Identification of an anthocyanin occurring in some red wines

• Published in: Phytochemistry (Oxford) Vol. 44; no. 7; pp. 1375 - 1382
• Main Authors: Bakker, Johanna, Bridle, Peter, Honda, Toshio, Kuwano, Harumitsu, Saito, Norio, Terahara, Norihiko, Timberlake, Colin F.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier Ltd 01-04-1997; Elsevier
• Subjects: anthocyanins; Biological and medical sciences; chemical constituents of plants; chemical structure; Fermented food industries; food composition; Food industries; fruits; Fundamental and applied biological sciences. Psychology; glucosides; malvidin 3-glucoside; spectral analysis; Vitis vinifera; vitisin a; wines; Wines and vinegars; Portugal; Southern Europe; Europe; NMR; anthocyanins; FAB mass spectrometry; Red wine; vitisin A; vitisidin A; Anthocyanin; Characterization; Molecular structure; Vitidaceae; Dicotyledones; Grape; Angiospermae; Aglycone; Pigments; Isolation; Spermatophyta
• ISSN: 0031-9422; 1873-3700
• DOI: 10.1016/S0031-9422(96)00707-8

An anthocyanin-type pigment, vitisin A, was found in small amounts in some red wines and at trace levels in stored grapes. HPLC and spectrophotometric analysis showed that vitisin A exhibited a unique UV-Vis spectrum. Vitisin A was isolated, purified and identified using FAB mass spectrometry and NMR. The aglycone, vitisidin A, is 68 mass units greater than malvidin, accounted for by an additional C
3O
2 substituent. Further accurate mass determinations and NMR studies of both malvidin 3-glucoside and vitisin A confirmed that vitisin A is based on malvidin 3-glucoside with an additional C
3O
2 between position 4 and the 5-hydroxyl of the molecule. Five different isomers were distinguished by NMR, namely the flavylium cation, quinonoidal base, chalcone form and two carbinol pseudobases. The assignment of one of the protons remains tentative due to the rapid hydrogen/deuterium exchange. The structure was determined to be 3-formyl-4-
d-β-glucopyranosyloxy-8-hydroxy-5-(4-hydroxy-3,5-dimethoxy)phenyl-2-oxo-1,6-dioxa-2,3-dihydrophenalene.