• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Synthesis of New Highly-strained Cyclophanes Bridged by Cyclobutane Rings and Use of Their Properties

Research Project

Project/Area Number 01470093
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionGunma University

Principal Investigator

NISHIMURA Jun  Gunma University, Chemistry, Prof., 工学部, 教授 (10107352)

Co-Investigator(Kenkyū-buntansha) OKADA Yukihiro  Gunma University, Chemistry, Assistant prof., 工学部, 助手 (80211118)
TAKAHASHI Hideo  Gunma University, Chemistry, Assistant prof., 工学部, 助手 (80008458)
KAMEYAMA Eiichi  Gunma Univ., Center for Coop. Res., Associate prof., 地域共同研究センター, 助教授 (40008438)
Project Period (FY) 1989 – 1990
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥5,800,000 (Direct Cost: ¥5,800,000)
Fiscal Year 1990: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1989: ¥4,500,000 (Direct Cost: ¥4,500,000)
KeywordsCyclophanes / Cyclobutane Ring / Styrene Derivatives / Photocycloaddition / Photochromism / Naphthaleneophanes / Phenanthrenophanes / Transannular Reaction / ビフェニロファン / 光環化付加反応 / パドラン / 高歪分子
Research Abstract

A novel synthesis of cyclophanes using intramolecular [2 + 2] photocycloaddition of styrene derivatives was developed in our laboratories. So we were prompted to study its mechanism, its scope and limitation as a synthetic method, further reactions of cyclophanes obtained, and the use of properties of unique cyclophanes. Results obtained in the two year period of this project are listed below ; (1) Many vinylarenes, including 1, 3-bis (6-viny-1-1-phenanthryl) propance and cis-1, 2-bis (-vinyphenyl) cyclobutane, were prepared and irradiated. The corresponding phanes like a phenanthrenphane and [2.2] metacyclophane bridged by two cyclobutane rings were obtained. These results suggest the wide applicability of the reaction for cycrophane synthesis. (2) As one of mechanistic investigations, the effects of substituents attaching at the vinyl groups of vinylnaphthalene derivatives was studied. The reaction courses were affected greatly by the position and sort of substituents. (3) In order t … More o shorten the linkage by making a small ring, 1, 2-ethano [2.3] paracyclophane was brominated at the trimethylene chain, followed by the treatment with n-butyllithium, to afford the desired [2.2]paracyclophane linked by a cyclobutane ring and cyclopropane ring in a reasonable yield. This compound gathers much attention as one of the unique paddlaes. (4) cis-1, 2-Ethano-syn-[2.3] (1, 4) -naphthalenophane produced a highly strained cubane-type compound by photoirradiation. The product showed an interesting thermal cycloreversion, whose late was determined. (5) Small cyclophanes obtained by the reaction underwent the ring opening reaction. The rates of the reaction depended on the strain energies of the cyclophanes. (6) Cyclophanes obtained showed several intriguing properties like photochromism mentioned above, but there were no compounds which could be applied to any advanced materials. We would like to stress, however, that several crown ethers possessing cyclophane structures were prepared in surprisingly high yields and that did exhibit quite high Li^+ selectivity at the transport experiments. Less

Report

(3 results)
  • 1990 Annual Research Report   Final Research Report Summary
  • 1989 Annual Research Report
  • Research Products

    (23 results)

All Other

All Publications (23 results)

