Kinetic investigations of sulfite addition to flavanols

Flavanols are an important class of natural products occurring in almost all plants, fruits and vegetables; they have a great influence on wine ageing potential, astringency, colour stability and biological activities. In wine, flavanols react with sulfur dioxide (SO2), the most widely used preservative in oenology, leading to sulfonated products. Here we report a kinetic investigation, through LC-MS quantitative measurements carried out at different pH (3 and 4) and temperature values (23, 30, 40, 50 and 60∘C), of the reaction products obtained by SO2 addition to both monomeric (epicatechin and catechin) and dimeric flavanols (procyanidin B2 and procyanidin B3). The results proved that: (a) the major sulfonation route that leads quickly and in good yields to monomeric 4β-sulfonated derivatives passes through the acid-catalysed depolymerisation of proanthocyanidins; (b) monomeric flavanols lead to the same 4β-sulfonated products, although in a considerably slower manner, and also to other sulfonated regioisomers; (c) the kinetic data in our hands, in particular the temperature dependence of the observed rates, suggest the involvement of two completely different reaction mechanisms for the SO2 addition to dimeric and monomeric flavanol substrates; (d) direct sulfonation of epicatechin is slightly faster than that of catechin.