由有机碱引发的羰基硫与环氧化物的封闭体系一锅法反应制备聚硫醚。
Poly(thioether)s from Closed-System One-Pot Reaction of Carbonyl Sulfide and Epoxides by Organic Bases.
机构信息
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering , Zhejiang University , Hangzhou 310027 , China.
Department of Chemistry , Zhejiang University , Hangzhou 310027 , China.
出版信息
J Am Chem Soc. 2019 Apr 3;141(13):5490-5496. doi: 10.1021/jacs.9b00544. Epub 2019 Mar 21.
The synthesis of poly(thioether), a highly desired sulfur-containing polymer, is still a key challenge. Herein, we report a simple and facile approach to poly(thioether)s by closed-system one-pot reaction of carbonyl sulfide (COS) and epoxides. This route underwent the coupling reaction of COS with epoxides, followed by decarboxylative ring-opening polymerization (ROP) of the generated mixed cyclic thiocarbonates with releasing of CO and a little bit of COS. Organic base was used as catalyst and initiator in the two steps, respectively. The oxygen/sulfur exchange reaction was driven by successive regioselective elementary reactions and spontaneous releasing of CO (COS), leading to the sulfur atom of COS transferring to poly(thioether)s, which was well demonstrated by DFT studies. This work provides an easy-to-handle, metal-free route to poly(thioether)s bearing diverse structures by using readily available chemicals.
聚（硫醚）的合成是一个极具挑战性的课题，而聚（硫醚）是一种非常理想的含硫聚合物。在此，我们报告了一种通过羰基硫（COS）和环氧化物的封闭体系一锅法反应来制备聚（硫醚）的简单方法。该路线经历了 COS 与环氧化物的偶联反应，随后生成的混合环状硫代碳酸酯发生脱羧开环聚合（ROP），释放出 CO 和少量的 COS。有机碱分别在这两个步骤中充当催化剂和引发剂。氧/硫交换反应是由连续的区域选择性基元反应和 CO（COS）的自发释放驱动的，导致 COS 的硫原子转移到聚（硫醚）上，这通过 DFT 研究得到了很好的证明。这项工作提供了一种易于操作的、无金属的方法，通过使用易得的化学品来制备具有不同结构的聚（硫醚）。
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