SnCl_(2)·2H_(2)O催化芳香酮肟贝克曼重排反应制备芳香胺  

Preparation of Aromatic Amines by Beckmann Rearrangement Reaction of Aromatic Ketoxime Catalyzed by SnCl_(2)·2H_(2)O

作　　者：卢玺盟 侯家宁 王琳[1] 冯玉玲[1] 孙晓兵 孙梦娜 孙京国[1] Lu Ximeng;Hou Jianing;Wang Lin;Feng Yuling;Sun Xiaobing;Sun Mengna;Sun Jingguo(College of Chemistry and Material Science,Chemistry National Experimental Teaching Demonstration Center,Hebei Normal University,Shijiazhuang,Hebei 050024,China)

机构地区：[1]河北师范大学化学与材料科学学院化学国家级实验教学示范中心,河北石家庄050024

出　　处：《化学世界》2023年第4期257-262,共6页Chemical World

基　　金：河北高等教育改革研究与实践(No.2018GJJG106);石家庄市科学技术研究与发展计划(No.199070371A)资助项目。

摘　　要：芳香胺是重要的医药中间体和化工原料,通过贝克曼重排反应合成芳香胺是一种有效途径。经典的贝克曼重排反应采用强酸催化,副反应多,并存在一定的环保问题。研究表明,采用SnCl_(2)·2H_(2)O催化芳香酮肟贝克曼重排反应能够实现芳香酮向芳香胺的高效转化。进一步研究贝克曼重排反应中芳香环上取代基性质、催化剂、溶剂、温度等的影响因素表明,带有给电子基团的苯乙酮肟衍生物有利于该类衍生物迁移基团进行贝克曼重排反应,带吸电子基团的苯乙酮肟衍生物与之相反。对甲氧基苯乙酮在以乙腈为溶剂、SnCl_(2)·2H_(2)O为催化剂、82℃条件下,合成对甲氧基乙酰苯胺收率>92%。产物经1H NMR、13 C NMR、IR等表征。Aromatic amines are important pharmaceutical intermediates and chemical raw materials,and it is an effective way to synthesize aromatic amines through Beckman rearrangement reaction.The classic Beckman rearrangement reaction is catalyzed by strong acid,which is easy to produce side reactions and cause environmental problems.The research shows that the use of SnCl_(2)·2H_(2)O to catalyze Beckmann rearrangement reaction of aromatic ketoxime could achieve efficient conversion of aromatic ketones to aromatic amines.Further studies in the properties of the substituents on the aromatic ring,catalysts,solvents,temperature and other influencing factors in Beckman rearrangement reaction showed that the acetophenone oxime derivatives with electron-donating groups are conducive to the migration of the derivatives of this type,while acetophenone oxime derivatives with electron-withdrawing groups are the opposite.Among them,the yield of p-methoxyacetophenone synthesized with acetonitrile as solvent and SnCl_(2)·2H_(2)O as catalyst at 82℃can exceed 92%and the product was identified by 1H NMR,13 C NMR,IR,etc.

关 键 词：SnCl_(2)·2H_(2)O催化 贝克曼重排 给电子 吸电子 

分 类 号：O625[理学—有机化学]