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2007 Fiscal Year Final Research Report Summary

Study on Reactive Small Molecules of Sulfur Generated by the Methods of Organic Chemistry

Research Project

Project/Area Number 16350019
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

NAKAYAMA Juzo  Saitama University, Graduate school of Science and Engineering, Professor (90092022)

Co-Investigator(Kenkyū-buntansha) SUGIHARA Yoshiaki  Saitama University, Graduate school of Science and Engineering, Associate Professor (00272279)
ISHII Akihiko  Saitama University, Graduate school of Science and Engineering, Professor (90193242)
Project Period (FY) 2004 – 2006
KeywordsDiatomic sulfur / Triatomic sulfur / Sulfur monoxide / Disulfur monoxide / Addition reaction / Diels-Alder reaction / Singlet SO / Thiirene oxide
Research Abstract

The following reactive small molecules of sulfur were generated from the organic sources and their chemistry was investigated: 1) diatomic sulfur (S_2) that corresponds to a sulfur analogue of molecular oxygen O_2, 2) triatomic sulfur (S_3) that corresponds to a sulfur analogue of ozone O_3, 3) sulfur monoxide (SO) where one of the oxygen atoms of O2 is replaced by sulfur, and 4) disulfur monoxide (S_2O) where one of the oxygen atoms of sulfur dioxide (S_2O) is replaced by S.
The bicylic compound that carries an -S-SO- bridge underwent a retro-Diels-Alder reaction to extrude disulfur monoxide (S=S=O) in a reversible way at room temperature in solution. The resulting S=S=O undergoes a disproportionation through self-dimerization to give S_3 and SO_2 in the absence of suitable trapping agents. The S_3 acts as a 1, 3-dipole just like ozone and underwent 1, 3-dipolar cycloaddition toward strained alkenes, for example, norbornene. On the other hand, the S=S=O is trapped by dienes and other r … More eagents in good yields. Reactivities and DFT calucations of the molecule leads to a conclusion that S=S^+-0 is the major contributor of the ground state of this reactive species.
The Diels-Alder adduct that was formed by Diels-Alder reaction of a thiophene 1-oxide with dimethyl acetylenedicarboxylate underwent the SO extrusion at room temperature in solution with a driving force of the formation of a benzene derivative. The resulting SO was found to undergo hitherto unknown cycloadditions, i.e., [1+2] cycloadditions to alkenes and alkynes to give thiirane oxides and thiirene oxides, respectively. In particular, the later [1+2] cycloaddition to alkynes is synthetically important as a synthetic method of thiirene 1-oxide. It also undergoes [1+4] cycloadditions to acyclic dienes and cyclic dienes (polyenes) to provide a variety of cyclic sulfoxides; the addition to cyclic dienes is stereospecific. The reactivities of the SO leads to a conclusion that the SO produced by the present method is singlet and reacted with trapping agents without decay to more stable triplet state.
In addition, a few new reactions that generate diatomic sulfur(S_2) were developed. Less

  • Research Products

    (19 results)

All 2007 2005 2004 Other

All Journal Article (19 results)

  • [Journal Article] [1+2]Cycloadditions of Sulfur Monoxide(SO)to Alkenes and Alkynes and [1+4] Cycloadditions to Dienes(Polyenes).Generation and Reactions of Singlet SO2007

    • Author(s)
      J. Nakayama, Y. Tajima, X. h. Piao, Y. Sugihara
    • Journal Title

      J.Am.Chem.Soc. 129

      Pages: 7250-7251

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Preparation and Properties of Nitrogen-substituted Thiosulfinyl Compounds and Related Nery Heterocycles2007

    • Author(s)
      S. Yoshida, Y. Sugihara, J. Nakayama
    • Journal Title

      Tetrahedron Letters 48

      Pages: 8116-8119

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] [1+2] Cycloaddtions of Sulfur Monoxide(SO) to Alkenes and Alkynes and[1+4] Cyclodditions to Dienes(Polyenes) Generation and Reactions of Singlet SO?2007

    • Author(s)
      J. Nakayama, Y. Tajirha, X-h. Piao, Y. Sugihara
    • Journal Title

      J. AM. Chew. Soc 129

      Pages: 7250-7251

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Preparation and Properties of Nitrogen-substituted Thiosulfinyl Compounds and Related New Heterocycles.2007

    • Author(s)
      S. Yoshida, Y. Sugihara, J. Nakayama
    • Journal Title

      Tetrahedron Lett 48

      Pages: 8116-8119

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] SO2-Extrusion of an 8-Thiabicyclo[3.2.1]octa-2,6-diene 8,8-Dioxide and Rearrangement of the Resulting Cycloheptatriene2005

    • Author(s)
      J. Takayama, Y. Sugihara, J. Nakayama
    • Journal Title

      Hetroatom Chemistry 16

      Pages: 132-138

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Inverse Electron-demand Diels-Alder Reaction of 3,4-Di-tert-butylthiophene 1-Oxide with Electron-rich Dienophiles2005

