Acid-Catalyzed Hydrolysis of Alcohols and Their β-d-Glucopyranosides

Abstract

The hydrolysis, in model wine at pH 3, of the allylic, homoallylic, and propargylic glycosides, geranyl-β-d-glucopyranoside, [3‘-(1‘ ‘-cyclohexenyl)-1‘-methyl-2‘-propynyl]-β-d-glucopyranoside, (3‘RS,9‘SR)-(3‘-hydroxy-5‘-megastigmen-7-yn-9-yl)-β-d-glucopyranoside, (3‘,5‘,5‘-trimethyl-3‘-cyclohexenyl)-β-d-glucopyranoside, E-(7‘-oxo-5‘,8‘-megastigmadien-3‘-yl)-β-d-glucopyranoside (3-hydroxy-β-damascone-β-d-glucopyranoside), and their corresponding aglycons has been studied. In general, aglycons were more rapidly converted to transformation products than were the corresponding glucosides. Glycoconjugation of geraniol in grapes is a process that reduces the flavor impact of this compound in wine, not only because geraniol is an important flavor component of some wines but also because the rate of formation of other flavor compounds from geraniol during bottle-aging is reduced. However, when flavor compounds such as β-damascenone are formed in competition with flavorless byproducts, such as 3-hydroxy-β-damascone, by acid-catalyzed hydrolytic reactions of polyols, then glycoconjugation is a process that could enhance as well as suppress the formation of flavor, depending on the position of glycosylation. (3‘RS,9‘SR)-(3‘-Hydroxy-5‘-megastigmen-7‘-yn-9‘-yl)-β-d-glucopyranoside hydrolyzed more slowly but gave a higher proportion of β-damascenone in the products than did the aglycon at 50 °C. Reaction temperature also effected the relative proportion of the hydrolysis products. Accelerated studies do not parallel natural processes precisely but only approximate them. Keywords: β-Damascenone; geraniol; monoterpenes; norisoprenoids; hydrolysis; glycosides; precursors