| Project/Area Number |
63850177
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| Research Category |
Grant-in-Aid for Developmental Scientific Research
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Kyoto University |
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Principal Investigator |
ITO Yoshihiko Kyoto University, Synthetic Chemistry, Professor, 工学部, 教授 (40026018)
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| Co-Investigator(Kenkyū-buntansha) |
KAWAMURA Norio Sumitomo Chemical Industry, Researcher, 大阪研究所, 研究員
MURAKAMI Masahiro Kyoto University, Synthetic Chemistry, Assistant Professor, 工学部, 助手 (20174279)
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| Project Period (FY) |
1988 – 1989
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| Project Status |
Completed (Fiscal Year 1989)
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| Budget Amount *help |
¥5,400,000 (Direct Cost: ¥5,400,000)
Fiscal Year 1989: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1988: ¥4,300,000 (Direct Cost: ¥4,300,000)
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| Keywords | Aromatic Isocyanide / ortho-Diisocyanoarenes / Quinoxaline Oligomers / Functional Polymers / オルトージイソシアノアレ-ン / οージイソシアノベンゼンの合成 / οージイソシアノベンゼンの重合 / キノキサリン骨格の合成 / キノキサリン・オリゴマー |
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| Research Abstract |
Mono-metallation of an Isocyanide with an Organozinc The reaction of a variety of isocyanides with dialkylzinc was examined and it was found that aromatic isocyanides underwent insertion into zinc-carbon bond of dialkylzinc to give [1- (arylimino)alkyl]zinc, whereas aliphatic isocyanides did not react at all. Treatment of [1- (arylimino)alkl]zinc with aromatic iodide in the presence of a catalytic amount of transition metal catalyst (1-2 mol%) produced the corresponding N-aryl aromatic imine.
Synthesis of Quinoxaline Oligomers by Reaction of o-Diisocyanoarene with Grignard Reagent The reaction of 1,2-diisocyano-3.4,5,6-tetramethylbenzene with Grignard reagents resulted in aromatization to give a variety of quinoxaline oligomers. The quinoxaline skeleton was regularly constructed by successive insertion of the two ortho isocyano groups into carbon- magnesium linkage. These oligomers are separated and isolated by preparative TLC on silica gel and/or recycling HPLC on polystyrene gel. UV spectra of the quinoxaline oligomers revealed their structural feature; quinoxaline trimer showed two absorptions at 260 and 280 nm, which can be ascribed to single isolated quinoxaline chromophore and conjugated quinoxaline chromophore, respectively. Tetramer and pentamer also showed the absorption at the same positions as trimer. This may indicate that an effective resonance conjugation over more than three sequential quinoxaline rings in the polymer chain may be inhibited by steric hindrance.
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