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Application to New Molecular Design : Synthesis and Properties of Strained Heterocyclic Compounds

Research Project

Project/Area Number 01430006
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionTsukuba University

Principal Investigator

ANDO Wataru  Tsukuba Univ., Dept. of Chemistry, Professor, 化学系, 教授 (30008429)

Project Period (FY) 1989 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥29,000,000 (Direct Cost: ¥29,000,000)
Fiscal Year 1991: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 1990: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 1989: ¥22,000,000 (Direct Cost: ¥22,000,000)
Keywordsalkylidene episulfides / thioally iron complexes / zirconocene dichloride / di-t-butylethanethial / 1, 2, 3, 4, 5-pentathiepane / 1, 2, 3-selenadiazole / thiadigermirane / silthiane / アレンエピスルフィド / βーチオアリル / チオアリル鉄トリカルボニル錯体 / チオアリルカチオン / 金属カルボニル / チオルテニウムクラスタ- / 1,2,3ーセレナジアゾ-ル / 硫黄 / 1,2,3ーブタトリエン / シクロドデカヘキサエン / ペンタスルフィド / 2原子硫黄 / エピスルフィド / シクロペンテンチオン / チオキシアリル / 1、2ージチオン / 1、2、3ーセレナジアゾ-ル / 1、2ージセレネタン
Research Abstract

The strain alkylidene episulfides were synthesized by carbene and alkylidene carbene addition to thiocarbonyl compounds. Thermal, photochemical and acid catalyzed reactions have been extensively investigated, and the transition metal promoted reaction results in the first isolation of thioally iron and ruthenium tricarbonyl complexes. The reaction of germylene with thioketene gave 3alkylidenethiagermirane. Thiagermetane is extremely sensitive toward oxygen as well as sulfur to yield corresponding ring expansion products. Zirconocene has been generated by various method. Addition of n-BuLi to zirconocene dichloride at -78゚C under agron followed by introduction of di-t-butylthioketene and work up with IO%HCI gave di-t-butylethanethial and its isomer, di-t-butylethenethiol. The intermediate, zirconocene thioacyl complex was formed in a moderated yield. Sulfurization of alkylideneallene was easily performed by heating with excess of elemental sulfur in DMF at 110o to give the corresponding allene episulfide. On the other hand, sulfurization of 1, 2, 3-butatriene with elemental sulfur gave 1, 2, 3, 4, 5-pentathiepane derivative as yellow crystals. On the other hand, 1, 2, 3-butatriene with selenium in the presence of DBU gave 1, 2, 5-triselenepane derivatives. Sulfurization of fused 1, 2, 3-selenadiazole with elemental sulfur at 120゚C gave nonathiacycloundecene, 1, 2, 3-trithiole. Photolysis or thermolysis of hexamesitylcyclotrigennane with elemental sulfur produced the thiadigermirane along with dithiadigermetane. On the other hand, the trihydrosilane bearing bulky substituent reacts with elemental sulfur and selenium to give the cage molecule such as adamantane type silthiane. All new compounds were characterized by NMR.

Report

(4 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • 1989 Annual Research Report
  • Research Products

    (28 results)

All Other

All Publications (28 results)

