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Chemistry of Sulfur-containing Heterocycles : from Three-membered to Macrocycles

Research Project

Project/Area Number 09440213
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  Faculty of Science, Saitama University Professor, 理学部, 教授 (90092022)

Co-Investigator(Kenkyū-buntansha) NAGASAWA Akira  Faculty of Science, Saitama University Professor, 理学部, 教授 (40108452)
SUGIHARA Yoshiaki  Faculty of Science, Saitama University Associate Professor, 理学部, 助教授 (00272279)
ISHII Akihiko  Faculty of Science, Saitama University Associate Professor, 理学部, 助教授 (90193242)
SAITO Hideki  Faculty of Science, Saitama University Assistant Professor, 理学部, 助手 (90272278)
KUMAKURA Shigekazu  Faculty of Science, Saitama University Associate Professor, 理学部, 助教授 (50008843)
Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥12,900,000 (Direct Cost: ¥12,900,000)
Fiscal Year 1999: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1998: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 1997: ¥7,500,000 (Direct Cost: ¥7,500,000)
Keywordsepisulfide / thiirene 1-oxide / tetrathiolane 3,4-dioxide / SィイD22ィエD2O / pentathiepane / thiophene 1-oxide / thiophene 1,1-dioxide / thiophenophane / テトラチオラン / 1,2-ジチエット / テトラチオラン2,3-ジオキシド / オリゴ(チオ-2,5-チエニレン) / ジベンゾトリチオシン / テトラチオン / ジチエット / トリチオシン / ジメチルジオキシラン / カリックスチオフェン
Research Abstract

The following are new results developed by the present project.
1. Sulfuration of anti- and syn-9,9'-bibenzonorbornenylidenes by elemental sulfur produced episulfides in high yields with retention of the configuration of the original alkenes.
2. Treatment of di-1-adamantylacetylene with disulfur dichloride furnished 2,3-di-1-adamantyl-thiirene 1-oxide, 3,4-di-1-adamantyl-1,2-dithiete, and 1,2-di-1-adamantyl-2-thioxoethanone.
3. Oxidation of tetrathiolanes, carrying two bulky substituents at the 5-position, with dimethyldioxirane, produced the corresponding tetrathiolane 3,4-dioxides, the first vic-disulfoxide isolated in pure form. The 3,4-dioxides decomposed in solution at room temperature to give dithiirane 1-oxides and a reactive species "SィイD22ィエD2O". Deoxygenation of the dithiirane 1-oxides with Lawesson's reagent provided dithiiranes.
4. Ring inversion energies of the trithiolane and pentathiepane rings were determined. A pair of conformational isomers was synthesized by making use of high inversion barrier of the pentathiepane ring.
5. Monocyclic thiophene 1-oxides, 1-imides, and related species were synthesized, and their structures and reactivities were investigated.
6. The parent thiophene 1,1-dioxide and monosubstitued derivatives were synthesized and isolated for the first time, and their spectroscopic properties and reactivities were fully characterized.
7. A wide variety of sulfur-containing large-membered heterocycles, such as thiophenophanes and crown thioethers, were synthesized.

Report

(4 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (44 results)

All Other

All Publications (44 results)

