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Measurement of Quantity of Heat and Thermodynamical Prameters for the Chemiluminescent Cycloreversion specific in the Solid State

Research Project

Project/Area Number 05453022
Research Category

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

Allocation TypeSingle-year Grants
Research Field Physical chemistry
Research InstitutionOkayama University

Principal Investigator

KIMURA Masaru  Okayama University, Faculty of Science Professor, 理学部, 教授 (30033442)

Co-Investigator(Kenkyū-buntansha) OKAMOTO Hideki  Okayama University, Faculty of Science Assis.Professor, 理学部, 助手 (30204043)
SATAKE Kyousuke  Okayama University, Faculty of Science Associ.Professor, 理学部, 助教授 (50033387)
Project Period (FY) 1993 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 1995: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1994: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1993: ¥3,600,000 (Direct Cost: ¥3,600,000)
KeywordsCHEMILUMINESCENCE / SOLID STATE / BIPLANEMER / Nd-YAG IR LASER / DSC / LOPHINEPEROXIDES / PYRROLES / 断熱的反応 / 熱的に禁制な反応形式 / バイプレンマー類 / ロフィン類 / ビシクロ〔b〕ピロール類 / 示差熱分析 / ロフィン系化学発光 / ミクロブタ[b]ピロール類 / 断熱過程 / 非断熱過程 / フッ素化学 / 光化学 / ロフィンペルオキシド / 有機固体化学
Research Abstract

We have investigated a thermally forbidden ring fission or ring opening reaction of biplanemers ([4+4] heterodimers of arenes) 1, lophine peroxides 2 and cyclobuta [b] pyroles 3 which are an energy rich system. The chemiluminescent thermal cycloreversion of 9-anthracenecarboxylic acid-benzene biplanemer and the chemiluminescent multiphoton cycloreversion of anthracene- p-difluoro-benzene biplanemer with Nd-Yag IR laser light gave off chemiluminescent light only in the solid phase. As there has not been any attempt to reveal the determinants in the solid state for the chemiluminescence from thermodynamical view points, this prompted us to collect the thermodynamic parameters by differential scanning calorimetry (DSC). In the cases of 1, two substantial exothermal processes are superimposed for the chemiluminescent crystals, whereas one main exothermal process is observed for a nonchemiluminescent powder sample. The thermodynamic parameters for the thermal cycloreversions were collected. Higher activation energy is characteristic of the chemiluminescent process prepared in the solid phase. Efficient chemiluminescence was observed in the thermal reaction of lophineperoxides 2 in both solid and liquid phases. Virtually same activation energies were obtained. The kinetic and thermochemical study of thermal ring opening reaction of 3,5- and 2,4-di-tert-butyl-3a, 5a-dihydro-3H-cyclobuta- [b] pyroles 3a and 3b to the corresponding di-tert-butyl substituted azepines was performed in the solid state, and provided activation energies 12 kcal/mol and 24 kcal/mol, respectively.

Report

(4 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • 1993 Annual Research Report
  • Research Products

    (31 results)

All Other

All Publications (31 results)

