对位-二取代氮苄叉苯胺还原电位的取代基效应

doi:10.6023/cjoc201411037

有机化学 ›› 2015, Vol. 35 ›› Issue (6): 1302-1309.DOI: 10.6023/cjoc201411037 上一篇下一篇

研究论文

对位-二取代氮苄叉苯胺还原电位的取代基效应

曹晨忠, 毕亚坤, 曹朝暾

湖南科技大学化学化工学院理论有机化学与功能分子教育部重点实验室分子构效关系湖南省普通高校重点实验室湘潭 411201

收稿日期:2014-11-25 修回日期:2014-12-16 发布日期:2015-02-02
通讯作者: 曹晨忠 E-mail:czcao@hnust.edu.cn
基金资助:
国家自然科学基金(No. 21272063)、湖南省教育厅科研(No. 14C0466)及湖南省自然科学基金(No. 14JJ3112)资助项目.

Effect of Substituents on Reduction Potential of Para-disubstituted N-Benzylidenebenzenamine Derivatives

Cao Chenzhong, Bi Yakun, Cao Chaotun

Key Laboratory of Theoretical Organic Chemistry and Function Molecule, Ministry of Education, Hunan Provincial University Key Laboratory of QSAR/QSPR, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201

Received:2014-11-25 Revised:2014-12-16 Published:2015-02-02
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21272063), the Scientific Research Fund of Hunan Provincial Education Department (No. 14C0466), and the Natural Science Foundation of Hunan Province (No. 14JJ3112).

文章分享

1. 对位-二取代氮苄叉苯胺还原电位的取代基效应.PDF(528KB)

摘要/Abstract

合成52种4,4'-二取代氮苄叉苯胺衍生物p-XPhCH=NC₆H₄Y-p作为模型化合物, 系统地研究了取代基效应对其还原电位E_Red的影响规律. 通过研究表明该类化合物的E_Red与桥连键C=N的¹³C NMR化学位移δ_C (C=N)没有线性关系, E_Red和δ_C(C=N)两者的影响因素有较大差别, 仅用Hammett取代基常数不能很好地表达E_Red的变化规律. 影响E_Red的主要因素有: 取代基X的场/诱导效应、取代基X和Y的共轭效应, 此外取代基X的激发态取代基参数也有重要影响. 上述4个参数与52种化合物的E_Red有良好的相关性, 相关系数为0.9756, 标准偏差为0.052 V. 在这4个影响因素中, 基团X的场/诱导效应、共轭效应和激发态取代基效应对E_Red改变的贡献都比较大, 而基团Y的共轭效应对还原电位E_Red改变的贡献相对较小, 但不能忽略它.

关键词: 取代氮苄叉苯胺, 还原电位, 取代基效应, 激发态取代基参数, 化学位移

52 samples of 4,4'-disubstituted N-benzylidenebenzenamine (p-XPhCH=NC₆H₄Y-p) derivatives were synthesized, the effect of substituents on the reduction potential E_Red of these compounds was systematically investigated. The result shows that there is not linear relation between their E_Red and the chemical shift δ_C(C=N) of the ¹³C NMR of C=N bridge bond in the molecules. The factors affecting E_Red are obvious different from that affecting on δ_C(C=N), and the change regularity of E_Red can not be expressed well by only employing Hammett substituent constant. The main factors affecting the E_Red are the field/inductive effect of substituent X, the conjugative effects of substituents X and Y, and the excited-state substituent constant of substituent X plays an important role of influence on E_Red. Above four parameters have good correlations with the E_Red of the 52 samples of compounds, the correlation coefficient of the correlation equation is 0.9756, and the standard derivation is 0.052 V. Among the four factors, the contributions of the field/inductive effect, the conjugative effect and the excited-state substituent constant of group X to the changes of E_Red are relative large, while the contribution of the conjugative effect of group Y is relative small, and can not be ignored.

Key words: substituented N-benzylidenebenzenamine, reduction potential, substituent effect, excited-state substituent parameter, chemical shift

引用此文

曹晨忠, 毕亚坤, 曹朝暾. 对位-二取代氮苄叉苯胺还原电位的取代基效应[J]. 有机化学, 2015, 35(6): 1302-1309.

