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

doi:10.6023/cjoc201411037

Chin. J. Org. Chem. ›› 2015, Vol. 35 ›› Issue (6): 1302-1309.DOI: 10.6023/cjoc201411037 Previous Articles Next Articles

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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).

1. Effect of Substituents on Reduction Potential of Para-disubstituted N-Benzylidenebenzenamine Derivatives.PDF(528KB)

Abstract

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

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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.

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[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

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