Spectroscopic and electrochemical properties of hydroxylated derivatives of 2,6-dimethoxy-1,4-benzoquinone

Haleh, Haeri and Gulaboski, Rubin and Bogeski, Ivan and Mirceski, Valentin and Markus, Hoth and Reinhard, Kappl (2011) Spectroscopic and electrochemical properties of hydroxylated derivatives of 2,6-dimethoxy-1,4-benzoquinone. In: ESR Spectroscopy, The 44th Annual Meeting, 3-7 April 2011, York, England.

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Methoxy-substituted 1,4-benzoquinones are interesting models for the biologically
important compounds of the coenzyme Q family, which have a key function in electrontransfer
and redox processes. Partially substituted 1,4-benzoquinones are known to be
hydroxylated at quinoid positions in alkaline media, forming intermediate semiquinone
radicals accessible to EPR spectroscopy.
Recently, we observed that hydroxylation also occurs at the methoxy-substituted
positions of partially (2,6-dimethoxy-1,4-benzoquinone, Q0) and, particularly, of fully
substituted 1,4-benzoquinones (Q1, Q10) yielding mono- and di-hydroxylated products.
EPR and cyclic voltammetry are utilised to investigate the transformation mechanism,
the kinetics of radical formation and the electrochemical properties of intermediates and
products, focusing here on 2,6-dimethoxy-1,4-benzoquinone (2,6-bq). The experimental
results are complemented with DFT calculations.
The transformation of 2,6-bq at pH>12 proceeds via a mono-hydroxylated intermediate
inducing a radical on the parental compound. Its spectral EPR signature in liquid state at
room temperature is consistent with two OCH3-groups and two equivalent ring protons.
DFT methods indicate that hydrogen bonding is essential to obtain the correct isotropic
hyperfine couplings. In the time course of the reaction a secondary radical slowly
appears which lacks a methoxy-group, and, on the basis of its couplings, is assigned to
the di-hydroxylated form of the compound. From several possible structures, DFT
calculations clearly favour one configuration. The loss of an OCH3-group should be
accompanied by formation of methanol, which was demonstrated by NMR. The
spectroscopic changes are also monitored in cyclic voltammetry at high pH values.
After neutralizing the solvent, the hydroxylated compound reveals a more negative
redox potential, and, importantly, has a strong binding capacity for divalent ions such as
Ca2+ and Ba2+ in its reduced state. The 2:1 stoichiometry (Ca2+:2,6-bq) matches with a
di-hydroxylated compound and is confirmed by DFT calculations.
The detailed information derived from the model transformation reaction of 2,6-bq will
be useful to understand possible reactions of the more complex, biologically relevant

Item Type: Conference or Workshop Item (Poster)
Subjects: Natural sciences > Chemical sciences
Medical and Health Sciences > Health sciences
Natural sciences > Physical sciences
Divisions: Faculty of Agriculture
Depositing User: Rubin Gulaboski
Date Deposited: 18 Nov 2012 21:29
Last Modified: 18 Nov 2012 21:29
URI: https://eprints.ugd.edu.mk/id/eprint/1081

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