  • [Publications] 木村 勝: "MAXIMIZATION OF THE CHEMILUMINESCENCE EFFICIENCY OF 1, 4, 5-TRIARYLHYDROXY-4H-ISOIMIDAZOLES" Chem. Lett.,. 505-508 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 岡本秀毅: "SYNTHESIS AND ADIABATIC PHOTOCHEMISTRY OF 1, 4-DIFLUOROBENZENE-NAPHTHALENE BIPLANE" Bull. Chem. Soc. Jpn. 66. 2436-2439 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 佐竹恭介: "THE SYNTHESIS OF 3H-AZEPINES: THERMAL REORGANIZATION OF 2, 4- AND 3, 5D_1-t-BUTYL-3a, 5a-DYHYDRO-3H-CYCLO-BUTA 〔b〕 RYRROLES TO 2, 5-AND 3, 6-DI-t-BUTYL-3H-AZEPINES" Heterocycles. 38. 769-778 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 木村 勝: "THE CHEMILUMINESCENT CYCLORE VERSION OF AN ANTHRACENE-BENZEN BIPLANEMER SYSTEM BOTH IN THE SOLID STATE AND IN THE LIQUID STATE" Bull. Chem. Soc. Jpn. 67. 2203-2212 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 岡本秀毅: "CHARACTERIZATION OF A LONGICYCLIC 〔2, 2, 2, 2〕-CONJUGATED π SYSTEM IN 1, 4-DIFLUOROBENZENE NAPHTHALENE BIPLANEMER" Bull. Chem. Soc. Jpn. 68. 3557-3562 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 佐竹恭介: "REAPRANGEMENT OF BICYCLO 〔2, 2, 2〕 OCTA -2, 5-DIENE AND BICYCLO 〔3, 2, 2〕 NONA-6, 8-DIENE UNDER THE CONDITION OF BROMINATION" Bull. Chem. Soc. Jpn. 69. 453-457 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 木村 勝ら: "有機固体化学" 三共出版, 160 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Kimura, H.Nishikawa, H.Kura, H.Lim, and E.H.White: "Maximization of the Chemiluminescence Efficiency of 1,4,5-Triarylhydroperoxy-4H-isoimidazoles" Chem.Lett.505-508 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] H.Okamoto, M.Kimura, K.Satake, and S.Morosawa: "Synthesis and Adiabatic Photochemistry of 1,4-Difluorobenzene- Naphthalene Biplaneme" Bull.Chem.Soc.Jpn.66. 2436-2439 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Kimura and M.Morita: "Isolation of (5-Cyclopentadienyl) (1,2,3,4,5,6-exo-methoxy-7-oxo-2,4-cyclo-heptadienyl) ruthenium (II) as a Key Intermediate for the Selective H/D Exchange on Its Coordinated Tropone Moiety by KOH/CD3OD" Bull.Chem.Soc.Jpn.66. 3120-3123 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Satake, H.Saito, M.Kimura, and S.Morosawa: "The Synthesis of 3H-Azepines : Thermal Reorganization of 2,4- and 3,5-Di-t-butyl-3a, 5a-dihydro-3H-cyclobuta [b] pyrroles to 2,5- and 3,6-Di-t-butyl-3H-azepines" Heterocycles. 38. 769-778 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Satake, R.Okuda, M.Hashimoto, Y.Fujiwara, H.Okamoto, M.Kimura, and S.Morosawa: "Demethoxycarbonylation of Methyl 2,5- and Methyl 3,6-Dialkyl-1H-azepine-1-carboxylates : Formation and Characterization of 2H-, 3H- and 4H-Azepiness" J.Chem Soc., Perkin Trans.1. 1753-1755 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Kimura, H.Okamoto, and S.Kashino: "The Chemiluminescent Cycloreversion of an Anthracene-Benzene Biplanemer System both in the Solid State and in the Liquid State" Bull.Chem.Soc.Jpn.67. 2203-2212 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] H.Okamoto, Kyousuke Satake and Masaru Kimura: "Characterization of a Longicyclic [2,2,2,2] conjugated p System in 1,4-Difluoro-benezene-Naaphthalene Biplanemer" Bull.Chem.Soc.Jpn.68. 3557-3562 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Satake, H.Itoh, M.Kimura, S.Morosawa and S.Kashino: "Dimethyl 4-exo, 9-endo-Dibromobicyclo [3.3.1] non-2-ene-2,3-dicarboxylate" Acta Crystallogr., Sect.C. 51. 1397 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Satake, K.Hikasa, H.Ito, H.Okamoto, M.Kimura, and S.Morosawa: "Rearrangement of Bicyclo [2.2.2] octa-2,5-diene and Bicyclo [3.2.2] -nona-6.8-diene under the Condition of Bromination" Bull.Chem.Soc.Jpn.69. 453-457 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] MASARU KIMURA et al.: "MAVIMIZATION OF THE CHEMILUMINESCENCE EFFICIENCY OF……" CHEMISTRY LETTERS. 505-508 (1993)

