Efeito da ligação de hidrogênio intramolecular na estabilidade conformacional de amino álcoois acíclicos 1,3-dissubstituídos por cálculos DFT, RMN e IV

Abstract

The conformational analysis covers aspects of the determination of molecular geometric structures, relative energies of conformers and interactions that control structural stabilities. In this sense, the conformational preferences of the compounds (1), 3-N-methylaminopropanol (2), 3-N,N-dimethylaminopropanol (3), 3-aminobutanol (4), 3-N-methylaminobutanol (5) and 3-N,N-dimethylaminobutanol (6) are evaluated experimentally through Infrared (IR) and Nuclear Magnetic Resonance (NMR) spectroscopies and theoretically by calculations using the Density Functional Theory (DFT). The study of these compounds was important because it will improve the understanding of the interactions that occur in these molecules in different chemical environments, since there is a wide range of amino alcohols with biological and synthetic applications. In view of this, theoretical calculations showed that the O-H···N intramolecular hydrogen bonding (IHB) governs the stability and the conformational preference of compounds 1-6. The IHB favors the formation of a chair like six member ring with substituents at pseudo-equatorial-axial positions, which exhibit repulsive interactions that also contribute significantly to the conformational stability, especially of compounds 4-6. The IR experimental results showed a OH band red shift of 193, 225, and 256 cm-1 for compounds 1, 2 and 3, respectively. These results were surprising and indicated that the strength of IHB increases in this order although the steric effect also increases. A first methodology for calculating the experimental molar fraction of hydrogen-bonded conformers (XIHB), in any solvent by 1H NMR, was proposed to attend 1,3-disubstituted acyclic compounds. The XIHB results showed that in non-polar solvents, such as CCl4 solvent, the hydrogen-bonded conformers predominate in the conformational equilibria (XIHB = 0.70, 0.69 and 0.78 for compounds 1-3). In polar solvents, such as DMSO-d6, the XIHB values decrease (0.10, 0.08 and 0.08 in compounds 1-3) indicating a change in conformational equilibria from hydrogenbonded conformers to non-hydrogen-bonded conformers. Quantum Theory of Atoms in Molecules and Non-Covalent Interactions analysis evidences, characterizes and quantifies the strength of IHB in compounds 1-6. These results agreed with the experimental data and indicated that both IHB and steric interactions significantly influence the conformational stability of all compounds studied.