取代亚胺中亚胺基^(15)N NMR化学位移规律的研究  

Calculation of ^(15)N NMR Chemical Shifts of Imine Groups in Imines

作　　者：李临生[1] 张丽娜[1] 兰云军[1] 张昌辉[2] 

机构地区：[1]温州大学浙江省皮革重点实验室,浙江温州325027 [2]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》2008年第3期391-396,共6页Chinese Journal of Magnetic Resonance

基　　金：陕西省自然科学基金资助项目(2003B17)

摘　　要：提出了计算苯甲醛亚胺、N-苯基亚胺、N-甲基亚胺、N-异丙基亚胺中亚胺基氮原子15N NMR化学位移的经验公式:δcal=δ0n+Δα+Δβ+Δγ+c.按亚胺基氮原子和碳原子上两类取代基的不同分别结合最小二乘法通过线性回归各得到5种取代基参数,计算结果分别以其化学位移数据为样本点作回归检验,置信度为99.5%,最大误差Δδ≤3.1,大约有95%的15N NMR化学位移计算值的计算误差小于3.0(相对误差小于0.3%).初步分析了芳香族亚胺苯环上对位取代基对亚胺基氮原子化学位移的影响.Abstract： An equation：δcal=δon＋△α＋□β＋△β＋△γ＋c,for the calculation of ^15N chemical shifts of substituted imines was provided. The five substituent parameters were obtained by linear least square regression analysis on the data from four different kinds of imines （PhCH=N-X, RHC=NC6H5, RHC=NCH3 and RHC=N--i-C3H7）. The ac-curacy of the results calculated with the model was checked using 34 ^15N NMR chemical shifts in 34 substituted imines as a test set. The confidence limit was found to be 99.5%, and the calculating errors for about 95% of the compounds were less than 3.0 （with relative errors of 0.3M）. The effects of p-substituent on the chemical shifts of the ^15N atoms of aromatic imines were also analyzed.

关 键 词：^15N NMR化学位移 取代基效应 亚胺 芳香族亚胺 

分 类 号：O482.53[理学—固体物理]