{"title":"通过使用改良施密特型反应的探索实验在重排反应中引入区域选择性","authors":"Yi-Chi Chen, Shengquan Zeng, Ke-Qing Xu, Xiao-Yu Ren, Qin-Fang Zhang","doi":"10.1021/acs.jchemed.3c01191","DOIUrl":null,"url":null,"abstract":"Rearrangement reactions, one of the most important transformations in organic chemistry, represent an important yet difficult aspect of the discipline. However, rearrangement reactions that involve regioselectivity are rarely covered in traditional experimental textbooks. Herein, a novel organic chemistry laboratory experiment centered around a Schmidt-type rearrangement was designed and presented, aimed at elucidating the mechanism of this reaction and its regioselective nature for students. Before conducting the experiment, students are tasked with previewing the mechanism underlying the formation of the observed amide product from the reaction between 4-nitrobenzophenone and <i>n</i>-PrNO<sub>2</sub>. Given the asymmetric nature of the ketone, the potential for obtaining different amide products depends on the priority of the migration of the two aryls of 4-nitrobenzophenone during rearrangement. Through this experiment, students can discover that the product arises from the migration of the more electron-rich aryl, thereby indicating a nucleophilic rearrangement with evident regioselectivity. Additionally, the concept of green chemistry was integrated into the organic chemistry curriculum, underscoring the contribution of this improved Schmidt-type reaction in reducing toxicity and enhancing safety. This approach prompts students to recognize the imperative of green chemistry in advancing sustainable societal development, emphasizing the collective responsibility of chemists to shoulder environmentally conscious practices.","PeriodicalId":43,"journal":{"name":"Journal of Chemical Education","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Introducing Regioselectivity in Rearrangement Reactions through a Discovery Experiment Using an Improved Schmidt-Type Reaction\",\"authors\":\"Yi-Chi Chen, Shengquan Zeng, Ke-Qing Xu, Xiao-Yu Ren, Qin-Fang Zhang\",\"doi\":\"10.1021/acs.jchemed.3c01191\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Rearrangement reactions, one of the most important transformations in organic chemistry, represent an important yet difficult aspect of the discipline. However, rearrangement reactions that involve regioselectivity are rarely covered in traditional experimental textbooks. Herein, a novel organic chemistry laboratory experiment centered around a Schmidt-type rearrangement was designed and presented, aimed at elucidating the mechanism of this reaction and its regioselective nature for students. Before conducting the experiment, students are tasked with previewing the mechanism underlying the formation of the observed amide product from the reaction between 4-nitrobenzophenone and <i>n</i>-PrNO<sub>2</sub>. Given the asymmetric nature of the ketone, the potential for obtaining different amide products depends on the priority of the migration of the two aryls of 4-nitrobenzophenone during rearrangement. Through this experiment, students can discover that the product arises from the migration of the more electron-rich aryl, thereby indicating a nucleophilic rearrangement with evident regioselectivity. Additionally, the concept of green chemistry was integrated into the organic chemistry curriculum, underscoring the contribution of this improved Schmidt-type reaction in reducing toxicity and enhancing safety. This approach prompts students to recognize the imperative of green chemistry in advancing sustainable societal development, emphasizing the collective responsibility of chemists to shoulder environmentally conscious practices.\",\"PeriodicalId\":43,\"journal\":{\"name\":\"Journal of Chemical Education\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-07-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Chemical Education\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.jchemed.3c01191\",\"RegionNum\":3,\"RegionCategory\":\"教育学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Education","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.jchemed.3c01191","RegionNum":3,"RegionCategory":"教育学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Introducing Regioselectivity in Rearrangement Reactions through a Discovery Experiment Using an Improved Schmidt-Type Reaction
Rearrangement reactions, one of the most important transformations in organic chemistry, represent an important yet difficult aspect of the discipline. However, rearrangement reactions that involve regioselectivity are rarely covered in traditional experimental textbooks. Herein, a novel organic chemistry laboratory experiment centered around a Schmidt-type rearrangement was designed and presented, aimed at elucidating the mechanism of this reaction and its regioselective nature for students. Before conducting the experiment, students are tasked with previewing the mechanism underlying the formation of the observed amide product from the reaction between 4-nitrobenzophenone and n-PrNO2. Given the asymmetric nature of the ketone, the potential for obtaining different amide products depends on the priority of the migration of the two aryls of 4-nitrobenzophenone during rearrangement. Through this experiment, students can discover that the product arises from the migration of the more electron-rich aryl, thereby indicating a nucleophilic rearrangement with evident regioselectivity. Additionally, the concept of green chemistry was integrated into the organic chemistry curriculum, underscoring the contribution of this improved Schmidt-type reaction in reducing toxicity and enhancing safety. This approach prompts students to recognize the imperative of green chemistry in advancing sustainable societal development, emphasizing the collective responsibility of chemists to shoulder environmentally conscious practices.
期刊介绍:
The Journal of Chemical Education is the official journal of the Division of Chemical Education of the American Chemical Society, co-published with the American Chemical Society Publications Division. Launched in 1924, the Journal of Chemical Education is the world’s premier chemical education journal. The Journal publishes peer-reviewed articles and related information as a resource to those in the field of chemical education and to those institutions that serve them. JCE typically addresses chemical content, activities, laboratory experiments, instructional methods, and pedagogies. The Journal serves as a means of communication among people across the world who are interested in the teaching and learning of chemistry. This includes instructors of chemistry from middle school through graduate school, professional staff who support these teaching activities, as well as some scientists in commerce, industry, and government.