Sergey I. Vdovenko

Solvent effects on the infrared spectra of β-alkoxyvinyl methyl ketones: I. Carbonyl and vinyl stretching vibrations

Infrared spectroscopy studies of six beta-alkoxyvinyl methyl ketones, with common structure R(1)O-CR(2)CH-COR(3), where R(1)=R(3)=CH(3), R(2)=H (1); R(1)=C(2)H(5), R(2)=H (2); R(3)=CF(3); R(1)=R(2)=CH(3), R(3)=CF(3) (3); R(1)=C(2)H(5), R(2)=C(6)H(5), R(3)=CF(3) (4); R(1)=C(2)H(5), R(2)=4-O(2)NC(6)H(4), R(3)=CF(3) (5); R(1)=C(2)H(5), R(2)=C(CH(3))(3), R(3)=CF(3) (6) in 11 pure organic solvents of different polarity were undertaken to investigate the solute-solvent interactions and to correlate solvent properties by means of linear solvation energy relationships (LSER) with the carbonyl and vinyl stretching vibrations of existing stereoisomeric forms. It was shown that contrary to simple carbonyl-containing compounds where solvent HBD acidity (alpha) has the largest influence on the nu (CO) band shift to lower wavenumbers, the dipolarity/polarizability (pi) term plays the main role in the interactions of conjugated enones with solvent molecules leading to the nu (CO) and nu (CC) bathochromic band shifts. The trifluoroacetyl group possesses a reduced ability to form hydrogen bonds with solvents. For the nu (CC) band of non-fluorinated enone 1 solvent HBD acidity (alpha) and solvent HBA basicity term (beta) play a perceptible role, whereas for 2 these terms are not significant. beta-Substituents in fluorinated enones such as R(2)=H, C(6)H(5), and C(CH(3))(3) assist in the intermolecular hydrogen bond formation of the carbonyl moiety with HBD solvents, while beta-substituents such as CH(3) and 4-NO(2)C(6)H(4) prevent the CO group to form the H-bonds with HBD solvents (the solvent HBD acidity term (alpha) is not significant). The comparison of four conformers of the enone 1 reveals that (EEE) form is the most polarizable conformer; the influences of the solvent dipolarity/polarizability (pi) and solvent HBD acidity (alpha) term on the bathochromic nu (CO) band shift are opposite to one another.

The conformational analysis of push-pull enaminones using Fourier transform IR and NMR spectroscopy, and quantum chemical calculations. IV. 4-(N,N-dimethylamino)-1,1,1-trifluoro-3-methylbut-3-en-2-one and 4-(N,N-dimethyl-amino)-1,1,1-trifluoropropen-3-en-2-one.

IR Fourier spectra of two enaminoketones with general formula (CH(3))(2)NCR(1)CR(2)C(O)CF(3), R(1)H, R(2)CH(3) (2); R(1)CH(3), R(2)H (3) were investigated in various pure solvents. For comparison results of earlier investigated enaminoketone R(1)H, R(2)H (1) were also presented. On the basis of NMR and IR spectra it was shown that enaminoketones 1 and 2 presented in solutions as an equilibrium of two conformers, (E-s-Z)⇌(E-s-E), whereas the enaminoketone 3 presented as equilibrium of two isomers, (E-s-Z)⇌(Z-s-Z). Quantum chemical calculations by the DFT methods were carried out to evaluate relative energy and dipole moment of each spatial form. For both (E-s-Z) and (E-s-E) conformer of the 1 and 2 the main influence on the ν(C=O) vibrations has the solvents hydrogen bond donor (HBD) acidity whereas for the 3 influence of the solvents polarity/polarizability dominated. Both the solvents polarity/polarizability and solvents hydrogen bond donor (HBD) acidity influenced on the ν(C=C) mode of the conformers of the 1 and 2. Solvent influence on the ν(C=C) vibrations of the 3 depended substantially whether the solvent is aprotic or an alcohol. In the former case the main contribution made the solvents hydrogen bond acceptor (HBA) basicity [(E-s-Z) isomer] or the solvents polarity/polarizability with solvents hydrogen bond donor (HBD) acidity [(Z-s-Z) isomer]. Alcohols influenced on the ν(C=C) vibrations of both isomers predominantly due to the solvents polarity/polarizability. In aprotic solvents the greatest contribution in solvent influence on thermodynamic parameters of both (E-s-Z)⇌(E-s-E) and (E-s-Z)⇌(Z-s-Z) equilibrium made the solvents hydrogen bond acceptor (HBA) basicity. Rotation around double C=C bond is characterized by higher sensitivity to the solvents hydrogen bond acceptor (HBA) basicity compared to the rotation around formally single C-C=O bond.

Solvent influence on the infrared spectra of β-alkoxyvinyl methyl ketones: II. Stretching vibrations and integrated intensities of carbonyl and vinyl bands of (3Z,E)-4-ethoxy-1,1,1-trifluoro-5,5-dimethylhex-3-en-2-one

Infrared spectroscopy studies of beta-alkoxyvinyl trifluoromethyl ketone, with structure C(2)H(5)O-C(C(CH(3))(3))CH-COCF(3) (1), in twenty three different pure organic solvents were undertaken to investigate the solvent-solute interactions and to correlate solvent properties such as Reichards parameter and solvatochromic parameters of Kamlet, Abbot, and Taft with carbonyl and vinyl stretching vibrations and their integrated intensities of existing spatial forms. It was shown that conjugation in CC-CO system of the (E-s-Z-o-Z) stereoisomer is higher than that in this system of the (Z-s-Z-o-Z) stereoisomer. From derived correlations of the v (CO) and v (CC) wavenumbers with solvatochromic parameters of Kamlet, Abbot, and Taft it is followed that the solvent polarity influences on the v (CO) and v (CC) wavenumbers more intense than the solvent HBD acidity, and, at the same time, the influence of these solvent properties is greater for the (E-s-Z-o-Z) stereoisomer. Analysis of derived KAT multiple regressions showed that the increase of the solvent polarity/polarizability (pi*) increased the conjugation in both stereoisomers, whereas the increase of the solvent HBD acidity (alpha) had opposite effect on conjugation in the (Z-s-Z-o-Z) and (E-s-Z-o-Z) stereoisomer. In the former case conjugation was weakened, whereas in the latter it was enhanced. These discrepancies were the consequence of different structure of H-bonded complexes between enone 1 and HBD solvents. The influence of the solvent HBA basicity (beta) also had peculiarity. The increase of the solvent HBA basicity disturbs the CC-CO conjugation in the (Z-s-Z-o-Z) stereoisomer due to carbonyl rotation, whereas in the (E-s-Z-o-Z) stereoisomer such increase enhanced this conjugation and, hence, increased the v (CO) and v (C==C) coupling.

The conformational analysis of push–pull enaminoketones using Fourier transform IR and NMR spectroscopy, and quantum chemical calculations: II. β-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 solvents 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 solvents atomic and electronic polarization and dispersive interactions.