Three-Component Polycondensation of Bis(diazoketone) with Dicarboxylic Acids and Cyclic Ethers: Synthesis of New Types of Poly(ester ether ketone)s

详细信息    查看全文

• 作者：Eiji Ihara ; Yuji Hara ; Tomomichi Itoh ; Kenzo Inoue
• 刊名：Macromolecules
• 出版年：2011
• 出版时间：August 9, 2011
• 年：2011
• 卷：44
• 期：15
• 页码：5955-5960
• 全文大小：884K
• 年卷期：v.44,no.15(August 9, 2011)
• ISSN：1520-5835

文摘

New types of poly(ester ether ketone)s 3 and 8 were prepared by three-component polycondensation of bis(diazoketone) 1 with a variety of dicarboxylic acids 2 and THF or THP catalyzed by Rh₂(OAc)₄. THF was ring-opened and incorporated into almost every carboxyl O鈥揌 of 2 via simultaneous insertion together with a diazocarbonyl-derived carbene, resulting in the formation of a unique poly(ester ether ketone) framework. On the other hand, when THP was used as a cyclic ether, insertion of carbene alone into the carboxyl O鈥揌 (normal insertion) competes with the simultaneous insertion of THP and carbene, and the ratio of the two modes of insertion depends on the kind of 2 employed. The mode and selectivity of the propagation were confirmed by conducting Rh-catalyzed model reactions of diazoacetophenone 4 with 4-tert-butylbenzoic acid 5 in THF and THP.