  • [Publications] W.Ando,N.Tokitoh,Y.Kade: "Synthesis and Reaction of Novel Sulfur Containins Heterocyclic Systems" Phosphorous,Sulfur and Silicon. 58. 179-205 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] B.Burkhart,S.Krill,Y.Okano,W.Ando,M.Regitz: "1,3-Selenaphospholes:A New Synthesis from 1,2,3-Selenadiazoles and Kinetically Stabilized Phosphaalkynes" SYN LETT.356-358 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] N.Choi,Y.kabe,W.Ando: "Formation of Sulfido Ruthenium Carbonyl Clusters via Thioallyl Cation Complex" Organometallics,.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] W.Ando,T.Ohtaki,T.Suzuki,Y.Kabe: "The first Stable Enethiolizable Thioaldehyde via Zirconocene η2-Thioacyl Complex" J.Am.Chem.Soc.113. 7782-7784 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] N.Choi,Y.Kabe,W.Ando: "Palladiium(0)Catalyzed Intra-and Intermolecular Cyclization Reaction of Allene Episulfides" Tetrahedron Lett.32. 4573-4576 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] N.Choi,Y.Kabe,W.Ando: "Formation of Thioruthenium Carbonyl Clusters via Thioallyl Cation Complex" Organometallics. 11. 605-613 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] N.choi,Y.Kabe,W.Ando: "(Thioally)iron Tricarbonyl Complex" Organometallics,in press.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] W. Ando, N. Tokitoh, Y. Kabe: "Synthesis and Reaction of Novel Sulfur Containing Heterocyclic Systems" Phosphorous, Sulfur and Silicon. 58. 179-205 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] B. Burkhart, S. Krill, Y. Okano, W. Ando, M. Regitz: "1, 3-Selenaphospholes : A New Synthesis from 1, 2, 3-Selenadiazoles and Kinetically Stabilized Phosphaalkynes" SYN LETT.356-358 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] N. Choi, Y. Kabe, W. Ando: "Formation of Sulfido Ruthenium Carbonyl Clusters via Thioallyl Cation Complex" Organometallics.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] W. Ando, T. Ohtaki, T. Suzuki, Y. Kabe: "The first Stable Enethiolizable thioaldehyde via Zirconocene eta2-Thioacyl Complex" J. Am. Chem. Soc.113. 7782-7784 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] N. Choi, Y. Kabe, W. Ando: "Palladiium (0) Catalyzed Intra-and Intermolecular Cyclization Reaction of Allene Episulfides" Tetrahedron Lett.32. 4573-4576 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] N. Choi, Y. Kabe, W. Ando: "Formation of Thioruthenium Carbonyl Clusters via Thioallyl Cation Complex" Organometallics. 11. 605-613 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] N. Choi, Y. Kabe, W. Ando: "(Thioally) iron Tricarbonyl Complex" Organometallics.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] W.Ando,N Tokitoh,Y.Kabe: "Synthesis and Reaction of Novel Sulfur Containins Heterocyclic Systems" Phosphorous,Sulfur and Silicon. 58. 179-205 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] B.Burkhart,S.Krill,Y.Okano,W.Ando,M.Regitz: "1,3ーSelenaphospholes: A New Synthesis from 1,2,3ーSelenadiazoles and Kinetically Stabilized Phosphaalkynes" SYNLETT.356-358 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] N.Choi,Y.Kabe,W.Ando: "Formation of Sulfido Ruthenium Carbony Clusters via thioallyl Cation Complex" Organometallics.

    • Related Report
      1991 Annual Research Report
  • [Publications] W.Ando,T.Ohtaki,T.Suzuki,Y.Kabe: "The first Stable Enethiolizable Thioaldehyde via Zirconocene η2ーThioacyl Complex" J. Am. Chem. Soc.113. 7782-7784 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] N.Choi,Y.Kabe,W.Ando: "Palladiium(0) Catalyzed Intraー and Intermolecular Cyclization Reaction of Allene Episulfides" Tetrahedron Lett.32. 4573-4576 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] N.Choi,Y.Kabe,W.Ando: "Formation of Thioruthenium Carbonyl Clusters via Thioallyl Cation Complex" Organometallics. 11. 605-613 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] N.Choi,Y.Kabe,W.Ando: "(Thioally)iron Tricarbonyl Complex" Organometallics.

    • Related Report
      1991 Annual Research Report
  • [Publications] N.Tokitoh,M.Noguchi,Y.Kabe and W.Ando: "Sulfurization of 1,4,7,10ーTetraarylcyclododecaー1,2,3,7,8,9ーhexanes" Tetrahedron Letters. 31. 7641-7644 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] N.Tokitoh,Y.Okano and W.Ando: "Novel Formation and Molecular Structure of 1,2,3,4,5,6,7,8,9ーNonathiacycloundecー10ーene" Tetrahedron Letters. 31. 5323-5326 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] W.Ando,H.Sonobe and T.Akasaka: "Selective Sulfurization of Olefins by 9,10ーEpidithio9,10ーdihydroanthracene:Intermediacy of Diatomic Sulfur" Tetrahedron. 46. 5093-5100 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] W.Ando: "Synthesis of Functionalized Episulfides" Strain and Its Implications in Organic Chemistry Ed.by A.de Meijere and S.Blechert. 273. 59-74 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] N.Tokitoh: "A Novel Formation and Photochemical Reaction of 3,3ーDiーtーButylー3^1,3^1ーdiphenyl(1,2)dithiolo(5,4ーd)(1,2)dithiole" Tetrahedron Letters. 30. 4825-4824 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] N.Tokitoh: "Formation of Cyclopentenethiones via Cyclization of ーThioallyl Cations" Journal of Organic Chemistry. 54. 4660-4663 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] 安藤亘: "1,2ージチオンおよびそのセレン類似体の化学" 日本化学会誌. 8. 1447-1455 (1989)

    • Related Report
      1989 Annual Research Report

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

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