H_(2)[SnCl_(6)]配位催化Beckmann重排反应研究  

Study on Beckmann Rearrangement Reaction of Catalyzed by HH_(2)[SnCl_(6)]Corrdination

作　　者：盛含晶 傅敏 洪菁铭 赵国良[1] SHENG Hanjing;FU Min;HONG Jingming;ZHAO Guoliang(Faculty of Science,Xingzhi College,Zhejiang Normal University,Lanxi 321100,Zhejiang,China)

机构地区：[1]浙江师范大学行知学院理学院,浙江兰溪321100

出　　处：《实验室研究与探索》2023年第4期60-64,83,共6页Research and Exploration In Laboratory

基　　金：浙江省教育厅一般课题项目(Y202146836);浙江省高校实验室工作研究立项项目(ZD202106);金华市公益性技术应用研究项目(2022-4-031)。

摘　　要：在反应条件相对温和且绿色环保高效的条件下,用成本低廉、方便易得的六氯合锡(IV)酸H_(2)[SnCl_(6)]作催化剂,实现了由二甲苯酮肟转变为N-苯甲酰替苯胺的Beckmann重排反应。在制备中间体酮肟的过程中,采用了流变相法,该法操作简便、反应时间短、且产率高,避免了强酸的使用;将酮肟转化为酰胺的Beckmann重排反应的过程中,选用了六氯合锡(IV)酸(H_(2)[SnCl_(6)])作为催化剂;同时,进一步探究催化剂使用的工艺条件,结果表明,当以乙腈为溶剂,反应温度78℃,催化剂用量为反应物物质的量的15%时,达到96.5%转化率和97.6%的选择性。在此条件下对另外所选的6种扩展底物进行了实验,结果显示当反应物的苯环上有推电子基团时转化率会提高,反之当有吸电子基团时则转化率则会降低;推测了可能的催化机理。The Beckmann rearrangement of dimethylketoxime to n-benzoylaniline was realized by using stannic hexachloride(IV)acid(H_(2)[SnCl_(6)])as catalyst under relatively mild,green and efficient reaction conditions.First of all,in the process of preparing intermediate ketoxime,rheological phase method is adopted,which is convenient to operate,short reaction time,high yield,and avoids the use of strong acid.Secondly,in the Beckmann rearrangement reaction of ketoxime to amide,hexachlorotin(IV)acid H_(2)[SnCl_(6)]was selected as catalysts.Thirdly,the process conditions of the catalyst were further explored.The results showed that when acetonitrile was used as solvent,reaction temperature was 78℃,and the amount of catalyst was 15%,the conversion rate was as high as 96.5%and the selectivity was 97.6%.The possible catalytic mechanism was deduced,and six other selected extended substrates were experimented under this condition.The results showed that the conversion rate would increase when there were electron pushing groups on the benzene ring of the reactants,while the conversion rate would decrease when there were electron withdrawing groups on the benzene ring of the reactants.

关 键 词：BECKMANN重排 流变相法 配位催化 

分 类 号：TQ453.2[化学工程—农药化工]