应用Suzuki偶联反应学习Hammett方程的实验教学设计

doi:10.3866/PKU.DXHX202211040

Abstract

Abstract:

This study introduced an innovative, comprehensive experiment of organic chemistry — "the experimental teaching scheme of learning the Hammett equation by Suzuki coupling reaction". The relationship curve of the Hammett equation was further obtained by exploring the influence of different substituted substrates on the reaction rate of the Suzuki coupling reaction. The results showed that the reaction rate was slowed down by the electron-withdrawing substituents on phenylboronic acid and accelerated by the electron-donating substituents. The influence of the metallization process on the Suzuki coupling reaction was also explored. In the process of literature research, experimental design, experimental operation, result analysis and report writing, students can learn the basic principle of Suzuki coupling reaction and understand the significance of the Hammett equation. The comprehensive experimental project is helpful to stimulate students' interest in scientific research of organic chemistry and improve their comprehensive quality.

Key words: Suzuki coupling reaction, Hammett equation, Reaction mechanism, Innovative experiment

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.

Figures/Tables 7

References 17

1	Miyaura N. ; Suzuki A. Chem. Rev. 1995, 95, 2457. doi: 10.1021/cr00039a007
2	Kurti L. ; Czako B. Strategic Applications of Named Reactions in Organic Synthesis Beijing: Science Press, 2008, 448- 449.
3	黄培强. 有机人名反应、试剂与规则, 第2版北京: 化学工业出版社, 2019, 148- 152.
4	Murphy S. K. ; Bruch A. ; Dong V. M. Chem. Sci. 2015, 6, 174. doi: 10.1039/C4SC02026J
5	Shi S. Y. ; Zhang Y. H. Green Chem. 2008, 10, 868. doi: 10.1039/b803917h
6	Tao L. M. ; Xie Y. X. ; Deng C. L. ; Li J. H. Chin. J. Chem. 2009, 27, 1365. doi: 10.1002/cjoc.200990228
7	Li X. M. ; Zhang H. ; Feng F. F. ; Hu Q. H. ; Yuan Z. L. Chem. Select. 2018, 3, 12287.
8	Keenan S. K. ; Peterson K. P. ; Peterson K. ; Jacobson K. J. Chem. Educ. 2008, 85, 558. doi: 10.1021/ed085p558
9	Ziegler B. E. J. Chem. Educ. 2013, 90, 665. doi: 10.1021/ed300549z
10	Yau H. M. ; Haines R. S. ; Harper J. B. J. Chem. Educ. 2015, 92, 538. doi: 10.1021/ed400701m
11	Hoogenboom R. ; Meier M. R. ; Schubert U. S. J. Chem. Educ. 2005, 82, 1693. doi: 10.1021/ed082p1693
12	周少林; 徐利文; 夏春谷; 李经纬; 李福伟. 有机化学, 2004, 24 (12), 1501. doi: 10.3321/j.issn:0253-2786.2004.12.002
13	Hartwig, J. F. Organotransition Metal Chemistry from Bonding to Catalysis; University Science Books: New York, NY, USA, 2009; pp. 890–898.
14	魏荣宝. 高等有机化学, 第4版北京: 高等教育出版社, 2021, 65- 70.
15	朱志昂; 阮文娟. 物理化学, 第5版北京: 科学出版社, 2014, 230- 250.
16	Hansch C. ; Leo A. ; Taft R. W. Chem. Rev. 1991, 91, 165. doi: 10.1021/cr00002a004
17	肖朵朵; 李翠妍; 熊敏东; 叶华清; 曾志威; 周建敏. 化学教育, 2022, 43 (6), 83.

反应编号	R₁	R₂	反应体系
1	―CH₃ (甲基)	―H (氢原子)	该反应体系中加入的苯硼酸量为1.2 mmol，对溴甲苯为1.0 mmol，催化剂Pd(PPh₃)₄量为0.005 mmol，TEAH为1 mL，THF为4.5 mL
2	―F (氟原子)	―H (氢原子)	该反应体系中加入的苯硼酸量为1.2 mmol，1-溴-4-氟苯为1.0 mmol，催化剂Pd(PPh₃)₄，TEAH和THF量跟反应1一致
3	―OMe (甲氧基)	―H (氢原子)	该反应体系中加入的苯硼酸量为1.2 mmol，4-溴苯甲醚为1.0 mmol，催化剂Pd(PPh₃)₄，TEAH和THF量跟反应1一致
4	―NO₂ (硝基)	―H (氢原子)	该反应体系中加入的苯硼酸量为1.2 mmol，1-溴4-硝基苯为1.0 mmol，催化剂Pd(PPh₃)₄，TEAH和THF量跟反应1一致
5	―CH₃ (甲基)	―NO₂ (硝基)	该反应体系中加入的4-硝基苯硼酸量为1.2 mmol，对溴甲苯为1.0 mmol，催化剂Pd(PPh₃)₄，TEAH和THF量跟反应1一致
6	―CH₃ (甲基)	―OMe (甲氧基)	该反应体系中加入的4-甲氧基苯硼酸量为1.2 mmol，对溴甲苯为1.0 mmol，催化剂Pd(PPh₃)₄，TEAH和THF量跟反应1一致
7	―CH₃ (甲基)	―Br (溴原子)	该反应体系中加入的4-溴苯硼酸量为1.2 mmol，对溴甲苯为1.0 mmol，催化剂Pd(PPh₃)₄，TEAH和THF量跟反应1一致
8	―CH₃ (甲基)	―F (氟原子)	该反应体系中加入的4-氟苯硼酸量为1.2 mmol，对溴甲苯为1.0 mmol，催化剂Pd(PPh₃)₄，TEAH和THF量跟反应1一致
9	―CH₃ (甲基)	―CF₃ (三氟甲基)	该反应体系中加入的4-三氟甲基苯硼酸量为1.2 mmol，对溴甲苯为1.0 mmol，催化剂Pd(PPh₃)₄，TEAH和THF量跟反应1一致
10	―CH₃ (甲基)	―CH₃ (甲基)	该反应体系中加入的4-甲基苯硼酸量为1.2 mmol，对溴甲苯为1.0 mmol，催化剂Pd(PPh₃)₄，TEAH和THF量跟反应1一致
11	―CH₃ (甲基)	―CH₂CH₃ (乙基)	该反应体系中加入的4-乙基苯硼酸量为1.2 mmol，对溴甲苯为1.0 mmol，催化剂Pd(PPh₃)₄，TEAH和THF量跟反应1一致

反应编号	反应速率常数k/(mol∙L⁻¹∙s⁻¹)	反应编号	反应速率常数k/(mol∙L⁻¹∙s⁻¹)
1	1.3 × 10⁻³	8	1.1 × 10⁻³
5	2.2 × 10⁻⁴	9	3.6 × 10⁻⁴
6	2.6 × 10⁻³	10	2.3 × 10⁻³
7	5.8 × 10⁻⁴	11	2.0 × 10⁻³

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An Experimental Teaching Design for Learning Hammett Equation Using Suzuki Coupling Reaction

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