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1997 Fiscal Year Final Research Report Summary

Construction of Organic Reaction Mechanism with Explicit Consideration of Solvent Thermal Fluctuations

Research Project

Project/Area Number 08454204
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKYUSHU UNIVERSITY

Principal Investigator

ASANO Tsutomu  Kyushu University, Institute for Fundamental Professor Research of Organic Chemistry, 有機化学基礎研究センター, 教授 (40094057)

Co-Investigator(Kenkyū-buntansha) SUMI Hitoshi  University of Tsukuba, Institute of Materials Professor Science, 物理工学系, 教授 (10134206)
Project Period (FY) 1996 – 1997
Keywordsreaction rate / solvent viscosity / pressure effect / dynamic solvent effect / solvent thermal fluctuations
Research Abstract

1.Viscosity measurements. Viscosity of 2,4-dicyclohexy1-2-methylpentane was measured at conditions of 25-150゚C and 0.1-430 MPa.
2.Measurements on a compound with a smaller degree of freedom of motion. Viscosity dependence of the Z/E isomerization of N,N'-dimethylindigo (DMIG) was measured in glycerol triacetate. The viscosity dependence was found to be comparable with those of other compounds with a larger degree of freedom of motion. The reaction deviated from the first-order rate law at high viscosities.
3.Measurements on a compound with a positive electrical charge. Viscosity dependence of the Z/E isomerization of 3,3'-diethyloxacarbocyanine iodide was measured in 2-methyl-2,4-pentanediol (MPD). Despite the existence of a positive charge, the viscosity dependence was similar to the ones observed for neutral compounds.
4.Measurements on a reaction with charge neutralization. Disappearance of a merocyanine formed from 1,3-dihydro-1,3,3-trimethylspiro [2H-indole-2,3'- [3H] naphth [2,1-b] [1,4] oxazine was kinetically studied in MPD at high pressures. Retarding viscosity effect was evident at much lower viscosities than other reactions.
Theoretical considerations. (1) A prediction by Biswas and Bagchi, i.e., isomerization rate will be inversely proportional to a logarithm of the solvent viscosity at high viscosities, was not supported by our results and it was concluded that the one-dimensional reaction coordinate model cannot describe our reaction systems. (2) It is deduced that the photo-produced (Z) -DMIG molecules do not obey Boltzmann distribution and, therefore, the reaction becomes multi-exponential. (3) In order to clarify the reason for the appearance of the viscosity effect at much lower values in the last reaction, further accumulations of experimental results are required.

Research Products

(12 results)

All Other

All Publications (12 results)

  • [Publications] R.Cimiraglia: "Mechanism of Thermal Z/E Isomerization of Aromatic Azo Compounds.Relataion between Rotation and Inversion States" Gazetta Chimica Intaliana. 126. 679-683 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 浅野 努: "高圧下のZ/E異性化反応" 化学工業. 47. 882-888 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Asano,: "Effects of Solvent Fluctuations on the Rate of the Thermal Z/E Isomerization of N-Benzylideneanilines in a Highly Viscous Liquid Hydrocarbon" Bulletin of the Chemical Society of Japan. 70. 239-244 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Sumi: "General Expression for Rates of Solution Reactions Influenced by Slow Solvent Fluctuations,and Its Experimental Evidence" Electrochimica Acta. 42. 2763-2777 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Asano: "Kinetics in Highly Viscous Liquid Phase Realized under High Pressure" The Review of High Pressure Science and Technology. 8(in press). (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Drljaca: "Activation and Reaction Volumes in Solution 3." Chemical Reviews. 98(in press). (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] R.Cimiraglia: "Mechanism of Thermal Z/E Isomerization of Aromatic Azo Compounds. Relations between Rotation and Inversion States" Gazetta Chimica Italiana. 126-10. 679-683 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Asano: "Z/E Isomerization under High Pressure" Chemical Industry. 47-11. 882-888 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Asano: "Effects of Solvent Fluctuations on the Rate of the Thermal Z/E isomerization of N-Benzylideneanilines in a Highly Viscous Liquid Hydrocarbon" Bulletin of the Chemical Society of Japan. 70-1. 239-244 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Sumi: "General Expression for Rates of Solution Reactions Influenced by slow Solvent Fluctuations, and Its Experimental Evidence" Electrochimica Acta. 42-18. 2763-2777 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Asano: "Kinetics in Highly Viscous Liquid Phase Realized under High Pressure" The Review of High Pressure Science and Technology. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A.Drljaca: "Activation and Reaction Volumes in Solution.3" Chemical Reviews. (in press).

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1999-03-15  

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