Novel Topological Polyphenylazomethines Having Controlled Metal-Assembling Properties
Novel Topological Polyphenylazomethines Having Controlled Metal-Assembling Properties
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具有受控金属组装性能的新型拓扑聚苯偶氮甲碱
DOI：
10.1002/chin.200305260
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发表时间：
2002
期刊：
影响因子：
--
通讯作者：
Kimihisa Yamamoto
中科院分区：
文献类型：
--
作者：
M. Higuchi;Kimihisa Yamamoto
以四氯化钛为催化剂，芳香酮和芳香胺为原料，采用收敛法合成了第四代树枝状聚苯基甲亚胺（DPA）。与传统的线型聚苯甲亚胺不同，DPA具有高的热稳定性和高的溶解性。以4-氨基二苯甲酮衍生物为原料，在TiCl 4或对甲苯磺酸（PTS）存在下，一步脱水合成了新型环状苯基甲亚胺三聚体（CPA）。当使用TiCl 4作为脱水剂时，在底物的α-位引入大体积取代基提高了CPA的产率。另一方面，PTS是合成苯基取代CPA的有效催化剂。超支化聚合物合成中的环化反应首先基于空间效应使用具有大体积配体的刘易斯酸来控制。通过控制环化反应，得到了一种具有环状结构的新型树枝状大分子。
Novel dendritic polyphenylazomethines (DPAs) were synthesized up to the fourth generation by the convergent method via dehydration of aromatic ketones with aromatic amines in the presence of titanium (IV) tetrachloride. DPAs show high thermal stability and high solubility unlike the con-ventional linear polyphenylazomethines. Novel cyclic phenylazomethine trimers (CPAs) were syn-thesized in a one-step dehydration of the 4-aminobenzophenone derivatives in the presence of TiCl4 or p-toluenesulfonic acid (PTS). When using TiCl4 as the dehydration agent, the introduction of bulky substituents as the α-position of the substrate enhanced the yields of the CPAs. On the other hand, PTS served as an effective catalyst for the synthesis of the phenyl-substituted CPA. Cyclization in hyperbranched polymer synthesis was first controlled on the basis of a steric effect using a Lewis acid with bulky ligands. A novel dendrimer with a cyclic structure was quantitatively obtained via controlled cyclization using a monomer with a bulky dendron.