大学有机化学中的重排反应及其归纳教学实践

doi:10.3866/PKU.DXHX202008027

Abstract

Abstract:

Rearrangement reaction is one of the most important contents in the course of college organic chemistry. These reactions can be found in many chapters, and might be easily forgotten by students in the learning process. Thus, it is of great importance to carry out inductive teaching for relevant contents. Herein, we summarize and analyze in depth the rearrangement reactions involved in college organic chemistry. These analyses at the mechanism level are beneficial for understanding and memorizing of the reactions. In addition, the application of inductive analysis of rearrangement reactions in teaching practice through several cases is also introduced. The results show that this teaching method played an important role in promoting the understanding and mastery of relevant knowledge. Similar method can also be applied to the teaching process toward other systematic knowledge.

Key words: College organic chemistry, Rearrangement reaction, Reaction mechanism, Inductive teaching

Ji Zhang. An Induction of Rearrangement Reactions in College Organic Chemistry and Its Application in Teaching Practice[J].University Chemistry, 2021, 36(7): 2008027.

Figures/Tables 12

References 11

1	Clayden J. ; Greeves N. ; Warren S. Organic Chemistry 2nd ed London, UK: Oxford University Press, 2012.
2	邢其毅; 裴伟伟; 徐瑞秋; 裴坚. 基础有机化学(下册), 第4版北京: 北京大学出版社, 2016, 1085- 1119.
3	喻克雄; 曾朝霞. 长江大学学报(自然科学版), 2004, 9 (1), 86. doi: 10.3969/j.issn.1673-1409-C.2004.01.025
4	张霜梅. 天中学刊, 1997, 12 (2), 101.
5	史春越. 化学教育, 2009, (5), 7. doi: 10.3969/j.issn.1003-3807.2009.05.003
6	许家喜. 大学化学, 2006, 21 (3), 28.
7	许家喜. 大学化学, 2013, 28 (5), 34.
8	Hou S. ; Li X. ; Xu J. Org. Biomol. Chem. 2014, 12, 4952.
9	Yang Z. ; Hou S. ; He W. ; Cheng B. ; Jiao P. ; Xu J. Tetrahedron 2016, 72, 2186.
10	李瑛; 张骥. 有机化学基础, 第3版北京: 科学出版社, 2020.
11	沈晓莉; 陈中元; 严剑锋; 尹玲飞. 杭州化工, 2006, 36 (2), 20.

重排反应	章节	重排底物^a	机理	类型^b
Wagner-Meerwein重排	烯烃、卤代烃、醇等	碳正离子	1, 2-重排	缺电子重排
频哪醇重排	醇	碳正离子^{c, d}	1, 2-重排	缺电子重排
Beckmann重排	醛酮	氮正离子^d	1, 2-重排	缺电子重排
Baeyer-Villiger氧化Dakin氧化	醛酮	氧正离子^{c, d}	1, 2-重排	缺电子重排
二苯羟乙酸重排	醛酮	邻二羰基化合物^c	1, 2-重排	缺电子重排
Hofmann及类似重排(Curtius重排Schmidt重排Lossen重排)	羧酸衍生物	酰基氮宾	1, 2-重排	缺电子重排
Demjanov重排	胺	碳正离子^d	1, 2-重排	缺电子重排
Tiffeneau-Demjanov重排重氮甲烷和羰基化合物的反应	胺重氮甲烷	碳正离子^{c, d}	1, 2-重排	缺电子重排
Wolff重排	重氮甲烷	酰基卡宾	1, 2-重排	缺电子重排
Stevens重排	醛酮、胺	α-碳负离子	1, 2-重排	富电子重排
Cope重排Claisen重排	酚醚	1, 5-己二烯衍生物酚烯丙醚	([3,3]-σ迁移	分子内重排
联苯胺重排	胺	联苯胺	[5,5]-σ迁移	分子内重排
Fries重排	酚	酚酯		分子间重排
N-取代苯胺的重排	胺	N上重氮/亚硝基/氯等取代的苯胺		分子间重排

