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
1. [1]
  Jinkang Jin , Yidian Sheng , Ping Lu , Zhan Lu . Introducing a Website for Learning Nuclear Magnetic Resonance (NMR) Spectrum Analysis. University Chemistry, 2024, 39(11): 388-396. doi: 10.12461/PKU.DXHX202403054
2. [2]
  Hao Wu , Zhen Liu , Dachang Bai . ¹H NMR Spectrum of Amide Compounds. University Chemistry, 2024, 39(3): 231-238. doi: 10.3866/PKU.DXHX202309020
3. [3]
  Haolin Zhan , Qiyuan Fang , Jiawei Liu , Xiaoqi Shi , Xinyu Chen , Yuqing Huang , Zhong Chen . Noise Reduction of Nuclear Magnetic Resonance Spectroscopy Using Lightweight Deep Neural Networ. Acta Physico-Chimica Sinica, 2025, 41(2): 100017-. doi: 10.3866/PKU.WHXB202310045
4. [4]
  Haiyang Jin , Yonghai Hui , Yongfei Zhang , Lijun Gao , Yun Wang . Application and Exploration of Nuclear Magnetic Resonance Spectrometer in Undergraduate Basic Laboratory Teaching. University Chemistry, 2025, 40(3): 245-250. doi: 10.12461/PKU.DXHX202406022
5. [5]
  Yaqin Zheng , Lian Zhuo , Meng Li , Chunying Rong . Enhancing Understanding of the Electronic Effect of Substituents on Benzene Rings Using Quantum Chemistry Calculations. University Chemistry, 2025, 40(3): 193-198. doi: 10.12461/PKU.DXHX202406119
6. [6]
  Zhuoming Liang , Ming Chen , Zhiwen Zheng , Kai Chen . Multidimensional Studies on Ketone-Enol Tautomerism of 1,3-Diketones By ¹H NMR. University Chemistry, 2024, 39(7): 361-367. doi: 10.3866/PKU.DXHX202311029
7. [7]
  Yi Li , Zhaoxiang Cao , Peng Liu , Xia Wu , Dongju Zhang . Revealing the Coloration and Color Change Mechanisms of the Eriochrome Black T Indicator through Computational Chemistry and UV-Visible Absorption Spectroscopy. University Chemistry, 2025, 40(3): 132-139. doi: 10.12461/PKU.DXHX202405154
8. [8]
  Qiaowen CHANG , Ke ZHANG , Guangying HUANG , Nuonan LI , Weiping LIU , Fuquan BAI , Caixian YAN , Yangyang FENG , Chuan ZUO . Syntheses, structures, and photo-physical properties of iridium phosphorescent complexes with phenylpyridine derivatives bearing different substituting groups. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 235-244. doi: 10.11862/CJIC.20240311
9. [9]
  Yi DING , Peiyu LIAO , Jianhua JIA , Mingliang TONG . Structure and photoluminescence modulation of silver(Ⅰ)-tetra(pyridin-4-yl)ethene metal-organic frameworks by substituted benzoates. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 141-148. doi: 10.11862/CJIC.20240393
10. [10]
  Kexin Dong , Chuqi Shen , Ruyu Yan , Yanping Liu , Chunqiang Zhuang , Shijie Li . Integration of Plasmonic Effect and S-Scheme Heterojunction into Ag/Ag₃PO₄/C₃N₅ Photocatalyst for Boosted Photocatalytic Levofloxacin Degradation. Acta Physico-Chimica Sinica, 2024, 40(10): 2310013-. doi: 10.3866/PKU.WHXB202310013
11. [11]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063
12. [12]
  Yanglin Jiang , Mingqing Chen , Min Liang , Yige Yao , Yan Zhang , Peng Wang , Jianping Zhang . Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone. Acta Physico-Chimica Sinica, 2025, 41(2): 100012-. doi: 10.3866/PKU.WHXB202309027
13. [13]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
14. [14]
  Jianjun LI , Mingjie REN , Lili ZHANG , Lingling ZENG , Huiling WANG , Xiangwu MENG . UV-assisted degradation of tetracycline hydrochloride by MnFe₂O₄@activated carbon activated persulfate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1869-1880. doi: 10.11862/CJIC.20240187
15. [15]
  Liyang ZHANG , Dongdong YANG , Ning LI , Yuanyu YANG , Qi MA . Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079
16. [16]
  Mengyao Shi , Kangle Su , Qingming Lu , Bin Zhang , Xiaowen Xu . Determination of Potassium Content in Tobacco Stem Ash by Flame Atomic Absorption Spectroscopy. University Chemistry, 2024, 39(10): 255-260. doi: 10.12461/PKU.DXHX202404105
17. [17]
  Jiahui CHEN , Tingting ZHENG , Xiuyun ZHANG , Wei LÜ . Research progress of near-infrared absorption inorganic nanomaterials in photothermal and photodynamic therapy of tumors. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2396-2414. doi: 10.11862/CJIC.20240106
18. [18]
  Zehua Zhang , Haitao Yu , Yanyu Qi . 多重共振TADF分子的设计策略. Acta Physico-Chimica Sinica, 2025, 41(1): 2309042-. doi: 10.3866/PKU.WHXB202309042
19. [19]
  Jizhou Liu , Chenbin Ai , Chenrui Hu , Bei Cheng , Jianjun Zhang . 六氯锡酸铵促进钙钛矿太阳能电池界面电子转移及其飞秒瞬态吸收光谱研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2402006-. doi: 10.3866/PKU.WHXB202402006
20. [20]
  Min LI , Xianfeng MENG . Preparation and microwave absorption properties of ZIF-67 derived Co@C/MoS₂ nanocomposites. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1932-1942. doi: 10.11862/CJIC.20240065

Get Citation

PDF

XML

Metrics

PDF Downloads(372)
Abstract views(746)
HTML views(57)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142