Oligomerizations of o-Diisocyanobenzenes by Organometallic Compounds - Synthesis of Functional Nitrogen-Containing Aromatic Polymers

有机金属化合物低聚邻二异氰苯-功能性含氮芳香族聚合物的合成

基本信息

  • 批准号:
    63850177
  • 负责人:
  • 金额:
    $ 3.46万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Developmental Scientific Research
  • 财政年份:
    1988
  • 资助国家:
    日本
  • 起止时间:
    1988 至 1989
  • 项目状态:
    已结题

项目摘要

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.
异氰化物与有机锌的单金属化考察了多种异氰化物与二烷基锌的反应,发现芳香族异氰化物插入二烷基锌的锌-碳键中,得到[1-(芳基亚氨基)烷基]锌,而脂肪族异氰化物根本不反应。在催化量的过渡金属催化剂(1-2 mol%)存在下,用芳香族碘化物处理[1-(芳基亚氨基)烷基]锌,生成相应的N-芳基芳香族亚胺。 邻二异氰基芳烃与格氏试剂反应合成喹喔啉低聚物 1,2-二异氰基-3.4,5,6-四甲基苯与格氏试剂发生芳构化,得到多种喹喔啉低聚物。喹喔啉骨架是通过将两个邻位异氰基连续插入到碳-镁键中而规则地构建的。这些低聚物通过硅胶上的制备型TLC和/或聚苯乙烯凝胶上的回收HPLC来分离和分离。喹喔啉低聚物的紫外光谱揭示了它们的结构特征;喹喔啉三聚体在 260 和 280 nm 处显示出两个吸收,这可分别归因于单个分离的喹喔啉生色团和缀合的喹喔啉生色团。四聚体和五聚体也在与三聚体相同的位置显示出吸收。这可能表明聚合物链中超过三个连续喹喔啉环的有效共振共轭可能受到空间位阻的抑制。

项目成果

期刊论文数量(22)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Yoshihiko Ito: "Aromatizing Oligomerization of 1,2ーDiisocyanoarene to Quinoxaline Oligomers" J.Chem.Commun.,Chem.Commun.(1990)
Yoshihiko Ito:“1,2-二异氰基芳烃芳香化低聚为喹喔啉低聚物”J.Chem.Commun.、Chem.Commun.(1990)
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Yoshihiko Ito: "Aromatizing Oligomerization of 1,2-Diisocyanoarene to Quinoxaline Oligomers" J.Chem.Soc.,Chem.Commun.(1990)
Yoshihiko Ito:“1,2-二异氰基芳烃芳香化低聚为喹喔啉低聚物”J.Chem.Soc.、Chem.Commun.(1990)
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    0
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Yoshihiko Ito: Synthesis. 714-715 (1988)
伊藤义彦:综合。
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    0
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Masahiro Murakami: "2-(Benzyloxy)-1-(N-2,6-xylylimino)ethylsamarium as a Synthetic Equivalent to α-Hydroxyacetyl Anion" J.Am.Chem.Soc.(1990)
Masahiro Murakami:“2-(苄氧基)-1-(N-2,6-xylylimino)乙基钐作为 α-羟基乙酰基阴离子的合成等价物”J.Am.Chem.Soc.(1990)
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    0
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  • 通讯作者:
M. Murakami, T. Kawano, and Y. Ito: "2-(Benzyloxy)-1-(N-2,6-xylylimino)ethylsamarium as a Synthetic Equivalent to alpha-Hydroxyacetyl Anion" J. Am. Chem. Soc.
M. Murakami、T. Kawano 和 Y. Ito:“2-(苄氧基)-1-(N-2,6-xylylimino)乙基钐作为 α-羟基乙酰基阴离子的合成等价物”J. Am。
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ITO Yoshihiko其他文献

ITO Yoshihiko的其他文献

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{{ truncateString('ITO Yoshihiko', 18)}}的其他基金

Asymmetric Synthesis of Usseful Natural Products by Means of Organosilicon Compounds
利用有机硅化合物不对称合成有用的天然产物
  • 批准号:
    07454164
  • 财政年份:
    1995
  • 资助金额:
    $ 3.46万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Preparation of Optically Active Helical Polymer Materials for Separation of Optically Active Compounds
用于光学活性化合物分离的光学活性螺旋聚合物材料的制备
  • 批准号:
    06555279
  • 财政年份:
    1994
  • 资助金额:
    $ 3.46万
  • 项目类别:
    Grant-in-Aid for Developmental Scientific Research (B)
Study on Synthesis and Properties of Functional Material Poly [Sila (N-Substituted) Imine]
功能材料聚[硅拉(N-取代)亚胺]的合成及性能研究
  • 批准号:
    01430017
  • 财政年份:
    1989
  • 资助金额:
    $ 3.46万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (A)
Synthesis of Biologically Active Natural Products on the Basis of Silafunctional Compounds
基于硅功能化合物的生物活性天然产物的合成
  • 批准号:
    61470093
  • 财政年份:
    1986
  • 资助金额:
    $ 3.46万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (B)
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