共轭体系的分类及结构特征

doi:10.3866/PKU.DXHX202007029

摘要/Abstract

摘要：

共轭体系是相邻原子或基团的电子轨道发生重叠，电子发生离域运动、体系能量降低、键长平均化的结构单元，具有独特的电子效应——共轭效应。共轭效应是有机化学课程的重点和难点内容，掌握共轭体系的分类及结构特征，对理解化合物的共轭效应以及物理化学性质具有重要作用。但一般的有机化学教材及文献对此没有系统的介绍。本文通过实例、价键（valence bond，VB）理论以及分子轨道（molecular orbital，MO）理论中的电子轨道示意图，阐明广义和狭义共轭体系的内涵，以及狭义共轭体系、超共轭体系、价键共轭与空间共轭的分类和结构特征。

关键词: 广义共轭体系, 狭义共轭体系, 超共轭, 价键共轭, 空间共轭

Abstract:

Conjugated system, the moiety that the electronic orbitals of adjacent atoms or groups overlap, the electrons delocalize and the bond lengths become average, has special electronic effects, i.e., the conjugate effect that is crucial and difficult in organic chemistry course. It is very important to master the classification and structural characteristics of conjugated systems for understanding the conjugate effect, as well as physical and chemical properties of compounds. However, these have not been systematically discussed in general organic chemistry textbooks and literature. Here, the broad and narrow sense of conjugated systems, the classification and structural characteristics of narrow-sense conjugated system, hyper-conjugated system, through-bond and through-space conjugations were illustrated through the molecular structures of examples and the electronic orbital figures of valence bond and molecular orbital theories.

Key words: Broad-sense conjugation, Narrow-sense conjugation, Hyper-conjugation, Through-bond conjugation, Through-space conjugation

朱秋华. 共轭体系的分类及结构特征[J]. 大学化学, 2021, 36(6): 2007029.

Qiuhua Zhu. Classification and Structural Characteristics of Conjugated System[J]. University Chemistry, 2021, 36(6): 2007029.

