiro Agou, Junji Kobayashi, Takayuki Kawashima

    CHEMISTRY-A EUROPEAN JOURNAL13 ( 28 ) 8051 - 8060   2007

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    Language:English  

    DOI: 10.1002/chem.200700622

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  • Fluoride ion complexation by a cationic borane in aqueous solution

    Min Hyung Lee, Tomohiro Agou, Junji Kobayashi, Takayuki Kawashima, Francois P. Gabbai

    CHEMICAL COMMUNICATIONS ( 11 ) 1133 - 1135   2007

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/b616814k

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  • Tuning of the optical properties and Lewis acidity of dibenzopnictogenaborins by modification on bridging main group elements

    Tomohiro Agou, Junji Kobayashi, Takayuki Kawashima

    INORGANIC CHEMISTRY45 ( 22 ) 9137 - 9144   10 2006

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/ic061055q

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  • Syntheses, structures, and reactions of heptacoordinate trihalogermanes bearing a triarylmethyl-type tetradentate ligand

    Kohei Iwanaga, Junji Kobayashi, Takayuki Kawashima, Nozomi Takagi, Shigeru Nagase

    ORGANOMETALLICS25 ( 14 ) 3388 - 3393   7 2006

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/om060031o

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  • Syntheses, structure, and optical properties of ladder-type fused azaborines

    Tomohiro Agou, Junji Kobayashi, Takayuki Kawashima

    ORGANIC LETTERS8 ( 11 ) 2241 - 2244   5 2006

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/ol060539n

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  • Reactivity of 1-hydro-5-carbaphosphatrane based on tautomerization between pentavalent phosphorane and trivalent cyclic phosphonite

    Junji Kobayashi, Kei Goto, Takayuki Kawashima, Michael W. Schmidt, Shigeru Nagase

    CHEMISTRY-A EUROPEAN JOURNAL12 ( 14 ) 3811 - 3820   5 2006

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/chem.200500864

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  • Evaluation of sigma-donating ability of a 9-phosphatriptycene and its application to catalytic reactions Peer-reviewed

    T Agou, J Kobayashi, T Kawashima

    CHEMISTRY LETTERS33 ( 8 ) 1028 - 1029   8 2004

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1246/cl.2004.1028

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  • A novel and convenient synthetic route to a 9-phosphatriptycene and systematic comparisons of 9-phosphatriptycene derivatives Peer-reviewed

    J Kobayashi, T Agou, T Kawashima

    CHEMISTRY LETTERS32 ( 12 ) 1144 - 1145   12 2003

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1246/cl.2003.1144

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  • Bonding properties of 5-carbaphosphatranes

    K Goto, J Kobayashi, T Kawashima, MW Schmidt, S Nagase

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS177 ( 8-9 ) 2037 - 2038   8 2002

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1080/10426500290094323

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  • Reactions of 1-hydro-5-carbaphosphatrane: Tautomerization between five-coordinate and three-coordinate species

    J Kobayashi, K Goto, T Kawashima

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS177 ( 6-7 ) 1405 - 1407   6 2002

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1080/10426500290092677

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  • Synthesis, structure, and bonding properties of 5-carbaphosphatranes: A new class of main group atrane

    J Kobayashi, K Goto, T Kawashima, MW Schmidt, S Nagase

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY124 ( 14 ) 3703 - 3712   4 2002

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/ja011458j

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  • 5-carbaphosphatranes: The first main group atrane bearing a 1-5 covalent bond

    J Kobayashi, K Goto, T Kawashima

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY123 ( 14 ) 3387 - 3388   4 2001

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/ja0056264

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  • Synthesis and structure of 5-carbaphosphatrane Peer-reviewed

    J Kobayashi, K Goto, T Kawashima

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS168   597 - 600   2001

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  • Synthesis and Structure of 5-Carbaphosphatrane

    Junji Kobayashi, Kei Goto, Takayuki Kawashima

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS169 ( 1 ) 273 - 276   2001

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1080/10426500108546641

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  • Synthesis, structure, and reducing ability of a stable organotrihydroaluminate bearing a novel bowl-type substituent

