The conformational analysis of push-pull enaminoketones using Fourier transform IR and NMR spectroscopy, and quantum chemical calculations: II. Beta-dimethylaminoacrolein.
IR Fourier and (1)H NMR spectra of beta-dimethylaminoacrolein (DMAA) were investigated in various pure solvents. Quantum chemical calculations by the method AM1 also was carried out to evaluate relative energy and dipole moment of each conformer. On the basis of NMR and IR-spectra we showed that the (DMAA) presented in solutions as equilibrium of two conformers, (E-s-Z) <==> (E-s-E). Constant of this equilibrium, K(eq) = C(E-s-E)/C(E-s-Z), depended strongly on the total (DMAA) concentration: ln K(eq) = ln K(eq0) + a(1 - e(-bC) total). Besides, (E-s-Z) conformer of the (DMAA) was more polar and more stable than the (E-s-E) conformer. Correlation of the out-of-phase nu(C=O) and in-phase nu(C=C) vibrations with solvatochromic parameters of Kamlet, Abbot, and Taft (KAT) revealed that the main contribution to the shift of the out-of-phase nu(C=O) vibrations of the both conformers made solvent's hydrogen bond acceptor (HBA) (beta) term, whereas hydrogen bond donor (HBD) acidity (alpha) term influenced predominantly on the shift of the in-phase nu(C=C) vibrations of the conformers. Moreover, influence of these dominated terms was more pronounced for the (E-s-Z) conformer in comparison with the (E-s-E) conformer, hence the first conformer was more polarized than the last. Investigations of the enthalpies of the (E-s-Z) <==> (E-s-E) equilibrium in carbon tetrachloride, 1,4-dioxane and their mixtures showed that these enthalpies depended predominantly on the solvent's atomic and electronic polarization and dispersive interactions.
Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, Str. Murmanska 1, 02094 Kiev, Ukraine. sergiusz@bpci.kiev.ua
Sergey I
SI
Vdovenko
Igor I
II
Gerus
Elena A
EA
Fedorenko
D000171:Acrolein / Q000031:analogs & derivatives* / Q000737:chemistry*; D002251:Carbon Tetrachloride / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008968:Molecular Conformation; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared; D013237:Stereoisomerism; D013816:Thermodynamics; D054159:Torsion, Mechanical; D014732:Vibration
D007659:Ketones; D012997:Solvents; C546462:beta-dimethylaminoacrolein; D000171:Acrolein; D002251:Carbon Tetrachloride