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DEVELOPMENT OF METHODS FOR QUANTITATIVE RATING OF LEWIS ACIDITY OF METAL IONS IN HYDROPHOBIC SOLUTION PHASES

Research Project

Project/Area Number 04650757
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionKYUSHU UNIVERSITY

Principal Investigator

KOBAYASHI Hiroshi  KYUSHU UNIVERSITY, INSTITUTE OF ADVANCED MATERIAL STUDY ; PROFESSOR, 機能物質科学研究所, 教授 (10037731)

Co-Investigator(Kenkyū-buntansha) SONODA Takaaki  KYUSHU UNIVERSITY, INSTITUTE OF ADVANCED MATERIAL STUDY ; ASSOCIATE PROFESSOR, 機能物質科学研究所, 助教授 (90108770)
Project Period (FY) 1992 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1993: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1992: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsLewis acidity / Alkali metal ion / Perfluoroalkyl effect / Lipophilic metal salt / Halochromism / Triphenylmethyl cation / Spiropyran / Azobenzene / 含フッ素テトラフェニルホウ素アート錯体 / アゾベンゼンのハロクロミズム / 脂溶性アルカリ金属塩 / スピロピラン・メロシアニン互変異性 / アルカリ金属イオンのLewis酸性 / ベタイン型〓性指示薬 / フェニルアゾスピロピラン / 結晶解析 / Diels-Alder反応触媒
Research Abstract

1. On purpose to incorporate alkali metal ion in a desolvated form into a hydrophobic solution phase, highly lipophilic and bulky perfluoroalkyl-substituted stable tetraphenylboron-ate complex were synthesized. Fluorine-substituent effects were evaluated in terms of their solubilities and decomposition rate constants in acid media.
2. Alkali metal salts of the lipophilic borate act as Lewis acid in CH_2Cl_2 to cleave (1) the C-Cl bond of triphenylmethyl chloride, giving triphenylmethyl cation and (2) the C-O bond of 1, 1, 3-trimethylspiro[indoline-2, 3'-[6]-naphtho-[2,1-b]pyrans], giving a corresponding merocyanine, accompanying color-developing. Lewis acidity of alkali metal ion was rated by the extent of induced spectroscopic shift and was discussed in terms of the ionic charge and radius.
3. Halochromic shifts induced by alkali metal salts of the lipophilic borate on 2,4,4', 6-tetramethoxyazobenzene in CH_2Cl_2 were correlated well with Lewis acidity of metal ion described above.
4. Halochromic shift induced by alkali metal salts of the lipophilic borate on 2,6-diphenyl-4-(2,4,6-triphenylpyridino)phenolate betaine was rapid rate process and difficult to be used as a measure of Lewis acidity of metal ion.
5. The observed spectroscopic shift was affected by the presence of nimute water in different manner from a solvent to another. The water concentration is, therefore, required to be precisely controlled for the quantitative rating of Lewis acidity of metal ion in a hydrophobic solution phase.

Report

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

    (13 results)

All Other

All Publications (13 results)

  • [Publications] FUJIKI,Kanji: "Syntheses and lipophilicities of tetraarylborate ions substituted with many trifluoromethyl groups." Journal of Fluorine Chemistry. 57. 307-321 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] 小林 宏: "アリルアゾ置換スピロピラン型色素の^1H-及び^<13>C-NMRスペクトル" 九州大学中央分析センター報告. 10. 50-57 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] KOBAYASHI,Hiroshi: "Synthesis of some arylazospirpyrans" Report of Institute of Advanced Material Study,Kyushu University. 6. 21-26 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] 小林 宏: "TFPBの溶液化学-裸のアルカリ金属イオンの親電子反応性について" 九州大学機能物質科学研究所報告. 10. 103-113 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] FUJIKI,Kanji: "Syntheses and lipophilicities of perfluoralkyl-substituted tetraarylborate ions." Journal of Fluorine Chemistry. (発表予定).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kanji Fujiki, Mituyoshi Kashiwagi, Hideyuki Miyamoto, Junji Ichikawa, Hiroshi Kobayashi, and Takaaki Sonoda: "Synthesis and lipophilicity of tetra-arylborate ions substituted with many trifluoromethyl groups." Jounal of Fluorine Chemistry. Vol.57. 301-321 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hiroshi Koabayashi, Akinari Sonoda, and Takaaki Sonoda: "Synthesis of some arylazospiropyrans" Reports of Institute of Advanced Material Study, Kyushu University. Vol.6, No.2. 87-92 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hiroshi Koabayashi, Takaaki Sonoda, Advanced and Akinari Sonoda: "^1H- and ^<13>C-NMR spectra of some arylazospiropyrans" Reports of the Center of Advanced Instrumental Analysis, Kyushu University. No.10. 50-57 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hiroshi Kobayashi, Kanji Fujiki, Akihisa Nagira, Jin Nie, Akinari Sonoda, and Takaaki Sonoda: "The solution chemistry of TFPB salts : The electrophilicity of "naked" alkali metal ions." Reports of Institute of Advanced Material Study, Kyushu University. Vol.7, No.1. 103-113 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hiroshi Kobayashi, Takaaki sonoda, Kanji Fujiki, Minoru Isshiki, and Akinari Sonoda: "Synthesis and lipophilicity of perfluoroalkyl-substituted tetraarylborate ions" Journal of Fluorine Chemistry. in preparation.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] FUJIKI,Kanji: "Syntheses and lipophilicities of tetraarylborate ions substituted with many trifluoromethyl groups" Journal of Fluorine Chemistry. 57. 307-321 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] 小林 宏: "アリルアゾ置換スピロピラン型色素の^1H-及び^<13>C-NMRスペクトル" 九州大学中央分析センター報告. 10. 50-57 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] KOBAYASHI,Hiroshi: "Synthesis of some arylazospiropyrans" Reports of Institute of Advanced Material Study Kyushu University. 6. 21-26 (1992)

    • Related Report
      1992 Annual Research Report

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

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