Beckmann重排反应的综合性实验设计与教学应用  

Comprehensive Experimental Design and Teaching Application of Beckmann Rearrangement Reaction

作　　者：周建钟[1] 郭明[1] 陶厚璜 郑泽涛 Jianzhong Zhou;Ming Guo;Houhuang Tao;Zetao Zheng(School of Chemical and Material Engineering,Zhejiang A&F University,Hangzhou 311300,China.)

机构地区：[1]浙江农林大学化学与材料工程学院,杭州311300

出　　处：《大学化学》2024年第1期239-247,共9页University Chemistry

基　　金：2022浙江农林大学教改项目(SZJY21003)。

摘　　要：Beckmann反应是含有羰基的醛、酮与羟胺反应生成有机肟,在催化剂作用下发生重排,在有机合成中具有重要意义。针对实验教学中有机肟Beckmann重排反应的实验原理直观性不足、反应机理佐证性欠缺等问题,通过二苯甲酮与盐酸羟胺反应生成二苯甲酮肟,多聚磷酸催化分子重排反应生成苯甲酰基苯胺为案例,交叉运用无机化学、分析化学、仪器分析的知识和实验技能,测定阶段产物和终产物的熔点、红外光谱、核磁共振谱并表征其结构,将宏观理化性质与微观结构相结合,解析和验证反应机理,达到Beckmann重排反应实验原理直观、反应机理佐证完善的结果,实验的综合设计与交叉创新提升了Beckmann重排实验的教学效果,并激发学生的创新意识。本文既可为肟类Beckmann重排反应的综合性、设计性实验提供借鉴,也可为教材及实验的改进提供有价值的参考。The Beckmann rearrangement,a pivotal reaction wherein carbonyl-rich aldehydes and ketones engage with hydroxylamines to forge organoximes,undergoes a rearrangement in the catalyst's presence and holds significant importance in organic synthesis.Addressing the perceptual gaps in understanding the experimental principles and the insufficient verification of reaction mechanisms during the instruction of Beckmann rearrangement of organoximes,this study utilizes the reaction between benzophenone and hydroxylamine hydrochloride.This reaction results in benzophenone oxime,which undergoes molecular rearrangement catalyzed by polyphosphoric acid to produce benzoyl aniline.This exercise adeptly interweaves elements from inorganic,analytical,and instrumental analysis chemistry,augmenting holistic design and innovative capabilities of students.Employing tools like melting point assessment,infrared spectroscopy,and nuclear magnetic resonance,this study elucidates the nuanced structures of both intermediate and final products.By juxtaposing macroscopic physicochemical attributes with their microscopic counterparts,it robustly deciphers and authenticates the underlying reaction mechanism,enhancing the pedagogical efficacy of the Beckmann rearrangement and kindling innovative sense.This paper can serve as a reference for comprehensive and design-focused experiments on oxime-type Beckmann rearrangements,and also provide valuable insights for the enhancement of teaching materials and experimental procedures.

关 键 词：BECKMANN重排 实验教学 二苯甲酮肟 反应机理 

分 类 号：G64[文化科学—高等教育学] O6[文化科学—教育学]