Citation: CAO Chao-Tun, WEI Bai-Ying, CAO Chen-Zhong. Effect of Substituents on the NMR and UV Spectra of N-(4-substituted benzylidene) Anilines and N-(4-substituted benzylidene) Cyclohexylamines[J]. Acta Physico-Chimica Sinica, ;2015, 31(2): 204-210. doi: 10.3866/PKU.WHXB201412191 shu

Effect of Substituents on the NMR and UV Spectra of N-(4-substituted benzylidene) Anilines and N-(4-substituted benzylidene) Cyclohexylamines

1.
Hunan Provincial University Key Laboratory of QSAR/QSPR, Key Laboratory of Theoretical Organic Chemistry and Function Molecule of Ministry of Education, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, Hunan Province, P. R. China

Received Date: 24 September 2014
Available Online: 19 December 2014
Fund Project: 国家自然科学基金(21272063, 21072053) (21272063, 21072053)湖南省自然科学基金(14JJ3112)项目资助 (14JJ3112)

Two series of compounds: N-(4-substituted benzylidene) anilines (1) and N-(4-substituted benzylidene) cyclohexylamines (2) were synthesized. Their ¹³C NMR and ¹H NMR chemical shifts and their UV absorption spectra were obtained. Compounds (1) and (2) were compared quantitatively to determine the effect of the substituents on the ¹³C NMR chemical shifts δ_C(C=N) and the ¹H NMR chemical shifts δ_H of the CH=N bond, and the UV absorption maximum wavelength energies v_max. Our results show that the substituents affect compounds (1) and (2) differently despite them having a similar molecular skeleton. These effects are: (i) a substituent specific cross-interaction effect (Δσ²) that significantly affects the δ_C(C=N), δ_H, and v_max of compounds (1) while its effect on the corresponding properties of compounds (2) is limited, (ii) for compounds (1) and compounds (2) the field/induced effect σ_F and the conjugation effect σ_R of the substituents negatively affect δ_C(C=N). However, they positively influence δ_H and thus both σ_F and σ_R showopposite behavior toward δ_C(C=N) compared with δ_H. In contrast the field/induced effect greatly affects the δ_C(C=N) of both (1) and (2) but does not affect their δ_H, (iii) the regular change in δ_C(C=N), δ_H, and the v_max of (1) as well as (2) can be expressed by a general equation in which the effect of the phenyl group attached to the N atom of the CH=N bond can be expressed by a dummy parameter I. The phenyl group has a constant contribution toward these three properties.
- Benzylidene-aniline,
- Substituent effect,
- Nuclear magnetic resonance,
- Ultraviolet absorption,
- Substituent specific cross-interaction
1. [1]
  
