1H NMR spectra part 31: 1H chemical shifts of amides in DMSO solvent.
The (1)H chemical shifts of 48 amides in DMSO solvent are assigned and presented. The solvent shifts Δδ (DMSO-CDCl3 ) are large (1-2 ppm) for the NH protons but smaller and negative (-0.1 to -0.2 ppm) for close range protons. A selection of the observed solvent shifts is compared with calculated shifts from the present model and from GIAO calculations. Those for the NH protons agree with both calculations, but other solvent shifts such as Δδ(CHO) are not well reproduced by the GIAO calculations. The (1)H chemical shifts of the amides in DMSO were analysed using a functional approach for near ( ≤ 3 bonds removed) protons and the electric field, magnetic anisotropy and steric effect of the amide group for more distant protons. The chemical shifts of the NH protons of acetanilide and benzamide vary linearly with the π density on the αN and βC atoms, respectively. The C=O anisotropy and steric effect are in general little changed from the values in CDCl3. The effects of substituents F, Cl, Me on the NH proton shifts are reproduced. The electric field coefficient for the protons in DMSO is 90% of that in CDCl3. There is no steric effect of the C=O oxygen on the NH proton in an NH…O=C hydrogen bond. The observed deshielding is due to the electric field effect. The calculated chemical shifts agree well with the observed shifts (RMS error of 0.106 ppm for the data set of 257 entries).
The Chemistry Department, University of Liverpool, Crown St., Liverpool, L69 7ZD, UK.
Raymond J
RJ
Abraham
Lee
L
Griffiths
Manuel
M
Perez
D000577:Amides / Q000737:chemistry*; D003198:Computer Simulation; D004121:Dimethyl Sulfoxide / Q000737:chemistry*; D008956:Models, Chemical; D066244:Proton Magnetic Resonance Spectroscopy / Q000379:methods*; D011522:Protons; D012997:Solvents / Q000737:chemistry
D000577:Amides; D011522:Protons; D012997:Solvents; D004121:Dimethyl Sulfoxide
1H chemical shifts; NMR; amides; solvent effects; π density