取代基效应对二芳基硝酮CH=N(O)桥基1H NMR化学位移的影响

doi:10.11938/cjmr20170109

摘要/Abstract

摘要： 合成一系列取代二芳基硝酮XArCH=N（O）ArY化合物，测定其核磁共振氢谱（¹H NMR），指认出桥基CH=N（O）上质子的化学位移δH[CH=N（O）]，定量研究取代基效应对δH[CH=N（O）]的影响.得到一个4参数定量方程，标准偏差（S）为0.020，较好地表达了δH[CH=N（O）]的变化规律.结果表明，该类化合物的δH[CH=N（O）]主要受4个因素影响：X基团的场/诱导效应[σ_F（X）]；Y基团的共轭效应[σ_R（X）]；基团X和Y之间的特殊交叉作用（Δσ²）；以及基团X和O^-之间的特殊交叉作用[Δσ²_（X-O^-）].其中，Δσ²_（X-O^-）对δ_{H[CH=N（O）]}变化的贡献超过70%.通过δH[CH=N（O）]与二芳基希夫碱XArCH=NArY桥基CH=N上质子化学位移的δH（CH=N）比较发现，这两类化合物桥基上质子的化学位移之间没有良好的线性关系.因而，在应用NMR谱图解析有机化合物分子结构时，不能简单地用δH（CH=N）的变化去类比δ_{H[CH=N（O）]}的变化.

关键词: ¹H NMR化学位移, 基团特殊交叉作用, 取代基效应, 二芳基硝酮, 二芳基希夫碱, 核磁共振(NMR)

Abstract: A series of substituted diaryl nitrones XArCH=N(O)ArY were synthesized, and their ¹H NMR spectra were measured. The ¹H chemical shift of the CH=N(O) bridge groups, δ_H[CH=N(O)], in each compound was determined. The effects of substituents X and Y on δ_H[CH=N(O)] were investigated quantitatively. A four parameters correlation equation was constructed to model the changes of δ_H[CH=N(O)] with substituents, yielding a standard error of 0.020. The result indicated that δ_H[CH=N(O)] in substituted diaryl nitrones are mainly affected by four factors:field/inductive effect (S) of substituent X[σ_F(X)], conjugative effect of substituent Y[σ_R(X)], substituent specific cross-interaction effect between X and Y (Δσ²) and substituent specific crossinteraction effect between X and O^-[Δσ²_(X-O^-)]. Among these factors, the contribution of Δσ²_(X-O^-) to δ_H[CH=N(O)] was more than 70%. A comparison of δ_H[CH=N(O)] in substituted diaryl nitrones to δH(CH=N) of the CH=N bridge group in diaryl Schiff base XArCH=NArY revealed no good linear relationship between δ_H[CH=N(O)] and δH(CH=N). Therefore it should be noted that one cannot simply use the change of δH(CH=N) to deduce the change of δ_H[CH=N(O)] when carrying out organic molecule structure elucidation with NMR spectra.

Key words: nuclear magnetic resonance (NMR), substituent specific cross-interaction effect, ¹H NMR chemical shift, substituent effect, diaryl nitrone, diaryl Schiff base

中图分类号:

O482.53

曹朝暾, 罗青青, 曹晨忠. 取代基效应对二芳基硝酮CH=N(O)桥基¹H NMR化学位移的影响[J]. 波谱学杂志, 2017, 34(1): 69-77.

CAO Chao-tun, LUO Qing-qing, CAO Chen-zhong. Substituent Effects on the ¹H NMR Chemical Shifts of CH=N(O) Bridge Group in Diaryl Nitrone[J]. Chinese Journal of Magnetic Resonance, 2017, 34(1): 69-77.

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取代基效应对二芳基硝酮CH=N(O)桥基¹H NMR化学位移的影响

Substituent Effects on the ¹H NMR Chemical Shifts of CH=N(O) Bridge Group in Diaryl Nitrone

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