1H NMR spectra. Part 30+: 1H chemical shifts in amides and the magnetic anisotropy, electric field and steric effects of the amide group

The H-1 spectra of 37 amides in CDCl3 solvent were analysed and the chemical shifts obtained. The molecular geometries and conformational analysis of these amides were considered in detail. The NMR spectral assignments are of interest, e. g. the assignments of the formamide NH2 protons reverse in going from CDCl3 to more polar solvents. The substituent chemical shifts of the amide group in both aliphatic and aromatic amides were analysed using an approach based on neural network data for near (<= 3 bonds removed) protons and the electric field, magnetic anisotropy, steric and for aromatic systems pi effects of the amide group for more distant protons. The electric field is calculated from the partial atomic charges on the N.C O atoms of the amide group. The magnetic anisotropy of the carbonyl group was reproduced with the asymmetric magnetic anisotropy acting at the midpoint of the carbonyl bond. The values of the anisotropies Delta chi(parl) and Delta chi(perp) were for the aliphatic amides 10.53 and -23.67 (x10(-6) angstrom(3)/molecule) and for the aromatic amides 2.12 and -10.43 (x10(-6) angstrom(3)/molecule). The nitrogen anisotropy was 7.62 (x10(-6) angstrom(3)/molecule). These values are compared with previous literature values. The H-1 chemical shifts were calculated from the semi-empirical approach and also by gauge-independent atomic orbital calculations with the density functional theory method and B3LYP/6-31G(++) (d,p) basis set. The semi-empirical approach gave good agreement with root mean square error of 0.081 ppm for the data set of 280 entries. The gauge-independent atomic orbital approach was generally acceptable, but significant errors (ca. 1 ppm) were found for the NH and CHO protons and also for some other protons. Copyright (C) 2013 John Wiley & Sons, Ltd.