    K Goto, J Kobayashi, R Okazaki

    ORGANOMETALLICS18 ( 8 ) 1357 - 1359   4 1999

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/om9805032

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  • Novel intramolecular cyclization reaction involving a thionitroso group: Formation of a 3,3a-dihydro-2,1-benzisothiazole from an o-alkylthionitrosoarene

    B Tan, K Goto, J Kobayashi, R Okazaki

    CHEMISTRY LETTERS ( 10 ) 981 - 982   10 1998

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1246/cl.1998.981

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Misc.

  • Synthesis and structure of a novel symmetrically substituted phosphatriptycene oxide

    J Kobayashi, T Agou, T Kawashima

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS179 ( 4-5 ) 959 - 960   4 2004

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    Language:English  

    DOI: 10.1080/10426500490429086

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  • Synthesis structure and reactivity of a symmetrically substituted 9-phosphatriptycene oxide and its derivatives

    T Agou, J Kobayashi, T Kawashima

    HETEROATOM CHEMISTRY15 ( 6 ) 437 - 446   2004

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    Language:English  

    DOI: 10.1002/hc.20038

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  • Bonding in an isoelectronic atrane series.

    MW Schmidt, S Nagase, J Kobayashi, K Goto, T Kawashima

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY222   U221 - U221   8 2001

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    Language:English   Publishing type:Research paper, summary (international conference)  

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Professional Memberships

Research Projects

  • Exhaustive syntheses of ambipolar molecules by utilizing pi-conjugated modules based on an ethynylene unit

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research 

    KOBAYASHI Junji

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    4 2013 - 3 2017

    Grant number:25410052

    Grant amount:\5200000 ( Direct Cost: \4000000 、 Indirect Cost:\1200000 )

    N-Silylethynylcarbazoles have been synthesized. The fluorescent spectra of these compounds showed excimer emission. Ethynyldibenzosilole, in which the dibenzosilole unit is utilized as an acceptor, has been also synthesized. By coupled with various iodoarenes, donor-acceptor dyes have ben synthesized. These dyes also showed the excimer emissions. As described, each module bearing donor unit or acceptor unit with ethynylene spacer have been successfully synthesized. These modules have been proved to be applicable for synthesis of various dyes.

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  • スマネン骨格を有する三座配位子を活用したバルクおよび金属表面での高次π空間の創出

    日本学術振興会  科学研究費助成事業 

    小林 潤司

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    4 2011 - 3 2013

    Grant number:23108722

    Grant amount:\4420000 ( Direct Cost: \3400000 、 Indirect Cost:\1020000 )

    ヘテロ-π共役化合物は典型元素の元素特性とπ共役系との相互作用に起因して、発光性や電子受容能の向上といった優れた物性を有することから、盛んに研究がなされている。しかし、既存のヘテロ-π共役化合物の多くは、アセン類のようにπ電子系を一次元的に伸長したものであり、より高次元に拡張したπ共役系に典型元素を組み込んだ例は限られていた。本研究では、2次元的に広がったπ共役系に対し典型元素を導入したヘテロ-π共役化合物を創製することで、拡張π共役系と典型元素固有の性質との相乗効果を活用した新規な光・電子物性の発現を目指した。基本骨格としてトリフェニレンを選定し、分子周縁部にケイ素、スズ、またはリンを導入することで、ディスク状の平面π共役分子であるトリヘテラスマネンの合成に成功している。リンを導入した分子については、リン原子上を硫化することでホスフィンスルフィドへの誘導化も行なった。さらに合成したトリヘテラスマネンのUV/visスペクトルでは、導入した典型元素に応じて吸収・発光波長が変化しており、典型元素とトリフェニレンπ電子系が良好に相互作用していることを確認している。本年度はさらに同様の手法を活用し、トリヘテラスマネン合成の共通前駆体であるヘキサリチオ体を用い、オキサリルクロリドと反応させることによって、コロネン誘導体へと変換することを試みた。その結果、トリフェニレンの湾部の2箇所、または3箇所で反応が進行したと思われる生成物を得た。さらに、リチオ化を経ない方法として、トリフェニレンと、アセチレンジカルボン酸ジエチルとのDiels-Alder反応によるコロネン誘導体の合成についても併せて検討した。また、ジベンゾシロール合成の新しい手法として、ラジカル環化反応を用いた合成法についても検討を行い、良好な収率でジベンゾシロールを与えることがわかり、新たな合成手法の確立に成功した。