链接本文: https://www.dxhx.pku.edu.cn/CN/10.3866/PKU.DXHX202007029

https://www.dxhx.pku.edu.cn/CN/Y2021/V36/I6/2007029

图/表 14

图1

图2

表1

图3

图4

图5

图6

图7

图8

图9

图10

图11

图12

图13

参考文献 38

1	Zhen S. ; Mao J.-C. ; Chen L. ; Ding S. ; Luo W. ; Zhou X.-S. ; Qin A. ; Zhao Z. ; Tang B. Nano Lett. 2018, 18, 4200. doi: 10.1021/acs.nanolett.8b01082
2	Shen P. ; Huang M. ; Qian J. ; Li J. ; Ding S. ; Zhou X. S. ; Xu B. ; Zhao Z. ; Tang B. Z. Angew. Chem. Int. Ed. 2020, 132, 4581.
3	Xiao K. ; Zhao Y. ; Zhu J. ; Zhao L. Nat. Commun. 2019, 10, 5639. doi: 10.1038/s41467-019-13663-8
4	Levandowski B. ; Raines R. ; Houk K. J. Org. Chem. 2019, 184, 6432.
5	Alabugin I. V. ; dos Passos Gomes G. ; Abdo M. A. WIRES Comput. Mol. Sci. 2019, 9, e1389.
6	Mulliken R. S. J. Chem. Phys. 1939, 7, 339. doi: 10.1063/1.1750446
7	Mulliken R. S. ; Rieke C. A. ; Brown W. G. J. Am. Chem. Soc. 1941, 63, 41. doi: 10.1021/ja01846a008
8	何福城; 朱正和. 结构化学, 北京: 高等教育出版社, 1987, 151
9	邢其毅, 徐瑞秋, 周政, 裴伟伟. 基础有机化学(上). 第2版. 北京: 高等教育出版社, 2005: 44; 55; 129; 236.
10	Zhu Q. ; Jiang H. ; Li J. ; Zhang M. ; Wang X. ; Qi C. Tetrahedron 2009, 65, 4604. doi: 10.1016/j.tet.2009.03.071
11	Gong Z..-L. ; Zhong Y. -W. ; Yao J. Chem. Eur. J. 2015, 21, 1554. doi: 10.1002/chem.201405332
12	Zhu Q. ; Huang L. ; Chen Z. ; Zheng S. ; Lv L. ; Zhu Z. ; Cao D. ; Jiang H. ; Liu S. Chem. Eur. J. 2013, 19, 1268. doi: 10.1002/chem.201203012
13	朱秋华, 刘淑文. 聚集诱导发光的五取代四氢嘧啶及其制备方法和应用: 中国, CN201110129857B[P]. 2011-05-19. 美国, 8906927 B2[P].
14	Zhu Q. ; Zhang Y. ; Nie H. ; Zhao Z. ; Liu S. ; Wong K. S. ; Tang B. Z. Chem. Sci. 2015, 6, 4690. doi: 10.1039/C5SC01226K
15	Zhang H. ; Zheng X. ; Xie N. ; He Z. ; Liu J. ; Leung N. ; Niu Y. ; Huang X. ; Wong K. S. ; Kwok R. T. K. J. Am. Chem. Soc. 2017, 139, 16264. doi: 10.1021/jacs.7b08592
16	Levitus M. ; Schmieder K. ; Ricks H. ; Shimizu K. D. ; Bunz U. H. F. ; Garcia-Garibay M. A. J. Am. Chem. Soc. 2001, 123, 4259. doi: 10.1021/ja003959v
17	Luo J. ; Xie Z. ; Lam J. W. ; Cheng L. ; Chen H. ; Qiu C. ; Kwok H. S. ; Zhan X. ; Liu Y. ; Zhu D. ; Tang B. Z. Chem. Commun. 2001, 18, 1740.
18	Zheng S. ; Huang C. ; Zhao X. ; Zhang Y. ; Liu S. ; Zhu Q. Spectrochim. Acta. A 2018, 189, 231. doi: 10.1016/j.saa.2017.08.016
19	Liu Y. ; Ye Z. ; Zhao M. ; Chen Q. ; Wang Y. ; Zhu Q. Dyes Pigments 2017, 145, 391. doi: 10.1016/j.dyepig.2017.06.001
20	Zhu Q. ; Huang L. ; Su J. ; Liu S. Chem. Commun. 2014, 50, 1107. doi: 10.1039/C3CC45244A
21	Wu S. ; Liang F. ; Hu D. ; Li H. ; Yang W. ; Zhu Q. Anal. Chem. 2020, 92, 4259. doi: 10.1021/acs.analchem.9b04638
22	Zhu Q. ; Yang W. ; Zheng S. ; Sung H. H. Y. ; Williams I. D. ; Liu S. ; Tang B. Z. J. Mater. Chem. C 2016, 4, 7383. doi: 10.1039/C6TC01887D
23	Holtz D. Chem. Rev. 1971, 71, 139. doi: 10.1021/cr60269a007
24	Weinhold F. Nature 2001, 411, 539. doi: 10.1038/35079225
25	Alabugin I. V. ; Manoharan M. J. Org. Chem. 2004, 69, 9011. doi: 10.1021/jo048287w
26	Alabugin I. V. ; Zeidan T. A. J. Am. Chem. Soc. 2002, 124, 3175. doi: 10.1021/ja012633z
27	Deslongchamps P. Pure Appl. Chem. 1993, 65, 1161. doi: 10.1351/pac199365061161
28	Edward J. T. Chem. Ind. (London) 1955, 36, 1102.
29	Lambert J. B. ; Wang G. T. ; Finzel R. B. ; Teramura D. H. J. Am. Chem. Soc. 1987, 109, 7838. doi: 10.1021/ja00259a036
30	张生勇; 何炜. 有机化学, 第4版北京: 科学出版社, 2015, 31
31	Pophristic V. ; Goodman L. Nature 2001, 411, 565. doi: 10.1038/35079036
32	洪鹄; 黄兆和; 柴正祺; 张沅珒. 大学化学, 2017, 32, 84.
33	Goodman L. ; Gu H. ; Pophristic V. J. Phys. Chem. A 2005, 109, 1223. doi: 10.1021/jp046290d
34	Gooseman N. E. J. ; O'Hagan D. ; Peach M. J. G. ; Slawin A. M. Z. ; Tozer D. J. ; Young R. J. Angew. Chem. Int. Ed. 2007, 46, 5904. doi: 10.1002/anie.200700714
35	Yamamoto T. ; Kaneno D. ; Tomoda S. Bull. Chem. Soc. Jpn. 2009, 81, 1415.
36	Wu J. I.-C. ; von RaguSchleyer P. Pure Appl. Chem. 2013, 85, 921. doi: 10.1351/PAC-CON-13-01-03
37	Lambert J. ; Ciro S. J. Org. Chem. 1996, 61, 1940. doi: 10.1021/jo951643d
38	Reed A. E. ; Curtiss L. A. ; Weinhold F. Chem. Rev. 1988, 88, 899. doi: 10.1021/cr00088a005

VB				MO
成键电子轨道	成/非键电子轨道			电子受体轨道	电子供体轨道
成键电子轨道	π	n	σ	电子受体轨道	π	n	σ
π	π-π	n-π		π*	π-π*	n-π*	σ-π*
σ	σ-π	σ-n	σ-σ	p	π-p	n-p	σ-p
				σ*	π-σ*	n-σ*	σ-σ*

[1]	吕萍, 王彦广. 超共轭效应对有机化合物结构和反应性的影响[J]. 大学化学, 2020, 35(7): 151 -165 .
[2]	洪鹄,黄兆和,柴正祺,张沅珒. 超共轭与立体电子效应[J]. 大学化学, 2017, 32(1): 84 -105 .