章节	反应类型	碳正离子的产生方式	重排后的碳正离子去向
烯烃	与卤化氢的亲电加成	H⁺对双键的亲电加成	和X⁻结合
芳香烃	傅-克烷化反应	卤代烃C-X键的异裂	对芳环亲电取代
卤代烃	S_N1亲核取代	卤代烃C-X键的异裂	和亲核试剂结合
卤代烃	E1消除	卤代烃C-X键的异裂	消除β-H
醇	消除反应	羟基质子化后离去	消除β-H

学年	相关题总分	实得分平均	得分率
2018–2019	25	18	72%
2019–2020	27	22	81%

[1]	Xiaowa Nie, Wenchao Yang, Xinwen Guo. A Computational Chemistry Experiment on the Reaction Mechanisms of Intra- and Intermolecular Ethanol Dehydration [J]. University Chemistry, 2023, 38(9): 179-187.
[2]	Jing Cheng, Xueping Yang, Jian Jin, Peng Ren. An Experimental Teaching Design for Learning Hammett Equation Using Suzuki Coupling Reaction [J]. University Chemistry, 2023, 38(9): 272-279.
[3]	Yan Zhang, Xiaoyi Wu, Yang Wu, Xiling Gao. Teaching Practice of Rearrangement Reactions Based on Deep Learning Theory [J]. University Chemistry, 2023, 38(8): 22-30.
[4]	Mingan Yang, Jun Li, Minsi Wu, Xiting Zhang. Analysis of Problems 9 and 10 of the Organic Chemistry in the 35th National Chemistry Olympiad Competition (Preliminary) [J]. University Chemistry, 2023, 38(8): 341-350.
[5]	Haonan Peng, Hong Li. Discovery, Reactive Mechanism and Applications of Polydopamine [J]. University Chemistry, 2023, 38(1): 103-110.
[6]	Wangze Song, Wenfeng Jiang. Research Progress in Achmatowicz Rearrangement Reaction [J]. University Chemistry, 2023, 38(1): 111-118.
[7]	Xiaoling Jin, Qiang Liu, Xinping Hui. Mechanisms and Selectivities of Electrophilic Addition Reaction to But-1-en-3-yne Based on Quantum Chemistry Calculation [J]. University Chemistry, 2022, 37(7): 2110047-.
[8]	Lei Zhang, Jianguo Zhou, Yongzhu Zhou. Further Discussion on the Mechanism of Hydroboration of Olefins [J]. University Chemistry, 2021, 36(6): 2008009-.
[9]	Xiyuan Zhang, Yuming Li, Zhiwei Miao. Research Progress in[1, 2]-Phospha-Brook Rearrangement Reaction [J]. University Chemistry, 2021, 36(6): 2008082-.
[10]	Zhiyou Hao, Hui Chen, Yangang Cao, Yanjun Sun, Hongwei Li, Xiaoke Zheng, Weisheng Feng. Molisch's Reaction: Discovery, Mechanism and Application [J]. University Chemistry, 2021, 36(12): 2101022-.
[11]	Yinghao Huo, Shuyong Zhang. On the Condition Optimization for Aromatic Nitration Reaction Based on the Mechanisms and Kinetic Equations [J]. University Chemistry, 2021, 36(12): 2102023-.
[12]	Ruming Yuan, Qiang Fu, Gang Fu. Teaching Reforms and Practices on Research-Oriented Computational Chemistry Experiment [J]. University Chemistry, 2020, 35(9): 141-147.
[13]	Guofang Jiang. Studies on Teaching and Learning of Organic Reaction Mechanism [J]. University Chemistry, 2020, 35(7): 82-87.
[14]	Pingping ZHAO,Kai HU,Ping CAI,Gongzhen CHENG. Recent Developments on Advanced Electrocatalysis for Oxygen Reduction Reaction [J]. University Chemistry, 2019, 34(5): 33-41.
[15]	Yida JIANG,Zhiwei JIANG,Bowen QI,Bingchen ZHONG,Jiang BIAN. Application of Arrow-Pushing Method in the Redox Mechanism of High-Valence Metallic (Cr, Mn, Fe) Oxysalts [J]. University Chemistry, 2018, 33(9): 105-110.

An Induction of Rearrangement Reactions in College Organic Chemistry and Its Application in Teaching Practice

RichHTML

PDF

Like

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 12

References 11

Related Articles 15

Metrics

Recommended 0