    • Author(s)
      J. Takayama, Y. Sugihara, T. Takayanagai, J. Nakayama
    • Journal Title

      Tetrahedron Letters 46

      Pages: 4165-4168

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Tetracyanoethylene Oxide Not Only Oxidizes Sulfides to Sulfoxides But Also Reduces Sulfoxides to Sulfides2005

    • Author(s)
      J. Nakayama, A. Tai, Y. Sugihara
    • Journal Title

      Tetrahedron Letters 46

      Pages: 1395-1397

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] SO_2-Extrusion of an 8-Thiabicyclo[3. 2. 1] octa-2, 6-diene 8, 8-Dixoide and Rearrangement of the Resulting Cyclohptatriene.2005

    • Author(s)
      J. Takayama, Y. Sugihara, J. Nakayama
    • Journal Title

      Hetroatom Chemistry 25

      Pages: 132-138

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Inverse Electron-demand Diels-Alder Reaction of 3, 4-Di-tert-butylthiophene 1-Oxide with Electron-rich Dienophiles.2005

    • Author(s)
      J. Takayama, Y. Sugihara, T. Takayanagi, J. Nakayama
    • Journal Title

      Tetrahedron Lett 46

      Pages: 4165-4168

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] The Chemistry of the Thiosulfinyl Group : Preparation, Structure, and Spectrbopic and Chemical Properties of Cyclic Thionosulfites.2005

    • Author(s)
      J. Nakayama, S. Yoshida, Y. Sugihara, A. Sakamoto
    • Journal Title

      Helv Chim. Acta 48

      Pages: 1451-1471

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Tetracyanoethylene Oxide Not Only Oxidizes Sulfides to Sulfoxides But Also Re4duces Sulfoxides to Sulfides.2005

    • Author(s)
      J. Nakayatha, A. Tai, Y. Sugihara
    • Journal Title

      Tetrahedron Lett 45

      Pages: 1395-1397

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Reversible Disulfur Monoxide(S_2O)-Forming Retro-Diels-Alder Reaction.Disproportionation of S_2O to Trithio-Ozone(S_3)and Sulfur Dioxide(SO_2)and Reactivities of S_2O and S_32004

    • Author(s)
      J. Nakayama, S. Aoki, J. Takayama, A. Sakamoto, Y. Sugihara, A. Ishii
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 9085-9093

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Pummerer Reaction of 3,6-Di-tert-butyl-2H,8H-1,2,5,6-di-thiadiazocine 1-Oxide2004

    • Author(s)
      」. Nakayama, S. Iida, Y. Sugihara, A. Ishii
    • Journal Title

      J.Sulfur Chem. 25

      Pages: 13-19

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Ishii : Reversible Disulfur Monoxide(S_2O)-Forming RetroDiels-Alder Reaction. Dispro-portionation of S_2O to Trithio-ozone(S_3) and Sulfur Dioxide and Reactivities of S_2O and S_3.2004

    • Author(s)
      J. Nakayama, S. Aoki, J. Takayama, A. Sakamoto, Y. Sugihara, A
    • Journal Title

      J Am. Chew. Soc 126

      Pages: 9085-9093

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Ishii : Pummerer Reaction of 3, 6-Di-tert-butyl-2H, 8H-1, 2, 5, 6-dithiadiazocine 1-Oxide.2004

    • Author(s)
      J. Nakayama, S. lida, Y. Sugihara, A
    • Journal Title

      J Sulfur Lett 25

      Pages: 13-19

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Rearrangement of the tert-Butyl Group of 5,6-Di-tert-butyl-2,3,7-trithiabicvlo[2.2.1]hept-5-ene 7-Endoxide

    • Author(s)
      S. Yoshida, Y. Morohashi, R. Fuiihara, J. Nakayama
    • Journal Title

      J.Sulfur Chem. 29(In press)

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Preparation of Sterically Congested Compounds:6,7-Di-tert-butylnaphthoquinone, 2,3,6,7-Tetra-t-butyl-anthraquinone,and 2,3,6,7-Tetra-t-butylanthracene

    • Author(s)
      K. Iguchi, Y. Sugihara, J. Nakayama
    • Journal Title

      Bull.Chem.Soc.Jpn (In press)

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Rearrangement of the tert-Butyl Group of 5, 6-Di-tert-butyl-2, 3, 7-trithiabicylo[2. 2. 1] hept-5-ene 7-Endoxide.

    • Author(s)
      S. Yoshida, Y. Morohashi, R. Fujiwara, Y. Sugihara, J. Nakayama
    • Journal Title

      J. Sulfur Lett (in press)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Preparation of Sterically Congested Compounds : 6, 7-Di-t-butyl-naphthoquinone, 2, 3, 6, 7-Tetra-t-butylanthraquinone, and 2, 3, 6, 7-t-butylanthracen

    • Author(s)
      K. Iguchi, Y. Sugihara, J. Nakayama
    • Journal Title

      Bull. Chew. Soc. Jpn (in press)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2010-02-04  

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