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Oxidation of Cyclic Oligosulfides and Structures and Decomposition Reactions of the Oxides

Research Project

Project/Area Number 12440174
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionSaitama University

Principal Investigator

ISHII Akihiko  Saitama University, Faculty of Science, Assoc Prof., 理学部, 助教授 (90193242)

Co-Investigator(Kenkyū-buntansha) SUGIHARA Yoshiaki  Saitama University, Faculty of Science, Assoc. Prof., 理学部, 助教授 (00272279)
NAKAYAMA Juzo  Saitama University, Faculty of Science, Prof., 理学部, 教授 (90092022)
Project Period (FY) 2000 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥5,100,000 (Direct Cost: ¥5,100,000)
Fiscal Year 2002: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 2001: ¥2,600,000 (Direct Cost: ¥2,600,000)
KeywordsDithiiranes / Tetrathiolanes / Pentathianes / 1,2,4-trithiolanes / Elemental sulfur / Dimethyldioxirane / Oxidation / Platinum complex / 1,2-ジオキシド / 硫黄酸化物 / 一酸化二硫黄 / X線結晶構造解析 / ジチイランオキシド / トリフルオロ過酢酸 / 二原子硫黄 / ジアゾアルカン
Research Abstract

1. The chemistry of Dithiiranes. (i) The reaction of S_8O, prepared by oxidation of elemental sulfur, with diazo compounds yielded the desired dithiirane 1-oxides. (ii) The dithiirane 1-oxides were reduced with Lawesson's reagent to give unoxidized dithiiranes. (iii) The reaction of the dithiirane 1-oxides and the dithiiranes thus obtained with (Ph_3P)_2Pt(C_2H_4) produced the Pt-insertion products in high yields.
2. The chemistry of tetrathiolanes. (i) Oxidation of a tetrathiolane with dimethyldioxirane (DMD) gave the 2-oxide and then 2,3-dioxide. The 2,3-dioxide decomposed in solution over -20℃ to give the dithiirane 1-oxide and disulfur monoxide. (ii) The reactions of the 2-oxide and the 2,3-dioxide with (Ph_3P)_2Pt(C_2H_4) produced the identical Pt-S_2O complex. The Pt-S_2O complex further reacted with (Ph_3P)_2 Pt(C_2H_4) to give the novel platinum dinuclear complex in high yield.
3. The chemistry of pentathianes. (i) Oxidation of a pentathiane with trifluoroperacetic acid and DMD g … More ave the 3-oxide and the 1-oxide, respectively. (ii) The reaction of the 3-oxide with (Ph_3P)_2 Pt(C_2H_4) yielded the cyclic (dithiolato-thiolato)-Pt complex and the Pt-S_2O complex in high yields.
4. The chemistry of 1,2,4-trithiolanes. (i) a cis-tetrasubstituted 1,2,4-trithiolane was allowed to react with DMD to give two 1-oxides. Oxidation of one of the 1-oxides yielded the desired 1,2-dioxide, while that of the other 1-oxide gave the 1,1-dioxide. The 1,1-dioxide decomposed in solution at room temperature to give two molar equiv of the thioketone. Similarly, the 1,2-dioxide decomposed to two molar equiv of the thioketone in refluxing chloroform, while the two 1-oxides decomposed to the identical thiirane in refluxing xylene. (ii) Oxidation of a trans-tetrasubstituted 1,2,4-trithiolane with MCPBA produced two 1-oxides. Further oxidation of one of the 1-oxides with DMD yielded two diastereoroeric 1,2-dioxdes and 1,1-dioxide, while that of the other 1-oxide gave only one of the 1,2-dioxides. We observed equilibrium between the two 1,2-dioxides. Less