  • [Publications] Akihiko Ishii: "First Synthesis of and Reactivities of Isolable Dithiiranes and Their 1-Oxides"Bulletin of the Chemical Society of Japan. 70. 509-523 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Juzo Nakayama: "Cyclic Oligo(thio-2,5-thienylenes)(Sulfur-bridged Calixarenes)"Chemistry Letters. 897-898 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Juzo Nakayama: "Preparation of Congested Thiophenes Carrying Bulky Substituents on the 3- and 4-Positions and Their Conversion to the Benzene Derivatives"Journal of Organic Chemistry. 63. 4912-4924 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Yosiaki Sugihara: "Synthesis of Pentathiepanes and Isolation of the Conformers Based on High Inversion Barrier of the Pentathiepane Ring"European Journal of Organic Chemistry. 597-605 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Hidehiro Nagasawa: "Thiophene 1,1-DIoxide : Synthesis, Isolation, and Properties"Bulletin of the Chemical Society Of Japan. 72. 1919-1926 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Akihiko Ishii: "1-Adamantyl-tert-butyltetrathiolane 2,3-Dioxide : First Isolable vic Disulfoxide and Efficient Precursor of S20"Journal of the American Chemical Society. 121. 7959-7960 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] J. Nakayama, T. Yu, Y. Sugihara, A. Ishii: "Synthesis of Highly Congested Bi- and Terthiophenes ; 3,4,3',4'-Tetra-tert-butylbithiophene and 3',4'-Di- tert-butyl- 2,2' : 5',2 " -terthiophene""Heterocycles. 44. 75-80 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y.-N. Jin, A. Ishii, Y. Sugihara, J. Nakayama: "Formation of Cyclic Oligosulfides by Reaction of Hydrazones with Disulfur Dichloride"Heterocycles. 44. 252-262 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Ishii, T. Akazawa, M.-X. Ding, T. Honjo, T. Maruta, H. Nagaya, M. Ogura, K. Teramoto, M. Shiro, M. Hoshino, J. Nakayama: "First Synthesis and Reactivities of Isolable Dithiiranes and Their 1-Oxides"Bull. Cem. Soc. Jpn. (headline article). 70. 509-523 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] J. Nakayama, T. Yu, Y. Sugihara, A. Ishii: "Sythesis and Cahracterization of thiophene 1-Oxides Kinetically Stabilized by Bulky Substituents at the 3- and 4-Positions"Chem. Lett.. 499-500 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Ishii, S. Nakamura, T. Yamada, J. Nakayama: "Stereochemistry of Dithiirance 1-Oxides : Optical Resolution, Absolute Configuration, and Racemization and Isomerization of Dithiirane 1-Oxides"Tetrahedron. 53. 12203-12214 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] J. Nakayama, J.-S. Lin: "An Organosilicon Dedrimer Composed of 16 thiophene Rings"Tetrahedron Lett.. 34. 6043-6046 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] J. Nakayama, N. Katano, Y. Sugihara, A. Ishii: "Cyclic Oligo (thio-2,5-thienylenes) (Sulfur-bridged Calixarenes)"Chem. Lett.. 897-898 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] J. Nakayama, H. Nagasawa, Y. Sugihara, A. Ishii: "Synthesis, Isolation, and Full Characterization of the Parent Thiophene 1,1- Dioxides"J. Am. Chem. Soc.. 119. 9077-9078 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] J. Nakayama, N. Masui, Y. Sugihara, A. Ishii: "Reductive and Ring-expansion Study of 3,4-Di(adamantyl)-1,2-dithiete"Bull. Chem. Soc. Jpn.. 71. 1181-1186 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Maruta, Y. Sugihara, S. Tanaka, A. Ishii, J. Nakayama: "Synthesis of Dibenzo[d,g][1,3,6]trithiocins"Bull. Chem. Soc. Jpn.. 71. 1187-1292 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Sugihara, H. Takeda, and J. Nakayama: "Stereoisomerism Based on High-energy Inversion Barrier of a Pentathiepane Ring. Synthesis and Isolation of Conformers"Tetrahedron Lett.. 39. 2605-2608 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y.-N. Jin, A. Ishii, Y. Sugihara, J. Nakayama: "Formation of Dithiirane 1-Oxides by Oxidation of Tetrathiolanes with Dimethyldioxirane"Tetrahedron Lett.. 39. 3525-3528 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] J. Nakayama, R. Hasemi, K. Yoshimura, Y. Sugihara, S. Yamaoka, N. Nakamura: "Preparation of Congested Thiophenes Carrying Bulky Substituents on the 3- and 4-Positions and Their Conversion to the Benzene Derivatives"J. Org. Chem.. 63. 4912-4924 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] J. Nakayama, S. Tanaka, Y. Sugihara, A. Ishii: "Synthesis with Bis(o-mercapto)phenyl Sulfide : An Easy Access to Sulfur-containing 16- Membered Heterocycles"Heterocycle. 50. 103-108 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] J. Nakayama, Y. Hasegawa, Y. Sugihara, A. Ishii: "Acid-catalyzed Intramolecular Disproportionation of 3,4-Diphenylthiophene-2,5-dimethanol. Formation of 5-Methyl-3,4-diphenylthiophene-2-carbaldehyde"Sulf. Lett.. 22. 