Abstract
Oxidation of quercetin by air oxygen takes place in water and aqueous ethanol solutions under mild conditions, namely in moderately-basic media (pH approximately 8-10) at ambient temperature and in the absence of any radical initiators, without enzymatic catalysis or irradiation of the reaction media by light. The principal reaction products are typical of other oxidative degradation processes of quercetin, namely 3,4-dihydroxy-benzoic (proto-catechuic) and 2,4,6-trihydroxybenzoic (phloroglucinic) acids, as well as the decarboxylation product of the latter--1,3,5-trihydroxybenzene (phloroglucinol). In accordance with the literature data, this process involves the cleavage of the gamma-pyrone fragment (ring C) of the quercetin molecule by oxygen, with primary formation of 4,6-dihydroxy-2-(3,4-dihydroxybenzoyloxy)benzoic acid (depside). However under such mild conditions the accepted mechanism of this reaction (oxidative decarbonylation with formation of carbon monoxide, CO) should be reconsidered as preferably an oxidative decarboxylation with formation of carbon dioxide, CO2. Direct head-space analysis of the gaseous components formed during quercetin oxidation in aqueous solution at ambient temperature indicates that the ratio of carbon dioxide/carbon monoxide in the gas phase after acidification of the reaction media is ca. 96:4%. Oxidation under these mild conditions is typical for other flavonols having OH groups at C3 (e.g., kaempferol), but it is completely suppressed if this hydroxyl group is substituted by a glycoside fragment (as in rutin), or a methyl substituent. An alternative oxidation mechanism involving the direct cleavage of the C2-C3 bond in the diketo-tautomer of quercetin is proposed.
Highlights
Quercetin [3,5,7,3′,4′-pentahydroxyflavone, 5,7,3′,4′-tetrahydroxyflavonol (1)] and its glycosides [e.g., 3-O-rhamnoside and especially 3-O-rutinoside] are among the most frequently mentioned natural flavonoids isolated from various plant extracts [1,2,3]
The first anomalous area at pH ≈ 7.2-7.1 was caused by the storage of the solution under titration during ca. 30 min; the second one was caused by its storage for one week
The reaction under consideration may be one of the general biotransformation paths of quercetin and other flavonols, and this process may explain the low concentrations of these compounds in blood in the presence of oxygen
Summary
Quercetin [3,5,7,3′,4′-pentahydroxyflavone, 5,7,3′,4′-tetrahydroxyflavonol (1)] and its glycosides [e.g., 3-O-rhamnoside (quercitrin) and especially 3-O-rutinoside (rutin)] are among the most frequently mentioned natural flavonoids isolated from various plant extracts [1,2,3]. Kaempferol Luteolin Fisetin Daidzein Myricetin Quercetin Rutin Table 1
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