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Control of Reactivity and Selectivity through Elucidiation of Activation Mechanisms of Sonochemical Reactions

Research Project

Project/Area Number 04453021
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionSHIGA UNIVERSITY OF MEDICAL SCIENCE

Principal Investigator

ANDO Takashi  SHIGA UNIVERSITY OF MEDICAL SCIENCE,DEPARTMENT OF CHEMISTRY,PROFESSOR, 医学部, 教授 (70029867)

Co-Investigator(Kenkyū-buntansha) FUJITA Mitsue  SHIGA UNIVERSITY OF MEDICAL SCIENCE,DEPARTMENT OF CHEMISTRY,RESEARCH ASSISTANT, 医学部, 教務職員 (40175576)
SOHMIYA Hajime  SHIGA UNIVERSITY OF MEDICAL SCIENCE,DEPARTMENT OF CHEMISTRY,ASSOCIATE, 医学部, 助手 (80211324)
KIMURA Takahide  SHIGA UNIVERSITY OF MEDICAL SCIENCE,DEPARTMENT OF CHEMISTRY,RESEARCH ASSOCIATE P, 医学部, 助教授 (70167378)
Project Period (FY) 1992 – 1994
Project Status Completed (Fiscal Year 1994)
Budget Amount *help
¥5,500,000 (Direct Cost: ¥5,500,000)
Fiscal Year 1994: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1993: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1992: ¥3,200,000 (Direct Cost: ¥3,200,000)
KeywordsSonochemistry / Ultrasound / Lead Tetraacetate / Photochemistry / 光反応 / テトラヒドロフラン / ヒドロペルオキシド / 標準化 / 光化学 / 二酸化マンガン / 担持試薬
Research Abstract

Mechanisms of sonochemical activation in several reactions were studied in order to establish it as the novel and general method of controlling the reactivity and selectivity of chemical reactions. Results are summarized below :
1. In several reactions of lead tetraacetate, we found that : (1) stirenes whose reaction courses become more radical at higher temperatures showed the acceleration in their rates with more radical products under ultrasonic irradiation ; (2) a triarylmethane which reacts by increasing ionic mechanisms at higher temperatures showed no definite results ; and (3) 2-octanol whose reactivity does not change at higher temperatures does not show any clear effect of ultrasound. The results showed that the effect of ultrasound originates from the thermal effect.
2. Thermodynamic study on the reaction of lead tetraacetate with trans-beta-methylylstirene indicated that the chain propagation step involving methyl radical occurs at a temperature only slightly higher than that … More determined by a thermocouple. The result indicated that the cite of the reaction is not in the interface but in the bulk liquid.
3. Catalytic reactions of active manganese dioxide with mixtures of different classes of compounds showed the characteristic selectivity based of the adsorption on the surface.
4. Sonochemical switching from aliphatic nucleophilic substitution to aromatic electrophilic substitution by selective poisoning of the basic cites on the alumina surface with acidic salts by accelerating solid-solid interaction with ultrasonic irradiation was tried in the mixtures of organic halides, salts, and alumina in aromatic solvents without much success.
5. Simultaneous irradiation of a tetrahydrofuran solution of benzophebnone with ultrasound and UV light gave tetrahydrofuran hydroperoxide, while their separate of sequential irradiation did not. The mechanisms are not clear yet.
6. Standardization of the power of ultrasound was studied by using calorimetry and the Weissler reaction. Less

