Ru-Catalyzed Polycondensation of Dialkyl 1,4-Phenylenebis(diazoacetate) with Dianiline: Synthesis of Well-Defined Aromatic Polyamines Bearing an Alkoxycarbonyl Group at the Adjacent Carbon of Each Nitrogen in the Main Chain Framework
Ru-Catalyzed Polycondensation of Dialkyl 1,4-Phenylenebis(diazoacetate) with Dianiline: Synthesis of Well-Defined Aromatic Polyamines Bearing an Alkoxycarbonyl Group at the Adjacent Carbon of Each Nitrogen in the Main Chain Framework
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DOI：
10.1021/acs.macromol.7b01994
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发表时间：
2017-12-12
期刊：
影响因子：
5.5
通讯作者：
Iharee, Eiji
中科院分区：
文献类型：
--
作者：
Shimomoto, Hiroaki;Mukai, Hiroto;Iharee, Eiji
本文首次将过渡金属催化的重氮羰基化合物的N-H插入反应用于缩聚反应，合成了一种新型的芳香族多胺。通过[RuCl2(对伞花烃)](2)催化1，4-二乙基-1，4-苯双重氮乙酸酯与两个苯胺单元之间带有不同连接基的二苯胺反应，得到了定义良好的多胺。在30℃的CH2Cl2中，当金属Ru的摩尔分数为5.0mol%时，缩聚反应生成[NH2或N-2=C]，得到M-n=6400-28300的中高产率产物。位于NH相邻位置的乙氧基羰基赋予多胺溶解性，并且它们的玻璃化转变温度可以在88-173℃的范围内根据连接物的结构而变化。
Transition-metal-catalyzed N-H insertion of a diazocarbonyl compound is applied for polycondensation for the first time to give a new type of aromatic polyamine. The well-defined polyamines were obtained by [RuCl2(p-cymene)](2)-catalyzed reaction of diethyl1,4-phenylenebis(diazoacetate) with dianilines bearing a variety of linkers between two aniline units. The polycondensation proceeded at 30 degrees C in CH2Cl2 with 5.0 mol % of the Ru metal to [NH2 or N-2 = C] to afford the products with M-n = 6400-28 300 in moderate to high yield. Ethoxycarbonyl groups located at an adjacent position to NH imparted solubility to the polyamines, and their glass transition temperatures can be varied depending on the linker structure in a range of 88-173 degrees C.