含羟基化合物的17O-NMR化学位移研究

摘要/Abstract

摘要：

在系统地归纳总结前人对含羟基化合物¹⁷O-NMR化学位移研究成果的基础上，按伯、仲、叔醇，i-R—OH型化合物(i-R表示与羟基直接相连的原子为非链状烷烃碳原子的取代基)及苯酚类等五大类，提出了计算含羟基化合物¹⁷O-NMR化学位移的公式：δ_cal=δ₀+∑a_iΔδ_i，并通过线性回归法结合最小二乘法得到15种计算醇和羧酸中羟基¹⁷O-NMR化学位移时采用的取代基参数和23种计算酚羟基¹⁷O-NMR化学位移时采用的取代基参数，计算结果分别以伯、仲、叔醇、i-R—OH型化合物四类140种化合物和60种酚类在化合物为样本点作回归检验，置信度均为99.5% ，计算误差Δδ小于5(相对误差小于0.5%)的¹⁷O-NMR化学位移计算值均在90 %以上. 

关键词: ¹⁷O-NMR, 化学位移计算, 取代基效应, 回归分析, 羟基化合物

Abstract:

Based on systematical induction and summarization of data o f ¹⁷O-NMR chemical shifts of hydroxy-contained compounds already reported, the article provides the equation(1): δ_cal=δ_0n+Δα+Δβ+Δγ for primary, secondary, tertiary alcohol and i-R—OH(em-R refers to substituents whose atom directly connected with hydroxy not telong ed to chain alkane) and equation(2): δ_cal=δ₀+Δo+Δm+Δp for substituted hydroxybenzenes. 15 substituent parameters for calculating the ¹⁷O-NMR chemical shifts of alcoho ls and carboxylic acids and 23 substituent parameters for substituted hydroxybenze nes are gained with regression analysis in connection with least square. Equatio n(1) is checked regressively by the ¹⁷O-NMR chemical shifts of 140 compounds of primary, secondary, tertiary alcohol and i-R—OH, and equati on(2) is checked regressively by ¹⁷O-NMR chemical shifts of 60 compounds of substituted hydroxybenzenes. Consequently, their confidence limits both are 99. 5% and calculating errors(4δ) for over 90% compounds are less than (relatio nerrors 0.5%).

Key words: ¹⁷O-NMR, chemical shift, substituent ef fect, alcohol, hydroxybenzenes

中图分类号:

O482.53

李利东，李临生*. 含羟基化合物的¹⁷O-NMR化学位移研究[J]. 波谱学杂志.

LI Li-dong, LI Lin-sheng*. STUDY OF ¹⁷O-NMR CHEMICAL SHIFTS OF HYDROXY-CONT AINED COMPOUNDS[J]. Chinese Journal of Magnetic Resonance.

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含羟基化合物的¹⁷O-NMR化学位移研究

STUDY OF ¹⁷O-NMR CHEMICAL SHIFTS OF HYDROXY-CONT AINED COMPOUNDS

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