Salen配合物常温高效催化伯胺氧化偶联合成亚胺反应研究  

Oxidative self-coupling of primary amines to synthesized imines catalyzed by Salen complex under ambient conditions

作　　者：张弈宇 方杨杨 王晓钟[1] 陈英奇[1] 戴立言[1] ZHANG Yi-yu;FANG Yang-yang;WANG Xiao-zhong;CHEN Ying-qi;DAI Li-yan(Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology,College of Chemical and Biological Engineering,Zhejiang University,Hangzhou 310027,China)

机构地区：[1]浙江省化工高效制造技术重点实验室浙江大学化学工程与生物工程学院

出　　处：《高校化学工程学报》2020年第1期110-116,共7页Journal of Chemical Engineering of Chinese Universities

摘　　要：针对伯胺氧化偶联合成亚胺的反应,制备了多种Salen配合物进行催化尝试。实验首先以叔丁基过氧化氢(TBHP)氧化苄胺为探针反应,考察了配合物种类、溶剂、催化剂用量、氧化剂用量等因素对产率的影响。在优化得到较适宜的工艺条件下(10 mg Mn(Salophen)作为催化剂,乙腈为溶剂,0.8当量TBHP为氧化剂),将催化剂用于其他8种不同的胺类底物,探究催化剂对该反应的普适性。结果表明以苄胺为底物时,优化后可得到96.7%的收率。底物拓展中催化剂对底物的电子效应具有很强的耐受性,相对而言,底物的位阻效应对反应的影响更大。催化剂对二级胺的氧化脱氢也有较好的催化效果。最后根据实验结果,提出了可能的反应机理。相较于其他催化剂,该催化剂具有制备简单,反应条件温和等优势。Salen complexes were synthesized and applied as catalysts in the reaction of oxidative self-coupling of primary amines to imines under ambient conditions.Reaction parameters including complex form,solvent,oxidant and catalyst dosages were investigated using benzylamine oxidation by TBHP as the probe reaction.Under the optimal conditions(10 mg Mn(Salophen)as catalyst,acetonitrile as solvent,0.8 eq.TBHP as oxidant),8 different amines were introduced to test the applicability of the catalyst.The results indicate that an excellent yield of 96.7%can be achieved in the oxidative self-coupling of benzylamine.The catalyst has a good tolerance of electronic perturbation of the substrates.The reaction efficiency is relatively more sensitive to the steric hindrance.The catalyst is also suitable for the oxidation of secondary amines.Finally,a plausible mechanism is proposed based on the experimental results.The advantages of this catalyst include simple preparation and mild reaction conditions.

关 键 词：SALEN配合物 伯胺 亚胺 氧化 催化剂 

分 类 号：TQ426.92[化学工程]