Abstract
The molecular geometry and electronic structure of hydroxy-substituted naphthazarin (NZ)-7-ethyl-2,3,5,6,8-pentahydroxy-1,4-naphthoquinone (echinochrome A, (Et)NZ(β-OH)3, 1) were calculated by the B3LYP/6-311G(d) method. The influence of the (i) character of the β-OH groups dissociation and (ii) conformational mobility of molecule 1 and the anions, radicals, and radical anions derived from 1 on the energy of their reactions with hydroperoxyl radical was studied by the (U)B3LYP/6-31G and (U)B3LYP/6-311G(d) methods. The enol-enolic tautomerism due to the transfer of hydrogen atoms of α-OH groups and rotational isomerism of the β-OH groups at the C(2) and C(3) atoms and of the α-OH groups at the C(5) and C(8) atoms were studied. The equilibrium in the gas-phase reaction 1 + •OOH ⇄ (Et)(HO-β)2NZ(β-O•) + HOOH (1) (quenching of hydroperoxyl radical) is shifted to the separated reagents. Heterolysis of the O—H bond in one of the three β-hydroxy groups considerably reduces the energy of subsequent O—H bond homolysis in either of the two remaining β-hydroxy groups. As a consequence, the reaction (Et)(HO-β)2NZ(β-O−) + •OOH ⇄ (Et)(HO-β,−O-β)NZ(β-O•) + HOOH (2) (quenching of hydroperoxyl radical) becomes exothermic and the equilibrium is shifted to the formation of hydrogen peroxide. The Gibbs energy gain in reaction (2) varies from −6.4 to −10.9 kcal mol−1 depending on which β-hydroxy group is involved in the O—H bond homolysis.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 400–415, March, 2007.
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Berdyshev, D.V., Glazunov, V.P. & Novikov, V.L. 7-Ethyl-2,3,5,6,8-pentahydroxy-1,4-naphthoquinone (echinochrome A): A DFT study of the antioxidant mechanism. 1. Interaction of echinochrome A with hydroperoxyl radical. Russ Chem Bull 56, 413–429 (2007). https://doi.org/10.1007/s11172-007-0067-3
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DOI: https://doi.org/10.1007/s11172-007-0067-3