131-140 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] J. Nakayama, Y. Sano, Y. Sugihara, A. Ishii: "Thiophene Sulfoximides : 2,4- and 3,4-Di-tert-butyl-1-imino-1,1-dihydro-thiophene 1-Oxides"Tetrahedron Lett.. 40. 3785-3788 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Otani, Y. Sugihara, A. Ishii, J. Nakayama: "1-Imino and 1,1-Diimino Derivaties of 3,4-Di-tert butylthiophene"Tetrahedron Lett.. 40. 5549-5552 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] J. Nakayama, A. Kaneko, Y. Sugihara, A. Ishii: "Synthesis of Sulfur-containing Large-membered Heterocycles (Crown Thioethers) with Bis(o-mercapto)phenyl Sulfide"Tetrahedron. 55. 10057-10066 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Ishii, M. Nakabayashi, J. Nakayama: "1-Adamantyl-tert-butyltetrathiolane 2,3-Dioxide : First Isolable vic-Disulfoxide and Efficient Precursor of S2O"J. Am. Chem. Soc.. 121. 7959-7960 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Ishii, T. Nakaniwa, K. Umezawa, J. Nakayama: "Rearrangement of the Carbanion Generated from a Tied-back 1,4-Trithiolane Oxide (6,7,8-Trithiabicyclo[3,2,1]octane 6-Oxide)"Tetrahedron. 55. 10341-10350 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Sugihara, K. Abe, and J. Nakayama: "Synthesis, Structure, and Ring Inversion of a Trithiolane (6b,12b-Epitrithio-acenaphtho[1,2-a]- acenaphthylene)"Heteroatom. Chem.. 10. 638-641 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] J. Nakayama, H. Nagasawa, Y. Sugihara, A. Ishii: "Synthesis, Isolation, and Dimerization and Trimerization of Monosubstituted Thiophene 1,1-Dioxides"Heterocycles. 52. 365-382 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Juzo Nakayama: "Synthesis with Bis(o-mercapto)phenyl Sulfide: An easy Access to Sulfur-containing 16-Membered Heterocycles"Heterocycles. 50. 103-108 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Yoshiaki Sugihara: "Synthesis of Pentathiepanes and Isolation of the Conformers Based on High Inversion Barrier of the Pentathiepane Ring"European Journal of Organic Chemistry. 597-605 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Juzo Nakayama: "Thiophene Sulfoximides: 2,4-and 3,4-Di-tert-butyl-1-imino-1,1-dihydrophene 1-Oxides"Tetrahedron Letters. 40. 3785-3788 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takashi Otani: "1-Imino and 1,1-Diimino derivatives of 3,4-Di-tert-butylthiophene"Tetrahedron Letters. 40. 5549-5552 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Hidehiro Nagasawa: "Thiphene 1,1-Dioxide: Synthesis, Isolation, and Properties"Bulletin of the Chemical Society of Japan. 72. 1919-1926 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Akihiko Ishii: "1-Adamantyl-tert-butyltetrathiolane 2,3-Dioxides: First Isolable vic-Disulfoxide and Efficient Precursor of S2O"Journal of the American Chemical Society. 121. 7959-7960 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Juzo Nakayama: "Ring-Opening and Ring-Expansion Study of 3,4-Di(1-adamantyl)-1,2-dithiete" Bull.Chem.Soc.Jpn.71. 1181-1186 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Teruo Maruta: "Synthesis of Dibenzo[d.g][1,3,6]trithiocins" Bull.Chem.Soc.Jpn.71. 1187-1192 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Yoshiaki Sugihara: "Stereoisomerism Based on High-energy Ring Inversion Barrier of Pentathiepane Ring:Preparation and Isolation of Conformers" Tetrahedron Letters. 39. 2605-2608 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Yi-Nan Jin: "A New Route to Dithiirane 1-Oxides:Oxidation of Tetrathiolanes with Dimethyldioxirane" Tetrahedron Letters. 39. 3525-3528 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Juzo Nakayama: "Preparation of Congested Thiophenes Carrying Bulky Substituents on the 3-and 4-Positions and Their Conversion to the Benzene Derivatives" J.Org.Chem.63. 4912-4924 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Naoki Katano: "Synthesis and Structure of Sulfur-Bridged[1.n](2,5)Thiophenophanes" Bull.Chem.Soc.Jpn.71. 2695-2700 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 中山重蔵: "Synthesis,Isolation, and Full Characterization of the Parent Thiophene 1,1-Dioxide" Journal of the American Chemical Society. 119. 9077-9078 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 中山重蔵: "Cyclic Oligo(thio-2, 5-thienylenes)(Sulfur-bridged Calixarenes)" Chemistry Letters. 897-898 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 中山重蔵: "Synthesis of Dibenzo [d.g][1,3,6]trithiocins" Bulletin of the Chemical Society of Japan. (発表予定).

    • Related Report
      1997 Annual Research Report
  • [Publications] 中山重蔵: "Ring-opening and Ring-expansion Study of 3, 4-Di(1-adamantyl)-1, 2-dithiete" Bulletin of the Chemical Society of Japan. (発表予定).

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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