New Click Chemistry: Polymerization Based on 1,3-Dipolar Cycloaddition of a Homo Ditopic Nitrile N-Oxide and Transformation of the Resulting Polymers into Reactive Polymers
New Click Chemistry: Polymerization Based on 1,3-Dipolar Cycloaddition of a Homo Ditopic Nitrile N-Oxide and Transformation of the Resulting Polymers into Reactive Polymers
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DOI：
10.1021/ma9014577
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发表时间：
2009-09
期刊：
影响因子：
5.5
通讯作者：
Young-Gi Lee;Y. Koyama;Morio Yonekawa;T. Takata
中科院分区：
文献类型：
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作者：
Young-Gi Lee;Y. Koyama;Morio Yonekawa;T. Takata
利用腈N-氧化物作为聚合物合成中的1，3-偶极的新点击化学的适用性和生产率通过二炔与同二位芳族腈N-氧化物的聚合来证明。腈N-氧化物通过相应的异羟氨酰氯与4A分子筛反应原位合成。不同的ditopic二炔和腈N-氧化物的点击聚合有效地以高产率生产聚异恶唑。同二位腈N-氧化物也可用于连接双乙炔封端的聚合物，以非常高的产率得到多嵌段共聚物。所得聚异恶唑与1H和13 C NMR分析得到的结构归属一致。由于异恶唑部分的存在，所产生的聚异恶唑显示出改善的热稳定性。通过异恶唑部分选择性地转化为β-氨基烯酮或β-氨基醇部分，证实了所得聚异恶唑的分子多样性。
Applicability and productivity of new click chemistry that exploits a nitrile N-oxide as a 1,3-dipole in polymer synthesis were demonstrated by the polymerization of diynes with a homo ditopic aromatic nitrile N-oxide. The nitrile N-oxide was synthesized in situ by the reaction of the corresponding hydroxamoyl chloride with molecular sieves 4 A. The click polymerization of various ditopic diynes and the nitrile N-oxide efficiently produced polyisoxazoles in high yields. The homo ditopic nitrile N-oxide was also useful for the connection of bisacetylene-terminated polymers to give multiblock copolymers in very high yield. The resulting polyisoxazoles agree well with the structural assignment obtained by the 1H and 13C NMR analyses. The generated polyisoxazoles showed improved thermal stability due to the presence of isoxazole moieties. The molecular diversity of the obtained polyisoxazoles was confirmed by the selective transformations of the isoxazole moieties into β-aminoenone or β-aminoalcohol moieties ...