苯骈三氮唑改性β-环糊精及水相催化Suzuki偶联反应  

Modification ofβ-cyclodextrin by benzotriazole and catalyzed Suzuki coupling reaction in aqueous phase

作　　者：李瑞 焦彩虹 宋亚坤[1] 刘军辉 郭旭明[1] LI Rui;JIAO Cai-hong;SONG Ya-kun;LIU Jun-hui;GUO Xu-ming(College of Chemistry and Chemical Engineering,Henan University of Science and Technology,Luoyang 471023,China)

机构地区：[1]河南科技大学化学化工学院,河南洛阳471023

出　　处：《化学研究与应用》2023年第6期1356-1363,共8页Chemical Research and Application

基　　金：国家自然科学基金项目(21908043)资助;河南省国际科技合作项目(134500510034)资助。

摘　　要：以生化物质苯骈三氮唑(Ben)和β-环糊精(β-cyclodextrin,β-CD)为原料,通过两步反应合成了单-(6-苯骈三氮唑-6-脱氧)-β-CD(Ben-β-CD)。以Ben-β-CD与醋酸钯(Pd(OAc)2)反应得到了催化剂(Pd@Ben-β-CD)。通过核磁共振氢谱(1 H NMR)和碳谱(13 C NMR)、电喷雾质谱(ESI-MS)、红外光谱(IR)、能谱(EDS)以及X射线光电子能谱(XPS)对Ben-β-CD和Pd@Ben-β-CD的结构进行了表征和分析。研究发现,该催化剂能够高效催化水相Suzuki偶联反应。以对溴甲苯和苯硼酸为底物,K_(3)PO_(4)·7H_(2)O为缚酸剂,四丁基溴化铵(TB-AB)为相转移催化剂,催化剂物质的量分数为0.005 mol%,80℃反应2 h时,对溴甲苯转化率可达93%。在该催化剂作用下,包括氯代芳烃在内的所有底物都获得了中等以上的产率。该催化反应具有催化剂制备简单,催化反应在水相中进行,催化反应时间短,催化剂用量少且催化剂能循环使用5次以上等优点。Mono-(6-benzotriazole-6-deoxy)-β-CD(Ben-β-CD)was synthesized from biochemical regent benzotriazole(Ben)andβ-cyclodextrin(β-CD)by two-step reaction.Ben-β-CD reacted with palladium acetate(Pd(OAc)2)to form a catalyst system(Pd@Ben-β-CD).The structure of Ben-β-CD and the catalyst was analyzed and characterized by 1 H NMR,13 C NMR,ESI-MS,IR,EDS and XPS.It was found that the catalyst could efficiently catalyze the Suzuki coupling reaction in aqueous phase.The reaction uses p-bromotoluene and phenylboronic acid as substrates,K_(3)PO_(4)·7H_(2)O as acid-binding agent,tetrabutylammonium bromide(TBAB)as phase transfer catalyst,and the mass fraction of catalyst was as low as 0.005 mol%when reacting at 80℃for 2h,the conversion of p-bromotoluene was up to 93%.Under the action of the catalyst,all substrates,including chlorinated aromatics,obtained more than medium yields.The catalytic reaction had advantages of simple preparation of catalyst,the catalytic reaction was carried out in aqueous phase,the amount of catalyst was small and catalyst could be recycled above 5 times.

关 键 词：Β-CD 单-(6-苯骈三氮唑-6-脱氧)-β-CD SUZUKI偶联反应 水相催化 

分 类 号：O621.3[理学—有机化学]