Report

(4 results)
  • 1994 Annual Research Report   Final Research Report Summary
  • 1993 Annual Research Report
  • 1992 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] Takahide Kimura: "Selectivity in Catalytic Dehydrogenation with Active Manganese Dioxide" Bulletin of the Chemical Society of Japan. 65. 1149-1150 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Mitsue Fujita: "The effect of Added Pyridines on the Fulorination with Silver Fluoride Supported Rreagents" Chemistry Express. 7. 317-320 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Hajime Sohmiya: "Novel One-Step Synthesis of Sulfonyl Chlorides from Sulfides with Iodosobenzene and Hydrogen Chloride-Treated Silica Gel" Chemistry Letters. 1931-1932 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] David G.Cork: "Improved Fluorination with Supported Fluoride Reagents" Bulletin of Shiga University of Medical Science (General Education). 4. 7-11 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takashi Ando: "Effect of Ultrasound on the Reaction of trans-β-Methylstyrene with Lead Tetraacetate" Ultrasonics Sonochem. 1. S33-S35 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takahide Kimura: "Structual Effect on Chelation Selectivity of Alkaline Earth Metal Ions with Aminopolycarboxylate-Type Chelators" Bulletin of the Chemical Society of Japan. 67. 1615-1621 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takahide Kimura: "The Side of the Sonochemically-Initiated Radical Recation on Lead Tetraacetate with γ-Methylstyrene" Chemistry Letters. 55-56 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takashi Ando: "Inorganic Solid Supported Reagents as Acid and Bases,in "Acid-Base catalysis II",ed by, H.Hatton,M.Misono,and Y.Ono" Kodansha, 557 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takahide Kimura: "Selectivity in Catalytic Dehydrogenation with Active Manganese Dioxide" Bulletin of the Chemical Society of Japan. 65. 1149-1150 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Mitsue Fujita: "The Effect of Added Pyridines on the Fulorinatio with Silver Fluoride Supported Reagents" Chemistry Express. 7. 317-320 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Hajime Sohmiya: "Novel One-Step Synthesis of Sulfonyl Chlorides from Sulfides with Iodosobenzene and Hydrogen Chloride-Treated Silica Gel" Chemistry Letters. 891-892 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] David G.Cork: "Improved Fluorination with Supported Fluoride Reagents" Bulletin of Shiga University of Medical Science (General Education). 4. 7-11 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takashi Ando: "Effect of Ultrasound of the Reaction of trans-beta-Methylstirene with Lead Tetraacetate" Ultrasonics Sonochem. 1. s33-s35 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takahide Kimura: "Structual Effect on Chelation Selectivity of Alkaline Earth Metal Ions with Aminopolycarboxylate-Type Chelators" Bulletin of the Chemical Society of Japan. 67. 1615-1621 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takahide Kimura: "The Site of the Sonochemically-Initiated Radical Recation on Lead Tetraacetate with gamma-Methylstirene" Chemistry Letters. 55-56 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takashi Ando: Inorganic Solid Supported Reagents as Acid and Bases, in "Acid-Base catalysis II" , ed by, H.Hatton, M.Misono, and Y.Ono. Kodansha, 9-20 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takahide Kimura: "Structural Effect on Chelation Selectivity of Alkaline Earth Metal Ions with Aminopolycarboxylate-type Chelators" Bulletin of the Chemical Society of Japan. 1615-1621 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Takahide Kimura: "The Site of the Sonochemically-Initiated Radical Reaction of Lead Tetraacetate with β-Methylstyrene" Chemistry Letters. 67. 55-56 (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] Takashi Ando: "Acid-Base CatalysisII" Kodansha, 557 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Takashi Ando: "Effect of Ultrasound on the Reaction of trans-β-Methylstyrene with Lead Tetraacetate" Ultrasonics Sonochemistry. 1. 33-35 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Takahide Kimura: "Seleetivity in Catalytic Dehydrogenation with Active Monganese Dioxide" Bulletin of the Chemical Society of Japan. 65. 1149-1150 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] 藤田 光恵: "フッ化銀担持試薬を用いるフッ素置換反応における ビリジン類の添加効果" Chemistry Express. 7. 317-320 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Hajime Sohmiya: "Novel One-Step Synthesis of Sulfonyl Chlorides from Sulfides with Iodosobenzene and Hydrogen Chloride-Treated Silica Gel" Chemistry Letters. 891-892 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] David G.Cork: "Improved Fluorination with Supported Fluoride Reagents" Bulletin of Shiga University of Medical Science(General Education). 4. (1993)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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