1997 Fiscal Year Final Research Report Summary
Construction of Organic Reaction Mechanism with Explicit Consideration of Solvent Thermal Fluctuations
| Project/Area Number |
08454204
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | KYUSHU UNIVERSITY |
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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)
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| Co-Investigator(Kenkyū-buntansha) |
SUMI Hitoshi University of Tsukuba, Institute of Materials Professor Science, 物理工学系, 教授 (10134206)
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| Project Period (FY) |
1996 – 1997
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| Keywords | reaction rate / solvent viscosity / pressure effect / dynamic solvent effect / solvent thermal fluctuations |
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| 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.
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Research Products
(12 results)
