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

doi:10.11938/cjmr20170109

Abstract

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

CLC Number:

O482.53

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

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