取代基效应对二取代二苯基硝酮还原电位的影响

引用本文: 罗青青, 曹朝暾, 曹晨忠. 取代基效应对二取代二苯基硝酮还原电位的影响[J]. 物理化学学报, 2016, 32(7): 1691-1698. doi: 10.3866/PKU.WHXB201604061 shu

Citation: LUO Qing-Qing, CAO Chao-Tun, CAO Chen-Zhong. Effects of Substituents on Reduction Potentials of Disubstituted N-Phenyl-α-phenylnitrones[J]. Acta Physico-Chimica Sinica, 2016, 32(7): 1691-1698. doi: 10.3866/PKU.WHXB201604061 shu

取代基效应对二取代二苯基硝酮还原电位的影响

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, 湖南湘潭 411201
基金项目:
国家自然科学基金（21272063），湖南省教育厅科研项目（14C0466）和湖南省自然科学基金（14JJ3112）资助

摘要: 合成了36种二取代二苯基硝酮XArCH＝N（O）ArY （简称XPNY）化合物，研究了取代基效应对其还原电位（E_red）的影响，并系统对比了XPNY与XArCH＝NArY （简称XBAY）和XArC（Me）＝NArY （简称XPEAY）还原电位的差异。研究结果表明：XPNY的E_red与C＝N键的¹³C NMR化学位移δ_C（C＝N）没有线性关系；XPNY、XBAY和XPEAY三类化合物的E_red之间没有线性关系，表现出不同的变化规律；X基团的激发态取代基效应和间位基团位置指示变量对化合物XPEAY和XBAY的E_red都有贡献，而对化合物XPNY的E_red贡献都很小，可忽略；Y基团的激发态取代基效应对化合物XPNY的E_red有一定贡献，而对化合物XPEAY和XBAY的E_red贡献很小，可忽略；XBAY和XPNY的母体有近似的还原电位，而XPEAY的母体其还原电位更低，一般而言，X-Y基团对相同时，XPEAY化合物更难被还原。

关键词:

English

Effects of Substituents on Reduction Potentials of Disubstituted N-Phenyl-α-phenylnitrones

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, Hunan Province, P. R. China
Received Date: 14 December 2015
Revised Date: 05 April 2016
Available Online: 06 April 2016
Fund Project:
The project was supported by the National Natural Science Foundation of China (21272063), Scientific Research Fund of Hunan Provincial Education Department, China (14C0466), and Natural Science Foundation of Hunan Province, China (14JJ3112).

Abstract: Thirty-six samples of disubstituted N-Phenyl-α-phenylnitrones, XArCH＝N(O)ArY (XPNY), were synthesized. The effects of their substituents on their reduction potentials (E_red) were investigated by systematically comparing the E_red differences for XPNY versus XArCH ＝ NArY (XBAY) and XPNY versus XArC(Me)＝NArY (XPEAY). The results show the following: there is no linear relationship between the E_red values and ¹³C NMR chemical shifts, δ_C(C＝N), of the C＝N bridging bond for XPNY; there are no linear relationships among the E_red values for XPNY versus XBAY and XPNY versus XPEAY, i.e., their E_red values show their own specific regular changes; the excited-state substituent effect of X and the indicating parameter of the metaposition group make important contributions to the E_red values of XPEAY and XBAY, but have little effect on E_red of XPNY; the excited-state substituent effect of the Y group contributes to the XPNY E_red, but rarely contributes to the E_red values of XPEAY and XBAY, and can be ignored; the parents of XBAY and XPNY have similar reduction potentials, but the reduction potential of the parent of XPEAY is lower than those of XBAY and XPNY. In general, XPEAY is more difficult to be reduced than XBAY or XPNY, for these three types of compound with X-Y group couples.

Key words:

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取代基效应对二取代二苯基硝酮还原电位的影响

English

Effects of Substituents on Reduction Potentials of Disubstituted N-Phenyl-α-phenylnitrones

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取代基效应对二取代二苯基硝酮还原电位的影响

English

Effects of Substituents on Reduction Potentials of Disubstituted N-Phenyl-α-phenylnitrones

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