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ABSTRACT
The keto-enol tautomerization of chrysophanol anthrone was systematically investigated via a series of density functional theory computations using the M06-2X/6-31 + G(d,p) level of theory. Bulk solvent effects were taken into account implicitly using the polarisable continuum model and explicitly with one pyridine molecule. Moreover, the tautomeric equilibrium was estimated by calculating the equilibrium constant. The pyridine-assisted tautomerism was found to be the energetically preferred pathway, where the pyridine acts as a proton carrier through a two-step reaction, in which the first one corresponds to the deprotonation of the chrysophanol anthrone and the second step to the protonation yielding the enol form. The results show, in accordance with experimental reports, that in the process of dissociation of the protonated pyridine and the aryloxylate anion, the ion is quite susceptible to oxidation. The highly dipolar structures of the transition states and intermediates are stabilised by pyridine up to 7.0 kcal/mol. The non-covalent interactions stabilising the transition states and the intermediates were analysed. Additionally, an intermolecular hydrogen bonding between the enol form of chrysophanol anthrone and the pyridine is formed at the last stage of the reaction. The keto-enol equilibrium analysis shows that the enol form of chrysophanol anthrone must be present in small amounts in basic solvents.
Acknowledgements
This work was funded by grant FQUI-2014-0005 provided by Facultad de Química, UADY. We are also grateful to DGSCA, UNAM for supercomputer time. Part of this paper was taken from the bacheloŕs thesis of Fernando J. Tun Rosado.
Disclosure statement
No potential conflict of interest was reported by the authors.