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研究简报

六氯丙酮作为C2合成子绿色合成2,2’-联苯并唑类结构及其聚合物

沈晶茹, 王晓刚, 张甲男, 李利红, Jiang Zheng-lin   

  1. 上海工程技术大学化学化工学院 上海 200335
  • 收稿日期:2020-05-22 修回日期:2020-07-23 出版日期:2030-01-01 发布日期:2020-08-19
  • 通讯作者: 李利红 E-mail:msriac@163.com

Green Synthesis of 2,2’-Bibenzazole and its Polymers by Using Hexachloroacetone as C2 Synthon

Shen Jing-ru, Wang Xiao-gang, Zhang Jia-nan, Li Lihong, Jiang Zheng-lin   

  1. College of chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai, 200335
  • Received:2020-05-22 Revised:2020-07-23 Online:2030-01-01 Published:2020-08-19

研究了一种新颖、绿色的六氯丙酮成环反应。首先,以水做溶剂的条件下,对六氯丙酮合成联苯并噻唑的反应条件进行了优化,成功地合成了高纯的联苯并噻唑。研究发现,底物的亲核能力对成环反应起关键作用。进而通过隔氧和氯化银沉淀实验,确定了反应体系中,氧气的参与以及游离氯离子的存在,最后提出了成环反应机理:第一个噻唑环通过邻氨基苯硫醇亲核进攻六氯丙酮,氯仿离去,在氧气的氧化下而首先形成,随后,另一分子的邻氨基苯硫醇再次发起亲核进攻,三个氯离子离去,形成第二个噻唑环。该方法尝试应用于底物2,5-二氨基对苯硫醇和均苯四胺,分别成功地制得聚苯撑二噻唑和聚苯撑二咪唑两个高分子聚合物,实验条件温和、产率高,应用价值高。

关键词: 六氯丙酮, 联苯并噻唑, 联苯并咪唑, 聚苯撑二噻唑, 聚苯撑二咪唑

A novel cyclization reaction by using hexachloroacetone as C2 Synthon has been studied. The optimal condition was obtained by synthesis of bibenzothiazole in the presence hexachloroacetone in water. Experimental results showed that the nucleophilicity of substrates played a key role in the cyclization reaction, and catalytical amount of oxygen in reactions was also vital to trigger ring fusion in the formation of target compounds. Accordingly, mechanism of the cyclization reaction was proposed: The thiazole ring is formed in the first place by a nucleophillic attack of 2-aminobenzenethiol, followed by CCl3cleavage from hexachloroacetone, the second 2-aminobenzenethiol launched anothornucleophilic attack, departure of three chloride ions resulting in the second thiazole ring. The mild method was successfully applied to synthesize two polymers: polyphenylene dithiazole and polyphenylene diimidazole from s 2,5-diaminobenzene-1,4-dithiol and benzene-1,2,4,5-tetraamine respectly, providing a valuable polybenzazole polymer perparing method, in green and mild conditions, with high yield.

Key words: hexachloroacetone, bibenzothiazole, bibenzimidazole, polyphenylene dithiazole, polyphenylene diimidazole