Structural studies on aryl-substituted enaminoketones and their thio analogues. Part I. Analysis of high-resolution (1)H, (13)C NMR and (13)C CP MAS spectra combined with GIAO-DFT calculations.
A series of aryl-substituted enaminoketones and their thio analogues in CDCl(3) solution and in the solid state were studied by the use of high-resolution (1)H and (13)C as well as (13)C cross polarization magic angle spinning (CP MAS) NMR spectra in combination with gauge including atomic orbitals-density functional theory (GIAO-DFT) calculations performed at the B3PW91/6-311 + + G(d,p) level of theory using the B3PW91/6-311 + + G(d,p)-optimized geometries. The analysis of the (13)C NMR spectra in solution was done by using the Incredible Natural Abundance DoublE QUAntum Transfer Experiment (INADEQUATE) technique, whereas trends observed in the (13)C shielding constants, calculated for the compounds studied, were a great help in assigning most of the signals in the (13)C CP MAS NMR spectra. It was established on the basis of the experimental and theoretical NMR data that both groups of compounds exist in the form of Z-s-Z-s-E isomers in CDCl(3) solution as well as in the solid state, with the NH hydrogen atom involved in intramolecular hydrogen bonding. This conclusion is in agreement with the fact that some of the compounds studied reveal liquid-crystalline properties. Three-bond H, H and C, H coupling constants measured in solution played a crucial role in the structure elucidation.
Bugaj
Marta
M
Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Poland.
Baran
Piotr A
PA
Bernatowicz
Piotr
P
Brozek
Patrycja
P
Kamieńska-Trela
Krystyna
K
Krówczyński
Adam
A
Kamieński
Bohdan
B
D002247:Carbon Isotopes; D003198:Computer Simulation; D007659:Ketones / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods / Q000592:standards; D008956:Models, Chemical; D015394:Molecular Structure; D011522:Protons; D012015:Reference Standards; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D002247:Carbon Isotopes; D007659:Ketones; D011522:Protons; D013438:Sulfhydryl Compounds