  (1) Cao, C.; Chen, G.; Yin, Z. J. Phys. Org. Chem. 2008, 21 (9), 808. doi: 10.1002/poc.v21:9
2. [2]
  (2) Chen, G.; Cao, C. Chin. J. Chem. Phys. 2009, 22 (4), 366. doi: 10.1088/1674-0068/22/04/366-370
3. [3]
  (3) Chen, G.; Cao, C. J. Phys. Org. Chem. 2010, 23 (8), 776.
4. [4]
  (4) Cao, C.; Chen, G.;Wu, Y. Sci. China Chem. 2011, 54 (11), 1735. doi: 10.1007/s11426-011-4379-7
5. [5]
  (5) Cao, C.; Sheng, B.; Chen, C. J. Phys. Org. Chem. 2012, 25 (12), 1315. doi: 10.1002/poc.v25.12
6. [6]
  (6) Cao, C.; Zhu, Y.; Chen, G. J. Phys. Org. Chem. 2013, 26 (10), 834. doi: 10.1002/poc.v26.10
7. [7]
  (7) Chen, G.; Cao, C.; Lu, B.; Sheng, B. J. Phys. Org. Chem. 2012, 25 (4), 327. doi: 10.1002/poc.v25.4
8. [8]
  (8) Cao, C.; Fang, Z. Spectrochim. Acta A 2013, 111, 62. doi: 10.1016/j.saa.2013.03.082
9. [9]
  (9) Li, F. Y.; Zheng, J.; Liu, T. T.; Jin, L. P.; Zhao, X. S.; Guo, J. Q. Acta Phys. -Chim. Sin. 2000, 16, 787. [李富友, 郑杰, 柳汀汀, 金林培, 赵新生, 郭建权. 物理化学学报, 2000, 16, 787.] doi: 10.3866/PKU.WHXB20000906
10. [10]
  (10) Neuvonen, H.; Neuvonen, K.; Fülöp, F. J. Org. Chem. 2006, 71, 3141. doi: 10.1021/jo0600508
11. [11]
  (11) Chen, G.; Cao, C.; Sheng, B.; Zhu, Y.;Wu, Z.;Wu, X. J. Phys. Org. Chem. 2012, 25 (10), 828. doi: 10.1002/poc.v25.10
12. [12]
  (12) Chen, G.; Cao, C.; Zhu, Y.;Wu, Z.;Wu, X. Spectrochim. Acta A 2012, 99, 218. doi: 10.1016/j.saa.2012.09.028
13. [13]
  (13) Fang, Z.; Cao, C.; Chen, G. J. Phys. Org. Chem. 2012, 25 (12), 1343. doi: 10.1002/poc.v25.12
14. [14]
  (14) Fang, Z.; Cao, C. J. Mol. Struct. 2013, 1036, 447. doi: 10.1016/j.molstruc.2012.12.014
15. [15]
  (15) Fang, Z.; Cao, C.;Wu,W.;Wang, L. J. Phys. Org. Chem. 2013, 26, 249. doi: 10.1002/poc.v26.3
16. [16]
  (16) Cao, C.; Lu, B.; Chen, G. J. Phys. Org. Chem. 2011, 24 (4), 335. doi: 10.1002/poc.1760
17. [17]
  (17) Schmeyers, J.; Toda, F.; Boy, J.; Kaupp, G. J. Chem. Soc. Perkin Trans 2 1998, 989.
18. [18]
  (18) Lu, B. Substituent Effect on the Spectra and Molecular Configuration of 4,4′ -Disubstituted N-benzylidenebenzenamine Derivatives. Master Dissertation, Hunan University of Science and Technology, Hunan, 2011. [卢冰涛. 取代基效应对4,4′ -二取代氮苄叉苯胺衍生物光谱性能及分子构型的影响[D]. 湖南: 湖南科技大学, 2011.]
19. [19]
  (19) Keglevich, G.; Kiss, N. Z.; Menyhárd, D. K.; Fehérvári, A.; Csontos, I. Heteroatom Chem. 2012, 23 (2), 171. doi: 10.1002/hc.v23.2
20. [20]
  (20) Cao, C.;Wu, Y. Sci. China Chem. 2013, 56 (7), 883. doi: 10.1007/s11426-013-4890-0
21. [21]
  (21) Hansch, C.; Leo, A.; Taft, R.W. Chem. Rev. 1991, 91, 165. doi: 10.1021/cr00002a004
22. [22]
  (22) Jiang, X. K.; Zhang, J. S. Aggregation and Self-Coling of Organic Molecules; Shanghai Science and Technology Press: Shanghai, 1996; pp 94-112. [蒋锡夔, 张劲松. 有机分子的簇集和自卷. 上海: 上海科学技术出版社, 1996: 94-112.]
23. [23]
  (23) Cao, C. Z.; Chen, G. F.;Wu, Y. X. Sci. Sin. Chim. 2012, 42 (2), 127. [曹晨忠, 陈冠凡, 武亚新. 中国科学: 化学, 2012, 42 (2), 127.] doi: 10.1007/s11426-011-4379-7
24. [24]
  (24) Shetty, A. S.; Zhang, J.; Moore, J. S. J. Am. Chem. Soc. 1996, 118, 1019. doi: 10.1021/ja9528893
25. [25]
  (25) Jones, G., II; Vullev, V. I. J. Phys. Chem. A 2001, 105, 6402. doi: 10.1021/jp010087q
26. [26]
  (26) Venkataramana, G.; Sankararaman, S. Org. Lett. 2006, 8 (13), 2739. doi: 10.1021/ol060767h
27. [27]
  (27) on, P.; Das, S.; Clemett, C. J.; Tiddy, G. J. T.; Kumar, V. V. Langmuir 1997, 13, 5577. doi: 10.1021/la970502z
28. [28]
  (28) Luca, G. D.; Romeo, A.; Scolaro, L. M. J. Phys. Chem. B 2005, 109, 7149. doi: 10.1021/jp0448797
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