Cao Chenzhong, Bi Yakun, Cao Chaotun. Effect of Substituents on Reduction Potential of Para-disubstituted N-Benzylidenebenzenamine Derivatives[J]. Chin. J. Org. Chem., 2015, 35(6): 1302-1309.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Fang, Z.-J.; Cao, C.-Z.; Wu, W. H.; Wang, L. J. Phys. Org. Chem. 2013, 26, 249.
[2] Cao, C.-Z.; Chen, G.-F.; Yin, Z.-Q. J. Phys. Org. Chem. 2008, 21, 808.
[3] Cao, C.-Z.; Lu, B.-T.; Chen, G.-F. J. Phys. Org. Chem. 2011, 24, 335.
[4] Chen, G.-F.; Cao, C.-Z.; Lu, B.-T.; Sheng, B. J. Phys. Org. Chem. 2012, 25, 327.
[5] Paspalaev, E.; Pavlova, A.; Acad, C. R. Acad. Bulg. Sci. 1965, 18, 533.
[6] Dmitrieva, V. N.; Kononenko, L. V.; Bezuglyi, V. D. Teor. Eksp. Khim. 1965, 1, 456.
[7] Scott, J. M. V.; Jura, W. H. Can. J. Chem. 1967, 45, 2375.
[8] Bezuglyi, V. D.; Kononenko, L. V.; Forunova, A. F.; Dmitrieva, V. N.; Timan, B. L. Zh. Obshch. Khim. 1969, 39, 1680.
[9] Dmitrieva, V. N.; Rozanel’skaya, N. A.; Krasovitskii, B. M.; Stepanov, B. I.; Bezuglyi, V. D. Zh. Obshch. Khim. 1971, 41, 60.
[10] Zhu, X.-Q.; Liu, Q.-Y.; Chen, Q.; Lian. R.-M. J. Org. Chem. 2010, 75, 789.
[11] Sauro, V. A.; Workentin, M. S. J. Org. Chem. 2001, 66, 831.
[12] Celik, H.; Ekmekci, G.; Ludvik, J.; Picha, J.; Zuman, P. J. Phys. Chem. B 2006, 110, 6785.
[13] Ucar, M.; Polat, K.; Aksu, M. L.; Unver, H. Anal. Sci. 2004, 20, 1179.
[14] Hammett, L. P. J. Am. Chem. Soc. 1937, 59, 96.
[15] Hamer, G. K.; Peat, I. R.; Reynol, W. F. Can. J. Chem. 1973, 51, 897.
[16] Inamoto, N.; Masuda, S. Can. J. Chem. 1967, 45, 1185.
[17] Charton, M. Can. J. Chem. 1970, 48, 1748.
[18] Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.
[19] Neuvonen, H.; Neuvonen, K.; F. Fülöp. J. Org. Chem. 2006, 71, 3141～3148.
[20] Shen, T.; Yuan, Z.-L.; Xu, H.-J. Acta Chim. Sinica 1985, 43, 865 (in Chinese). (沈涛, 袁振利, 许慧君, 化学学报, 1985, 43, 865.)
[21] Needham, D. E.; Wei, I. C.; Seybold, P. G. J. Am. Chem. Soc. 1988, 110, 4186.
[22] Liu, F.-P.; Liang, Y.-Z.; Cao, C.-Z. Talanta 2007, 72, 1307.
[23] Banks, R. E.; DuBoisson, R. A.; Pritchard, R. G.; Tipping, A. E. Acta Crystallogr., Sect. C 1995, 51, 1470.
[24] Herrera, R.; Nagarajan, A.; Morales, M. A.; Mendez, F.; Jimenez-Vazquez, H. A.; Zepeda, L.G.; Tamariz , J. J. Org. Chem. 2001, 66, 1252.
[25] Vijayalakshmi, L.; Parthasarathi, V.; Manishanker, P. Acta Crystallogr., Sect. C 1997, 53, 1343.

对位-二取代氮苄叉苯胺还原电位的取代基效应

Effect of Substituents on Reduction Potential of Para-disubstituted N-Benzylidenebenzenamine Derivatives

PDF

补充材料

可视化

被引次数

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价

[1]	李征, 谷迎春, 徐大振, 费学宁, 张磊. 有机膦催化的[4+2]环加成反应机理的密度泛函理论研究[J]. 有机化学, 2022, 42(3): 830-837.
[2]	黄谋新, 贾宗宾, 罗三中, 程津培. 自由基的热力学和动力学定量参数[J]. 有机化学, 2021, 41(10): 3892-3902.
[3]	叶美君, 张培志, 吴军. 2-嘧啶氧基-N-芳基苄胺类衍生物的酸催化Smiles重排反应条件的快速筛选和产物的高效制备[J]. 有机化学, 2016, 36(12): 2997-3002.
[4]	冯长根,王建营. 螺噁嗪光致变色反应机理研究进展[J]. 有机化学, 2006, 26(07): 1012-1023.
[5]	冯长根,王建营. 螺噁嗪光致变色反应机理研究进展[J]. 有机化学, 2006, 26(07): 992-995.
[6]	王毅敏,周畅,傅尧,刘磊,郭庆祥. 烯丙位化学键均裂离解能及其取代基效应[J]. 有机化学, 2005, 25(11): 1398-1402.
[7]	陈东林,李正邦,彭崇胜,郑曦孜,陈巧鸿,王锋鹏. 两个特殊骨架的C_(20)－二萜生物碱的全部~1H(~(13)C)核磁共振信号指定[J]. 有机化学, 2003, 23(7): 674-677.
[8]	唐新德,张其震,王大庆,周期凤. 树枝状大分子催化剂的研究进展[J]. 有机化学, 2003, 23(3): 238-242.
[9]	李良超,吴廷华,胡德聪,杨远南. 链烷的物理化学性质及其分子参数的相关性研究[J]. 有机化学, 2003, 23(10): 1125-1130.
[10]	聂长明,李忠海,文松年. 离子性指数、极化效应指数烷烃^13C NMR化学位移的关系研究[J]. 有机化学, 2002, 22(1): 46-51.
[11]	黄齐茂,陈彰评,徐汉生,吴萱阶,赵勇刚,张小伟. 区域选择性合成2-硝基-5, 10, 15, 20-四芳基金属卟啉[J]. 有机化学, 2001, 21(10): 746-750.
[12]	周文富. 取代苯σ·Ⅱ效应分离与FMO能量的相关性 △E~X~.~σ~P^H^O研究[J]. 有机化学, 2000, 20(6): 905-909.
[13]	聂长明,夏良树. 基团共轭效应参数[J]. 有机化学, 2000, 20(2): 237-242.
[14]	何欣,牟丽媛,朱莉亚,林紫云,梁晓天. 取代α-苯基肉桂酸类化合物的合成及其光谱研究[J]. 有机化学, 1999, 19(1): 40-45.
[15]	吴萍,陈文森,俞千,吴毓林. 阿蒂莫耶根番荔枝内酯的研究[J]. 有机化学, 1999, 19(1): 46-52.