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  • Creation of Multi-dimensionally Extended Hetero-π Conjugate Molecules

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research 

    KAWASHIMA Takayuki, MOCHIDA Kunio, KANO Naokazu, KOBAYASHI Junji, AGOU Tomohiro

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    2009 - 2012

    Grant number:21350025

    Grant amount:\18850000 ( Direct Cost: \14500000 、 Indirect Cost:\4350000 )

    Triheterasumanenes, which are heteroatom analogues of bowl-shaped sumanene, containing heteroatoms such as Si, Sn, and P atoms were synthesized as disc-shaped hetero π -conjugate molecules. As starburst-type hetero π -conjugate molecules, oligo(phenylenevinylene)- substituted spirobiheterafluorenes bearing Si or P at the molecular centers were synthesized. These multi-dimensionally extended hetero π -conjugate molecules were found to show interesting properties such as intense blue-light emission and two-photon absorption.

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  • Synthesis of hexathiacoronene and construction of redox active dye system

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research 

    KOBAYASHI Junji

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    2010 - 2011

    Grant number:22750033

    Grant amount:\3900000 ( Direct Cost: \3000000 、 Indirect Cost:\900000 )

    Starting from 2, 3, 6, 7, 10, 11-hexabutoxytriphenylene, it was allowed to react with 8 equivalents of n-BuLi in the presence of TMEDA. When the reaction mixture was heated under reflux condition for 3 hours, hexalithiotriphenylene was generated effectively. Treatment of this hexalihiotriphenylene with excess amount of elemental sulfur gave the product, in which sulfur atoms were introduced into the bay position of triphenylene. This product was reduced by LiAlH4 to give hexamercaptotriphenylene, the precursor of hexathiacoronene.

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  • 球面型トリカルベン配位子の開発と高次π空間を有するメタロフラーレンの創発

    日本学術振興会  科学研究費助成事業 

    小林 潤司

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    2009 - 2010

    Grant number:21108507

    Grant amount:\4420000 ( Direct Cost: \3400000 、 Indirect Cost:\1020000 )

    トリフェニレンにヘテロールが縮環した化合物であるトリヘテラスマネン合成の別法としてトリフェニレンの湾部が6箇所リチオ化されたヘキサリチオ体経由の合成法を活用してトリヘテラスマネン類の合成を行った。2,3,6,7,10,11-ヘキサブトキシトリフェニレンを出発原料として、TMEDA存在下、過剰量のn-BuLiを作用させ、加熱かくはんを行ったところ、効率よくヘキサリチオ体が発生することを見いだしていたので、このヘキサリチオ体に、各種典型元素試薬を反応させトリヘテラスマネンの合成を検討することとした。ヘキサリチオ体にフェニルジクロロホスフィンを作用させ、引き続いて単体硫黄を作用させることで、トリホスファスマネントリオキシドの合成に成功しており、生成物の構造異性体の分離構造決定を行った。また、別の典型元素源として、ジアルキルジクロロスタンナンを作用させることで、ヘキサスタンナスマネンの合成にも成功した。有機スズ化合物は、その他の典型金属元素と効率よくトランスメタル化が進行することが知られているため、このトリスタンナスマネンを新たな出発原料として、新たなトリヘテラスマネンへと誘導することを検討した。そこで、母体のスマネンと同様な骨格的歪みを持ち、かつ物性材料としても有用性が期待されるトリボラスマネンの合成を目指し、ホウ素原子とのトランスメタル化を検討した。その結果、各種NMRスペクトルより、少なくとも湾部の1箇所がホウ素化されたと思われる化合物の生成が示唆された。

