title: Reactivity of anthocyanins and pyranoanthocyanins. Studies on aromatic hydrogen-deuterium exchange reactions in methanol.
abstract: Reactivity studies involving anthocyanin structures and their equilibrium forms will lead to better understanding of the properties of these antioxidants. Hydrogen-deuterium (H --> D) exchange reactions at various sites of the 3-glucosides of delphinidin (1), petunidin (2), malvidin (3), and the corresponding 3-glucosides of carboxypyranodelphinidin (4), carboxypyranopetunidin (5), carboxypyranomalvidin (6), and the flavonol quercetin 3-O-(6-alpha-rhamnopyranosyl-beta-glucopyranoside)(7) have been examined at room temperature in pure CD 3OD and in CD 3OD acidified with CF 3CO 2D. The H --> D exchange rate constants of H-6 and H-8 of 2 determined from (1)H NMR integration data were found to be independent upon pigment concentration (up to 4 x 10 (-2) M) and trifluoroactic acid concentration (0-15%, v/v), respectively. This suggest that these reactions follow first-order kinetics and unexpectedly to be independent of the acid concentration. H-6 and H-8 of the flavylium cation A-rings of 1- 3, and in the corresponding hydrogens of the hemiketal forms, exchanged with half-lives of approximately 100 h ( 1) and approximately 50 h ( 2 and 3), respectively. The pyranoanthocyanins (4-6) experienced no H --> D exchange for the analogous hydrogens, but H --> D exchange of H-beta (H-4)(t 1/2 approximately 25 h) for these compounds was observed. Only H-8 underwent significant H --> D exchange in 7. It is concluded that a stabilization of the sigma-complexes, assumed to be the intermediates in the reactions, takes place for the common anthocyanins (1-3) contrary to the pyranoanthocyanins (4-6).
authors.affiliation: Department of Chemistry, University of Bergen, Allégt. 41, 5007, Bergen, Norway.
authors.forename: Monica
authors.initials: M
authors.lastname: Jordheim
authors.forename: Torgils
authors.initials: T
authors.lastname: Fossen
authors.forename: Jon
authors.initials: J
authors.lastname: Songstad
authors.forename: Øyvind M
authors.initials: ØM
authors.lastname: Andersen
mesh_terms: D000872:Anthocyanins / Q000737:chemistry*; D000975:Antioxidants / Q000737:chemistry*; D041961:Deuterium Exchange Measurement; D009682:Magnetic Resonance Spectroscopy; D000432:Methanol / Q000737:chemistry; D009812:Odorants; D012431:Rutin / Q000737:chemistry
chemical_list: D000872:Anthocyanins; D000975:Antioxidants; D012431:Rutin; D000432:Methanol