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Study of Organic Reaction Processes by the Use of Low-Temperature Matrix-Isolation Technique

Research Project

Project/Area Number 09440214
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

MURATA Shigeru  Graduate School of Arts and Sciences, The University of Tokyo, Associate Professor, 大学院・総合文化研究科, 助教授 (40192447)

Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥6,100,000 (Direct Cost: ¥6,100,000)
Fiscal Year 1999: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1998: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 1997: ¥2,800,000 (Direct Cost: ¥2,800,000)
KeywordsMatrix Isolation Technique / Short-lived Reactive Intermediate / Photochemistry / Carbene
Research Abstract

The object of this research is to establish the low-temperature matrix-isolation method as a general technique for the study of an organic reaction mechanism by the expansion of the application range of this technique. In order to make possible to apply this technique to less volatile substrates and to reactive intermediates generated by a large apparatus such as laser and flash vacuum pyrolysis, an inner-rotation mechanism was employed in the low-temperature matrix-isolation apparatus which was designed and set up with the aid of this grant. The ability of this new apparatus to make a low-temperature matrix satisfactory for spectroscopic observations was confirmed by the isolation of p-nitorophenyl azide in an argon matrix and comparison of its IR spectrum with that recorded previously using the other apparatus. The direct observation of the processes of the reaction of p-nitrophenylcarbene (1) with acetonitrile was examined next. Irradiation of (p-nitrophenyl)diazomethane matrix-isolated in argon doped with acetonitrile at 10K gave the carbene 1, which reacted with acetonitrile photochemically or thermally. The reactions were nicely monitored by IR and UV-Vis spectroscopy to find that the product formed by the further photolysis of 1 in an acetonitrile-doped matrix was different from that obtained thermally in the matrix. The structure of these products was estimated on the basis of the isotope experiment and DFT calculations. These preliminary results were suggested that the low-temperature matrix-isolation technique would be a powerful method for studying the reaction mechanism of organic reactive intermediates.

Report

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

    (19 results)

All Other

All Publications (19 results)

  • [Publications] Shigeru Murata: "Photochemical Reactions of Mesity1 Azide with Tetracyanoethylene : Competitive Trapping of Singlet Nitrene and Didehydroazepine"Journal of Organic Chemistry. Vol.62 No.5. 3055-3061 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Shigeru Murata: "Large Deuterium Isotope Effects for Intramolecular CH Insertion Reaction of 2-Alkyphenylnitrenes"Chemistry Letters. No.6. 549-550 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Shigeru Murata: "Photochemistry of 2,4-Bis(diazo)-1,2,3,4-tetrahydronaphthalene-1, 3-dione : Selective Photodecomposition of One of the Two Inequivalent Diazo Goups"Journal of the American Chemical Society. Vol.120 No.35. 9088-9089 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Nicolaides: "Direct Observation and Characterization of p-Phenylenebisnitrene. Alabile Quinoidal Diradical"Journal of the American Chemical Society. Vol. 120 No.44. 11530-11531 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Shigeru Murata: "New Findings in Photochemistry of p-Nitrophenyl Azide in the Presence of an Amine : Generation and Trapping of Enamines"Chemistry Letters. No. 7. 597-598 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Shingo Ikeda: "Remarkable Effect of Electron Acceptors on Pyrene-Sensitized Decomposition of N-Phenylglycine"Chemistry Letters. No. 10. 1009-1010 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Shigeru Murata: "Photochemical Reactions of Mesityl Azide with Tetracyanoethylene : Competitive Trapping of Singlet Nitrene and Didehydroazepine"Journal of Organic Chemistry. Vol. 62, No. 5. 3055-3061 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Shigeru Murata: "Large Deuterium Isotope Effects for Intramolecular CH Insertion Reaction of 2-Alkylphenylnitrenes"Chemistry Letters. No. 6. 549-550 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Shigeru Murata: "Photochemistry of 2, 4-Bis(diazo)-1, 2, 3, 4-tetrahydronaphthalene-1, 3-dione : Selective Photodecomposition of One of the Two Inequivalent Diazo Groups"J. Am. Chem. Soc.. Vol. 120, No. 35. 9088-9089 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Nicolaides: "Direct Observation and Characterization of p-Phenylenebisnitrene. A Labile Quinoidal Diradical"J. Am. Chem. Soc.. Vol. 120, No. 44. 11530-11531 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Shigeru Murata: "New Findings in Photochemistry of p-Nitrophenyl Azide in the Presence of an Amine : Generation and Trapping of Enamines"Chemistry Letters. No. 7. 597-598 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Shingo Ikeda: "Remarkable Effect of Electron Acceptors on Pyrene-Sensitized Decomposition of N-Phenylglycine"Chemistry Letters. No. 10. 1009-1010 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Shigeru Murata: "New Findings in Photochemistry of p-Nitrophenyl Azide in the Presence of an Amine : Generation and Trapping of Enamines"Chemistry Letters. No.7. 597-598 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Sigeharu Wakabayashi: "Self-Assembly of 3-[4'-(Diethylboryl)phenyl]pyridine and 3-[3 '-(Diethylboryl)phenyl]-pyridine : Synthesis, Structural Features, and Stability in Solution"Journal of Organic Chemistry. Vol.64 No.19. 6999-7008 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Shingo lkeda: "Remarkable Effect of Electron Acceptors on Pyrene-Sensitized Decomposition of N-Phenylglycine"Chemistry Letters. No.10. 1009-1010 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Shigeru Murata: "Large Deuterium Isotope Effects for Intramolecular CH Insertion Reaction of 2-Alkylphenylnitrenes" Chemistry Letters. No.6. 549-550 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Shigeru Murata: "Photochemistry of 2, 4-Bis(diazo)-1, 2, 3, 4-tetrahydronaphthalene-1, 3-dione : Selective Photodecomposition of One of the Two Inequivalent Diazo Groups" Journal of the American Chemical Society. Vol.120 No.35. 9088-9089 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] A.Nicolaides: "Direct Observation and Characterization of p-Phenylenebisnitrene. A Labile Quinoidal Diradical" Journal of the American Chemical Society. Vol.120 No 44. 11530-11531 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Shigeru Murata: "Photochemical Reactions of Mesityl Azide with Tetracyanoethylene:Competitive Trapping of Singlet Nitrene and Didehydroazepine" The Journal of Organic Chemistry. Vol.62 No.10. 3055-3061 (1996)

    • Related Report
      1997 Annual Research Report

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

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