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 ([Formula: see text]), 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 [Formula: see text]), of the reaction products obtained by [Formula: see text] 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 4[Formula: see text]-sulfonated derivatives passes through the acid-catalysed depolymerisation of proanthocyanidins; (b) monomeric flavanols lead to the same 4[Formula: see text]-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 [Formula: see text] addition to dimeric and monomeric flavanol substrates; (d) direct sulfonation of epicatechin is slightly faster than that of catechin.