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  • Development of novel ligands occupying the specified positions and their application to the synthesis of new hypervalent compounds

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research 

    KAWASHIMA Takayuki, KANO Naokazu, KOBAYASHI Junji

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    2003 - 2007

    Grant number:15105001

    Grant amount:\107120000 ( Direct Cost: \82400000 、 Indirect Cost:\24720000 )

    The object of this study is to develop novel ligands, which occupy the specific positions of hypervalent main group compounds on the basis of the steric and electronic stabilization effects, and synthesize the hypervalent compounds with novel frameworks by use of these ligands. Mainly, we have developed several ligands for pentacoordinated main-group-element compounds, such as a planar tridentate ligand which occupies two apical positions and one equatorial position, tetradentate ligands which occupy three equatorial positions and one apical position, a bulky dendrimer-type ligand which occupies the equatorial position, and the dithiocarboxylato ligand which bridges two highly coordinate main-group elements. As a result, we succeeded in applying tetracoordinated 1,2-iodoxetane as a thermally stable oxidant, synthesizing carbaphosphatranes and a carbasilatrane where three oxygen atoms and one arbon atom occupy the equatorial and apical positions, respectively, and synthesizing disilanes with bonds between pentacoordinated silicon atoms and between heptacoordinated silicon atoms.
    In addition, we also succeeded in synthesizing their related compounds such as prophosphaalatrane containing phosphorus and aluminum, a cationic silanolatozirconium complex that has olefin polymerization activity, and an amino(ylide)carbene having the highest electron donating ability among the related carbenes known to date. As mentioned above, we achieved the construction of the novel hypervalent compounds bearing a thermodynamically unfavorable configuration by taking advantages of the ligands that we developed by ourselves and elucidation of their structures, bonding modes, and reactivities. We could obtain new knowledge based on new structures that would contribute significantly to the development of a new paradigm in main group chemistry.

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  • 新規エクアトリアル位占拠型配位子を用いたシリカートの合成と有機合成反応への応用

    日本学術振興会  科学研究費助成事業 

    小林 潤司

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    2002 - 2004

    Grant number:14740340

    Grant amount:\3100000 ( Direct Cost: \3100000 )

    まず昨年度の検討によって合成したAr_3CSiCl_3,1(Ar=2-MeO-5-t-Bu-C_6H_3)の官能基変換を検討した。1に対してAgBF_4を反応させたところ、1の塩素原子がフッ素原子に置き換わったAr_3CSiF_3,2の合成に成功した。この反応機構は次のように考えられる。すなわち、銀により塩化物イオンが引き抜かれ生成したシリセニウムカチオンが、テトラフルオロボラートからフッ化物イオンを引き抜き、Ar_3CSiFCl_2を与え、この反応を繰り返すことで2が得られたものと考えられる。2のX線結晶構造解析を行ったところ、三つのメトキシ基が中心ケイ素原子に対してフッ素原子のちょうど反対側に位置し、メトキシ基の酸素原子の孤立電子対がSi-Fの反結合性軌道と相互作用しており、ケイ素原子周りは7配位構造をとっていることがわかった。またメトキシ基の酸素原子とケイ素原子間の原子間距離は1に比べて若干短くなっており、ケイ素原子と酸素原子との間に吸引的な相互作用があることが示唆された。続いて1のメトキシ基の脱メチル化を検討した。脱メチル化試剤としてはTMSI, BBr_3を検討した。TMSIとの反応においては生成物の同定には至らなかったが、1に対してBBr_3を作用させた後、エタノールで処理をしたところ、3段階の脱メチル化が進行した後、三つのケイ素-酸素結合が生成した結果、三環性のシラン3に対して、エタノールが1分子配位したと思われる化合物4を得た。4の水処理を行ったところ、配位エタノール分子が水分子へと置き換わった5が得られた。化合物4および5の構造の詳細について現在検討中である。以上のように、本計画は計画通り遂行できた。

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