CuCl_(2)-N-甲基咪唑催化合成2,4,4,4-四氯丁腈  

Synthesis of 2,4,4,4-tetrachlorobutyronitrile catalyzed by N-methylimidazole-CuCl_(2) complexes

作　　者：肖自胜[1,2] 陈烨 刘健 兰支利 尹笃林[1,2] XIAO Zisheng;CHEN Ye;LIU Jian;LAN Zhili;YIN Dulin(College of Chemistry and Chemical Engineering,Hunan Normal University,Changsha 410081,Hunan,China;National&Local Joint Engineering Laboratory for New Petro-Chemical Materials and Fine Utilization of Resources,Changsha 410081,Hunan,China)

机构地区：[1]湖南师范大学化学化工学院,湖南长沙410081 [2]石化新材料与资源精细利用国家地方联合工程实验室,湖南长沙410081

出　　处：《精细化工》2022年第5期927-932,共6页Fine Chemicals

基　　金：国家自然科学基金(21776068)。

摘　　要：以N-甲基咪唑(N-Mim)与CuCl_(2)·2H_(2)O合成了一系列N-甲基咪唑-CuCl_(2)配合物CuL_(n)Cl_(2)[L为N-甲基咪唑(N-Mim),n=1、2、4]。采用XRD、FTIR及TG对其结构进行了表征。比较了CuL_(n)Cl_(2)催化CCl_(4)与丙烯腈(AN)的原子转移自由基加成(ATRA)反应合成2,4,4,4-四氯丁腈(TBN)的催化性能。考察了反应温度、反应时间、催化剂用量及溶剂的协同催化效应对TBN收率的影响.结果表明,CuL_(2)Cl_(2)的空间配位构建的Cu活性中心呈现最优的催化性能,以乙腈(MeCN)为溶剂,n(CuL_(2)Cl_(2)):n(AN)=1:100,100℃下,反应9 h,TBN的收率可达91.6%,且催化剂可简便回收使用4次而活性无明显降低。基于相关的实验结果,提出了CuL_(2)Cl_(2)催化CCl_(4)和AN的ATRA反应中Cu(Ⅱ)/Cu(Ⅰ)的氧化-还原催化循环机理。A series of N-methylimidazole-CuCl_(2)complexes CuL(n)Cl_(2)(L=N-methylimidazole=N-Mim,n=1,2,4)were synthesized from N-Mim and CuCl_(2)·2H_(2)O and characterized by XRD,FTIR and TG.The catalytic performance of Cu L_(n)Cl_(2)in the synthesis of 2,4,4,4-tetrachlorobutyronitrile(TBN)by atom transfer radical addition(ATRA)reaction of CCl_(4)and acrylonitrile(AN)were compared.The effects of reaction temperature,reaction time,catalyst dosage and synergistic catalytic effect of solvent on the yield of TBN were investigated.The results showed that the Cu active center constructed by the spatial coordination of CuL_(2)Cl_(2)showed the best catalytic performance.Under the conditions of acetonitrile(MeCN)as solvent,n(CuL_(2)Cl_(2))∶n(AN)=1∶100,the yield of TBN could reach 91.6%at 100℃for 9 h.After being reused for 4 times,and the activity of catalyst did not decrease significantly.Based on the relevant experimental results,the oxidation-reduction catalytic cycle mechanism of Cu(Ⅱ)/Cu(Ⅰ)in the ATRA reaction of CCl_(4)and AN catalyzed by CuL_(2)Cl_(2)was proposed.

关 键 词：N-甲基咪唑-CuCl_(2)配合物 CCl_(4)丙烯腈 ATRA反应 氧化-还原催化循环 催化技术 

分 类 号：O643.32[理学—物理化学] TQ226.6[理学—化学]