| Project/Area Number |
08651046
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
高分子合成
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
KAKIMOTO Masa-aki Tokyo Institute of Technology, Department of Organic and Polymeric Materials, Professor, 工学部, 教授 (90152595)
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| Project Period (FY) |
1996 – 1997
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| Project Status |
Completed (Fiscal Year 1997)
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| Budget Amount *help |
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1997: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1996: ¥1,400,000 (Direct Cost: ¥1,400,000)
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| Keywords | Chromium complex / nucleophilic substitution / thioether / absorption spectrum / HPLC / Decomplexation / クロム-カルボニル錯体 / チオフェノール / モデル反応 / 重縮合 |
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| Research Abstract |
Chromium-arene complex was prepared from p-dichlorobenzene and chromium hexacarbonyl. Stability in organic solvents and reactivity of the complex for nucleophilic aromatic substitution were investigated in detail.
The complex was prepared from chromium-hexacarbonyl and p-dichlorobenzene, as reported in literature. The final purification process was changed to sublimation instead of column chromatography. Spectroscopic data and its melting point were consistent with those in literature.
Stability of the complex in organic solvents is investigated by the change of absorption at 325 nm. The absorption decreased to 70% from the initial one after 1 h in non-polar solvents. The decrease is independent on the presence of water and oxygen. Exchange reaction or dissociation of ligand may exist in the solution.
Nucleophilic aromatic substitutions by phenol and thiophenol were carried out in DMSO at 100ﾟC.The ratio of mono and disubstituted product was estimated from the crude product without isolation by HPLC measurements. Disubstituted product was obtained by the reaction of thiophenol. The fact indicates that second substitution by thiophenol proceeds smoothly whereas ether bond retard the second substitution by phenol. Decomplexation reaction proceeded efficiently by oxidation by I_2.
Polymerization of the complex has not been investigated because the complex is not very stable in organic solvents. Rapid propagation reaction is required to use the complex as a monomer for polycondensation.
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