  • [Publications] J.Nishimura,Y.Horikoshi Y.Wada,H.Takahashi,M.Sato: "Intramolecular[2+2]photocycloaddition.10.Conformationally Stable synー[2+2]Metacyclophane" J.Am.Chem.Soc.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] J.Nishimura,M.Takeuchi,H.Takahashi,M.Sato: "Intramolecular[2+2]Photocycloaddition.9.Stereoselective Synthesis of Naphthalenophanes and Effects of the Tether Length and Substituents on the Photochemical Reaction Courses of Vinylnaphthalenophanes" Tetrahedron Letters. 31. 2911-2914 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Y.Okada,K.Sugiyama,Y.Wada,and J.Nishimura: "Synthesis of MultiーBridged Cyclophanes by Means of[2+2]Photocycloaddition.Stereocontrol of CyclobutaneーLinkage by Methoxyl Group" Tetrahedron Letters. 31. 107-110 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] S.Inokuma,T.Yamamoto,and J.Nishimura: "Efficient Intramolecular[2+2]Photocycloaddition of Styrene Derivatives toward New Crown Ethers" Tetrahedron Letters. 31. 97-100 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] J.Nishimura,Y.Horikoshi,Y.Wada,and H.Takahashi: "Intramolecular[2+2]Photocycloaddition.6.Synthesis and Properties of Oxacyclophanes" Tetrahedron Letters. 30. 5439-5442 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] J.Nishimura,M.Takeuchi,H.Takahashi,E.Ueda,Y.Matsuda,and A.Oku: "Intramolecular[2+2]Photocycloaddition.5.Synthetic Method toward[2.n]ー,[3.n]ー,and[4.n]Naphthalenophane Skeletons by Using α,ωーBis(vinylnaphthyl)alkanes." Bull.Chem.Soc.Jpn.62. 3161-3166 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] J. Nishimura, M. Takeuchi, H. Takahashi, E. Ueda, Y. Matsuda, and A. Oku,: "Intramorecular [2 + 2] Photocycloaddition. 5. Synthetic Methods toward [2. n]-, [3. n]-, and [4. n]Naphthalenophane skeletons by Using alpha, omega-Bis(vinylnaphthyl)alkanes" Bull. Chem. Soc. Jpn.,. 62. 3161-3166 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] J. Nishimura, Y. Horikoshi, H. Takahashi, S. Machino, and A. Oku,: "Intramolecular [2 + 3] photocycloaddition. 6. Synthesis and Properties of Oxacyclophanes" Tetrahedron Lett.,. 30,. 5439-5442 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] S. Inokuma, T. Yamamoto, and J. Nishimura,: "Efficient Intramolecular [2 + 2] Photocycloaddition of Styrene derivatives toward New Crown Ethers" Tetrahedron Lett.,. 31. 97-100 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Y. Okada, K. Sugiyama, Y. Wada, and J. Nishimura,: "Synthesis of Multi-Bridged Cyclophanes by Means of [2 + 2] Photocycloaddition. Stereocontrol of Cyclobutane-Linkage by Methoxyi Group" Tetrahedron Lett.,. 31,. 107-110 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] J. Nishimura, M. Takeuchi, H. Takahashi, and M. Sato,: "Intramolecular [2+2] Photocycloaddition. 9. Stereoselective Synthesis of Naphthalenophanes and Effects of the Tether Length and Substituents on the Photochemical Reaction Courses of Vinylnaphthalenes" Tetrahedron Lett.,. 31,. 2911-2914 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] J. Nishimura, Y. Horikoshi, Y. Wada, H. Takahashi, and M. Sato,: "Intramolecular [2+2] Photocycloaddition. 10. Conformationally Stable syn-[2.2]Metacyclophane" J. Am. Chem. Soc.,. 113. (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] J.Nishimura,M.Takeuchi,H.Takahashi,M.Sato: "Tntramolecular[2+2]Photocycloaddition.9.Stereoselective Synthesis of Naphthalenophanes and Effects of the Tether Length and Substituents on the Photochemical Reaction Courses of Vinylnaphthalenophanes" Tetrahedron Letters. 31. 2911-2914 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] J.Nishimura,Y.Horikoshi,Y.Wada,H.Takahashi,M.Sato: "Intramolecular[2+2]Photocycloaddition.10.Conformationally Stable synー[2.2]Metacyclophane" J.Am.Chem.Soc.

    • Related Report
      1990 Annual Research Report
  • [Publications] Y.Okada,K.Sugiyama,M.Kurahayashi,J.Nishimura: "Synthesis of ThreeーBridged Cyclophanes via Metaーand Orthoーcyclophane" Tetrahedron Letters.

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Inokuma,T.Yamanoto,J.Nishimura: "Selective LiーTransport by Means of Crownophanes" Chem.Letters.

    • Related Report
      1990 Annual Research Report
  • [Publications] Y.Okada,S.Mabuchi,M.kurahayashi,J.Nishimura: "Synthesis and Structural Analysis of Dimethoxy[2.n]metacyclophanes" Chem.Letters.

    • Related Report
      1990 Annual Research Report
  • [Publications] J.Nishimura,Y.Horikoshi,Y.Wada,H.Takahashi,S.Machino,A.Oku: "Intramolecular〔2+2〕Photocycloaddition.6.Synthesis and Properties of Oxacyclophanes" Tetrahedron Letters. 30. 5439-5442 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] J.Nishimura,M.Takeuchi,H.Takahashi,E.Ueda,Y.Matsuda,A.Oku: "Intramolecular〔2+2〕Photocycloaddition.5.Synthetic Methods toward〔2.n〕-,〔3.n〕-,and〔4.n〕Naphthalenophane skeletons by Usingα,ω-Bis(vinylnaphthyl)alkanes" Bull.Chem.Soc.Japan. 62. 3161-3166 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] S.Inokuma,T.Yamamoto,J.Nishimura: "Efficient Intramolecular〔2+2〕Photocycloaddition of styrene Derivatives Toward New Crown Ethers" Tetrahedron Letters. 31. 97-100 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] Y.Okada,K.Sugiyama,Y.Wada,J.Nishimura: "Synthesis of Multi-Bridged Cyclophanes by Means of〔2+2〕Photocycloaddition.Stereocontrol of cyclobutane-linkage by Methoxyl Group" Tetrahedron Letters. 31. 107-110 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] J.Nishimura,M.Takeuchi,H.Takahashi,M.Sato: "Intramolecular〔2+2〕Photocycloaddition.9.Stereoselective Synthesis of Naphthalenophanes and Effect of the Tether Length and Substituents on the Photochemical reaction Courses of Vinylnaphthalenes"

    • Related Report
      1989 Annual Research Report
  • [Publications] Y.Okada,K.Sugiyama,M.Kurahayashi,J.Nishimura: "Transformation of a Cyclophanyl Triflate by Means of Paradium Catalyst"

    • Related Report
      1989 Annual Research Report

URL: 

Published: 1989-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi