含羟基化合物的^(17)O-NMR化学位移研究  

STUDY OF^(17) O-NMR CHEMICAL SHIFTS OF HYDROXY-CONTAINED COMPOUNDS

作　　者：李利东[1] 李临生[1] 

机构地区：[1]陕西科技大学应用化学研究所,陕西咸阳712081

出　　处：《波谱学杂志》2002年第2期115-123,共9页Chinese Journal of Magnetic Resonance

摘　　要：在系统地归纳总结前人对含羟基化合物1 7O 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1 7O NMR化学位移的公式 :δcal =δ0 + ∑aiΔδi,并通过线性回归法结合最小二乘法得到 1 5种计算醇和羧酸中羟基1 7O NMR化学位移时采用的取代基参数和 2 3种计算酚羟基1 7O 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 1 40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1 7O NMR化学位移计算值均在 90Based on systematical induction and summarization of data of 17 O 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( i R refers to substituents whose atom directly connected with hydroxy not telonged to chain alkane) and equation(2): δ\-\{ cal \}=δ\-\{0\}+Δo+Δm+Δp for substituted hydroxybenzenes. 15 substituent parameters for calculating the 17 O NMR chemical shifts of alcohols and carboxylic acids and 23 substituent parameters for substituted hydroxybenzenes are gained with regression analysis in connection with least square. Equation(1) is checked regressively by the 17 O NMR chemical shifts of 140 compounds of primary, secondary, tertiary alcohol and i R-OH, and equation(2) is checked regressively by 17 O NMR chemical shifts of 60 compounds of substituted hydroxybenzenes. Consequently, their confidence limits both are 99.5% and calculating errors(4δ) for over 90% compounds are less than (relation errors 0.5%).

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 核磁共振 

分 类 号：O657.61[理学—分析化学] O482.532[理学—化学]