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
-
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 δC(C=N) and the 1H NMR chemical shifts δH of the CH=N bond, and the UV absorption maximum wavelength energies vmax. 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 δC(C=N), δH, and vmax 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 σF and the conjugation effect σR of the substituents negatively affect δC(C=N). However, they positively influence δH and thus both σF and σR showopposite behavior toward δC(C=N) compared with δH. In contrast the field/induced effect greatly affects the δC(C=N) of both (1) and (2) but does not affect their δH, (iii) the regular change in δC(C=N), δH, and the vmax 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.
-
-
-
[1]
(1) Cao, C.; Chen, G.; Yin, Z. J. Phys. Org. Chem. 2008, 21 (9), 808. doi: 10.1002/poc.v21:9
-
[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) Chen, G.; Cao, C. J. Phys. Org. Chem. 2010, 23 (8), 776.
-
[4]
(4) Cao, C.; Chen, G.;Wu, Y. Sci. China Chem. 2011, 54 (11), 1735. doi: 10.1007/s11426-011-4379-7
-
[5]
(5) Cao, C.; Sheng, B.; Chen, C. J. Phys. Org. Chem. 2012, 25 (12), 1315. doi: 10.1002/poc.v25.12
-
[6]
(6) Cao, C.; Zhu, Y.; Chen, G. J. Phys. Org. Chem. 2013, 26 (10), 834. doi: 10.1002/poc.v26.10
-
[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) Cao, C.; Fang, Z. Spectrochim. Acta A 2013, 111, 62. doi: 10.1016/j.saa.2013.03.082
-
[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) Neuvonen, H.; Neuvonen, K.; Fülöp, F. J. Org. Chem. 2006, 71, 3141. doi: 10.1021/jo0600508
-
[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) 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) Fang, Z.; Cao, C.; Chen, G. J. Phys. Org. Chem. 2012, 25 (12), 1343. doi: 10.1002/poc.v25.12
-
[14]
(14) Fang, Z.; Cao, C. J. Mol. Struct. 2013, 1036, 447. doi: 10.1016/j.molstruc.2012.12.014
-
[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) Cao, C.; Lu, B.; Chen, G. J. Phys. Org. Chem. 2011, 24 (4), 335. doi: 10.1002/poc.1760
-
[17]
(17) Schmeyers, J.; Toda, F.; Boy, J.; Kaupp, G. J. Chem. Soc. Perkin Trans 2 1998, 989.
-
[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) 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) Cao, C.;Wu, Y. Sci. China Chem. 2013, 56 (7), 883. doi: 10.1007/s11426-013-4890-0
-
[21]
(21) Hansch, C.; Leo, A.; Taft, R.W. Chem. Rev. 1991, 91, 165. doi: 10.1021/cr00002a004
-
[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) 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) Shetty, A. S.; Zhang, J.; Moore, J. S. J. Am. Chem. Soc. 1996, 118, 1019. doi: 10.1021/ja9528893
-
[25]
(25) Jones, G., II; Vullev, V. I. J. Phys. Chem. A 2001, 105, 6402. doi: 10.1021/jp010087q
-
[26]
(26) Venkataramana, G.; Sankararaman, S. Org. Lett. 2006, 8 (13), 2739. doi: 10.1021/ol060767h
-
[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) 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]
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]
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]
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]
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]
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]
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]
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]
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]
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]
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]
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]
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]
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]
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]
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]
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]
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]
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]
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
-
[1]
Metrics
- PDF Downloads(372)
- Abstract views(743)
- HTML views(57)