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Pd/C催化Suzuki反应合成2,3’,5’-三氯联苯

Pd/C-catalyzed Synthesis of 2,3’,5’-TrichloroBiphenyl via Suzuki-Miyaura Coupling Reaction

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【作者】 李雨欣贾瑶邹莉朱学茹刘思雨罗通黄飞薛智

【Author】 Li Yuxin;Jia Yao;Zou Li;Zhu Xueru;Liu Siyu;Luo Tong;Huang Fei;Xue Zhi;Department of International Applied Technology, Yibin University;Yibin Collaborative Workstation of Nobel Laureate Team Member, Yibin University;College of Resources & Environment, Aba Teachers University;

【通讯作者】 黄飞;薛智;

【机构】 宜宾学院国际应用技术学部宜宾学院诺贝尔获奖专家联合工作站阿坝师范学院资源与环境学院

【摘要】 本文通过无配体Pd/C催化Suzuki-Miyaura偶联反应,以2-氯溴苯和3,5-二氯苯硼酸为原料,以碳酸钾作为碱,研究了不同反应温度对2,3’,5’-三氯联苯合成的影响。作为对比,本文平行进行了Pd(PPh3)4催化合成目标产物的实验,涉及Pd(PPh3)4催化的反应要求惰性气体反应氛围,且需在80℃下反应12小时。GC-MS跟踪监测显示:Pd/C催化的反应室温下反应12小时,几无产物生成。反应温度升至50℃时,反应2小时得到较多产物。50℃时,增加3,5-二氯苯硼酸至2倍当量,最终产率达到90%。有关催化剂回收方面,Pd(PPh3)4对空气敏感,反应结束后,未能回收,而无配体的Pd/C催化剂可循环使用5次以上而几无活性损失。与传统的含配体的Pd催化剂比较,无配体Pd/C催化在经济、环保以及实验操作方面表现出巨大的优势。

【Abstract】 Synthesis of 2,3’,5’-trichlorobiphenyl via Pd/C-catalyzed Suzuki-Miyaura coupling reaction was studied, using 2-chlorobromobenzene and 3,5-dichlorobenzeneboronic acid as raw materials and potassium carbonate as base. The reaction temperature played an important role in the process. As a comparison, experiments on the synthesis of target products catalyzed by Pd(PPh3)4 were carried out in parallel in this paper. The reactions involving Pd(PPh3)4catalysis require an inert gas reaction atmosphere, and the reaction needs to be carried out at 80 ℃ for 12 hours. GC-MS tracking monitoring showed that the Pd/C-catalyzed reaction was reacted at room temperature for 12 hours, and nearly no product was produced. When the reaction temperature was raised to 50 ℃, a large amount of products were obtained in the reaction for two hours. At 50 ℃, 3,5-dichlorophenylboronic acid was increased to 2 equivalent(with 2-chlorobromobenzene), and the final yield reached 90 %. As for the recyclability of Pd catalyst, Pd(PPh3)4 was sensitive to air and no record of its recyclability was reported, while the recycled Pd/C can be reused for 5 times only with a slightly prolonged reaction time. The successful application of Pd/C as Suzuki coupling catalyst showed a great advantage in the area of economy, environment and easy manipulation.

【基金】 四川省科技计划项目(2020JDRC0064);宜宾学院省级大学生创新创业训练计划项目基金(S201910641058,S201910641084)
  • 【文献出处】 广东化工 ,Guangdong Chemical Industry , 编辑部邮箱 ,2023年05期
  • 【分类号】O625.21
  • 【下载频次】40
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