Report

(4 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] A.Ishii, M.Nakabayashi, Y.-N.Jin, J.Nakayama: "Oxidation of Tetrathiolanes : Isolation of a vic-Disulfoxide, 5-(1-Adamantyl)-5-tert-butyltetrathiolane 2,3-Dioxide and its Decomposition to the Dithiirane 1-Oxide and 'S_2O'"J. Organomet. Chem.. 611. 127-135 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Ishii, H.Oshida, J.Nakayama: "An S-oxide of 6-tert-Butyl-6-phenylpentathiane. Structure in the Crystalline State and in Solution and Thermal Decomposition"Tetrahedron Lett.. 42. 3117-3119 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Ishii, T.Kawai, K.Tekura, H.Oshida, J.Nakayama: "A Convenient Method for Generation of a Disulfur Monoxide Equivalent and Its Reaction with Diazoalkanes to Yield Dithiirane 1-Oxides"Angew. Chem. Int. Ed.. 40. 1924-1926 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Ishii, H.Oshida, J.Nakayama: "Structure Elucidation of 6-tert-Butyl-6-phenylpentathiane Monoxides by X-ray Crystallography and DFT Calculations"Bull. Chem. Soc. Jpn.. 75. 319-328 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Ishii, M.Saito, M.Murata, J.Nakayama: "Reaction of Dithiirane 1-Oxides with a Platinum(O) Complex"Eur. J. Org. Chem.. 979-982 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Ishii, K.Furusawa, T.Omata, J.Nakayama: "Reactions of Sterically Congested 1,6-and 1,7-Bis(diazo)alkanes with Elemental Sulfur and Selenium : Formation of Cyclohexene, 1,2-Dithiocane, 1,2-Diselenocane, and 1,2,3-Triselenecane Derivatives"Heteroatorn Chem.. 13. 351-356 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Oshida, A.Ishii, J.Nakayama: "Oxidation of cis-3,5-Di-tert-alkyl-3,5-diphenyl-1,2,4-trithiolanes : Isolation and Some Properties of the 1-Oxides and the 1,2-Dioxides"Tetrahedron Lett.. 43. 5033-5037 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Ishii, R.Yamashita, M.Saito, J.Nakayama: "Deoxygenation of Dithiirane 1-Oxides with Lawesson's Reagent Leading to the Corresponding Dithiiranes"J. Org. Chem.. 68. 1555-1558 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Ishii, M. Nakabayashi, Y.N.Jin, J. Nakayama: "Oxidation of Tetrathiolanes : Isolation of a vic-Disulfoxide, 5-(1-Adamantyl)-5-tert-butyltetrathiolane 2,3-Dioxide and its Decomposition to the Dilhiirane 1-Oxide and 'S_2O'"J.Organomet. Chem. 611. 127-135 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Ishii, H. Oshida, J. Nakayama: "An S-oxide of 6-tert-Bulyl-6-phenylpentathiane. Structure in the Crystalline State and in Solution and Thermal Decomposition"Tetrahedron Lett.. 42. 3117-3119 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Ishii, T. Kawai, K.Tekura, H. Oshida, J. Nakayama: "A Convenient Method for Generation of a Disulfur Monoxide Equivalent and Its Reaction with Diazoalkanes to Yield Dithiirane 1-Oxid"Angew. Chem. Int. Ed.. 40. 1924-1926 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Ishii, H. Oshida, J. Nakayama: "Structure Elucidation of 6-tert-Butyl-6-phenylpentathiane Monoxides by X-ray Crystallography and DFT Calculations"Bull. Chem. Soc. Jpn.. 75. 319-328 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Ishii, M. Saito, M. Murata, J. Nakayama: "Reaction of Dithiirane 1-Oxides with a Platinum(O) Complex"Eur. J. Org. Chem.. 979-982 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Ishii,K. Furusawa, T. Omata, J. Nakayama: "Reactions of Sterically Congested 1,6- and 1,7-Bis(diazo)alkanes with Elemental Sulfur and Selenium : Formation of Cyclohexene, 1,2-Dithiocane, 1,2-Diselenocane, and 1,2,3-Triselenecane Derivatives"Heteroatom Chem.. 13. 351-356 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H. Oshida, A. Ishii, J. Nakayama: "Oxidation of cis-3,5-Di-tert-alkyl-3,5-diphenyl-1,2,4-trithiolanes : Isolation and Some Properties of the 1-Oxides and the 1,2-Dioxides"Tetrahedron Lett.. 43. 5033-5037 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Ishii, R. Yamashita, M. Saito, J. Nakayama: "Deoxygenation of Dithiirane 1-Oxides with Lawesson's Reagent Leading to the Corresponding Dithiiranes"J. Org. Chem.. 68. 1555-1558 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Hideaki Oshida, Akihiko Ishii, Juzo Nakayama: "Oxidation of cis-3,5-Di-tert-alkyl-3,5-diphenyl-1,2,4-trithiolanes : Isolation and Some Properties of the 1-Oxides and the 1,2-Dioxides"Tetrahedron Letters. vol.43. 5003-5037 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Akihiko Ishii, Masashi Saito, Tetsuhiko Kawai, Masami Murata, Juzo Nakayama: "Physical and Chemical Properties of Four-Membered Bis(Triphenylphospane)platinum(II) Sulfenato Thiolato Complexes"Phosphorus, Sulfur and Silicon. vol.177. 2025-2026 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Akihiko Ishii, Remi Yamashita, Masashi Saito, Juzo Nakayama: "Deoxygenation of Dithiirane 1-Oxides with Lawesson's Reagent Leading to the Corresponding Dithiiranes"Journal of Organic Chemistry. vol.68. 1555-1558 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Akihiko Ishii, Hideaki Oshida, Juzo Nakayama: "Structure Elucidation of 6-t-Butyl-6-phenylpentathiane Monoxides by X-ray Crystallography and DFT Calculations"Bull.Chem.Soc.Jpn.. Vol.75No.2. 319-328 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Akihiko Ishii, Masashi Saito, Masami Murata, Juzo Nakayama: "Reaction between Dithiirane 1-Oxides and a Plutinum(0)Complex"Eur.J.Org.Chem.. issue 6. 979-982 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Akihiko Ishii, Ken Furusawa, Takenori Omata, Juzo Nakayama: "Reactions of Sterically Conjested 1,6- and 1,7-Bis(diazo)alkanes with Elemental Sulfur and Selenium"Heteroatom Chem.. (印刷中).

    • Related Report
      2001 Annual Research Report
  • [Publications] Akihiko Ishii: "A Convenient Method for Generation of A Disulfur Monooxide (S_2O) Equivalent and Its Reaction with Diazoalkanes to Yield Dithiirane 1-Oxides"Angew.Chem.Int.Ed.Engl.. (印刷中).

    • Related Report
      2000 Annual Research Report
  • [Publications] Akihiko Ishii: "An S-Oxide of 6-tert-Butyl-6-phenylpentathiane. Structure in the Crystalline State and in Solution and Thermal Decomposition"Tetrahedron Lett.. (印刷中).

    • Related Report
      2000 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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