SIOC 中文
CJOG
Adv search

Chinese Journal of Organic Chemistry >

2015 , Vol. 35 >Issue 6: 1302 - 1309

DOI: https://doi.org/10.6023/cjoc201411037

Articles

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

  • Cao Chenzhong ,
  • Bi Yakun ,
  • Cao Chaotun
Expand
  • 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 date: 2014-11-25

  Revised date: 2014-12-16

  Online 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).

Fold

Abstract

52 samples of 4,4'-disubstituted N-benzylidenebenzenamine (p-XPhCH=NC6H4Y-p) derivatives were synthesized, the effect of substituents on the reduction potential ERed of these compounds was systematically investigated. The result shows that there is not linear relation between their ERed and the chemical shift δC(C=N) of the 13C NMR of C=N bridge bond in the molecules. The factors affecting ERed are obvious different from that affecting on δC(C=N), and the change regularity of ERed can not be expressed well by only employing Hammett substituent constant. The main factors affecting the ERed 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 ERed. Above four parameters have good correlations with the ERed 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 ERed 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

Cite this article

Cao Chenzhong , Bi Yakun , Cao Chaotun . Effect of Substituents on Reduction Potential of Para-disubstituted N-Benzylidenebenzenamine Derivatives[J]. Chinese Journal of Organic Chemistry, 2015 , 35(6) : 1302 -1309 . DOI: 10.6023/cjoc201411037

References

[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.

Options
Outlines

/

〈 〉