Catalyst‐Free Multicomponent Tandem Polymerizations of Aliphatic Amines, Activated Alkyne, and Formaldehyde toward Poly(tetrahydropyrimidine)s

Abstract

Poly(tetrahydropyrimidine)s are promising heterocyclic polymers with unique biocompatibility, antibacterial ability, inherent fluorescence property, and so on, whose development is limited by their synthetic approaches. Multicomponent polymerizations (MCPs) are a group of powerful tools for the facile construction of heterocyclic polymers from simple monomers. Herein, a catalyst-free multicomponent tandem polymerization of aliphatic diamines, activated alkyne, and formaldehyde was developed at 60 °C in methanol in air to construct poly(tetrahydropyrimidine)s with well-defined structures, high molecular weights (M w up to 57700 g mol −1 ), high yields (up to 84%), and satisfactory thermal stability. The MCP was featured with commercially available monomers, high efficiency, catalyst-free economic and mild condition, which was applicable to aliphatic diamines with complicated chemical reactivity, providing a robust and efficient approach for the synthesis of diversified heterocyclic polymers such as poly(tetrahydropyrimidine)s.

One-pot multicomponent polymerization towards heterocyclic polymers: a mini review

“…This research has offered a quick and environmentally friendly method to create PTHPs with adjustable anchoring features this study highlights the advantages of the MCTP, including its catalyst-free nature, use of commercially available monomers, and ability to synthesize PTHPs with varying molecular weights and thermal stability. 100 It is definitely possible to control polymer sequence structures by adjusting the feeding sequence depending on the reaction preference between the thiol/amino and vinyl/alkynyl groups. By controlling the sequence of alkyne and amine, functional polymers can be prepared easily and efficiently.…”

Access to 2,4‐Disubstituted Pyrrole‐Based Polymer with Long‐Wavelength and Stimuli‐Responsive Properties via Copper‐Catalyzed [3+2] Polycycloaddition

“…[23][24][25][26] In particular, isocyanide groups [27][28][29] are rather versatile building blocks that are frequently employed in the construction of heterocyclic structure decorated polymers (Scheme 1b). [30] Recently, Dong, [31,32] Li, [33,34] Tang [35][36][37][38] group and many other groups have made a significant contribution to the extension of polycycloaddition for the discovery of novel macromolecules, bearing different types of heterocycles that are constructed by classical synthetic Scheme 1. Synthetic approach for pyrrole-based polymer.…”