    • Related Report
      1995 Annual Research Report
  • [Publications] HIDEKI OKAMOTO et al.: "SYNTHESIS AND ADIABATIC PHOTOCHEMISTRY OF A 1,4-DIFWORO……" Bull.CHEM.Soc.JPN. 66. 2436-2439 (1993)

    • Related Report
      1995 Annual Research Report
  • [Publications] MASARU KIMURA et al.: "THE CHEMILUMINESCENT CYCLOREVERSION OF AN ANTHRACENE-" Bull.CHEM.Soc.JPN. 67. 2203-2212 (1994)

    • Related Report
      1995 Annual Research Report
  • [Publications] HIDEKI OKAMOTO: "CHARACTERIZATION OF A LONGICYCLIC (2,2,2,2) CONJUGATED" Bull.CHEM.Soc.JPN. 68. 3557-3562 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] KYOSUKE SATAKE: "DEMETHOXYCARBONYLATION OF METHYL 2,5-AND METHYL 3,6……" J.CHEM.Soc.PERKIN TRANCF.I.1753-1757 (1994)

    • Related Report
      1995 Annual Research Report
  • [Publications] KYOSUKE SATAKE: "THE SYNTHESIS OF 3H-AZEPINES : THERMAL REOQGANIZATION" HETEROCYCLES. 38. 769-778 (1994)

    • Related Report
      1995 Annual Research Report
  • [Publications] 木村 勝: "有機固体化学" 三共出版株式会社 萩原町子, 160 (1993)

    • Related Report
      1995 Annual Research Report
  • [Publications] 木村 勝: "THE CHEMILUMINE SENT CYCLOREVERSION OF A ANTHRACENE-BENZENE BIPLANEMER S YSTEM BOTH IN THE SOLID STATE AND INTEELIQUID STATE" BULL.CHEM.,SOC.JPN. 67. 2203-2212 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 佐竹 恭介: "THE SYNTHESIS OF 3H-AZEPINES:THERMAL REORGANIZATION OF 2,4-AND 3,5-Di-t-BUTYL-3a,5a-DIHYDRO-3H-CYCLOBUTA[b]PYRROLES……" HETEROCYCLES. 38. 769-778 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 佐竹 恭介: "DEME THOXYCALBONYLATION OF METHYL 2,5-AND METHYL 3,6-DIALKYL・IH-AZEPINE-1-CARBOXYLATES:FORMATION AND CHARAC TERIZATION……" J.CHEM.SOC.,PERKIN TRANS.1.1753-1755 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 木村勝: "Maximization of Chemiluminescence Efficiency of 1,4,5-Triarylhydroperoxy-4H-isoimidazoles" Chem.Lett.505-508 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] 木村勝: "Isolation of (η^5-Cyclopentadienyl)(1,2,3,4,5-η^5-exo-methoxy-7-oxo-2,4-cycloheptadienyl)-ruthenium(II)" Bull.Chem.Soc.Jpn. 66. 3120-3123 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] 岡本秀毅: "Synthesis and Adiabatic Photochemistry of 1,4-Difluorobenzene-Naphthalene Biplanemer" Bull.Chem.Soc.Jpn. 66. 2436-2439 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] 佐竹恭介: "The Synthesis of 3H-Azepines:Thermal Reorganization of 2,4-and 3,5-Di-t-Buthyl-3H-Azepines" Heterocycles. 38. 0000-0000 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] 木村勝編著: "有機固体化学" 三共出版株式会社, 160 (1993)

    • Related Report
      1993 Annual Research Report

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Published: 1993-04-01   Modified: 2016-04-21  

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