Chemical radiolytic oxidation induced by OH addition on 1-(2-furan-2-yl-5-hydroxy6-hydroxymethyl-[1,3]dioxan-4-yl)-ethan-1,2-diol (sorbitylfurfural, SF) leads, in the presence of controlled amounts of oxygen, to a permanent functional modification of the target molecule. The yield of conversion reaches 60% of the starting material. LC-MS analysis allowed the identification, as final products, of carboxylic acids, butenal and hydroxy-furan derivatives in which the sugar chain remains unbroken, while the furanic ring is attacked first by OH and then by oxygen, giving in succession an intra-/inter-molecular rearrangement of the allylperoxyl radicals thus formed. The proposed oxidation of the furanic ring envisages the peroxyl intermediates undergoing mono- and/or bi-molecular reactions; a reaction path has been outlined and is reported here. The presence of unsaturated bonds in the final products could provide a further site for radical scavenger activity. Therefore, the fast reaction with O-2 and the rearrangement of the produced peroxyl radicals to species, which are likely to be effective OH-capturers, reinforces the antioxidant ability of SF.
OH radical oxidation of Sorbitylfurfural furanic ring to sugar derivatives, induced by radiolysis in aerobic environment.
2005
Abstract
Chemical radiolytic oxidation induced by OH addition on 1-(2-furan-2-yl-5-hydroxy6-hydroxymethyl-[1,3]dioxan-4-yl)-ethan-1,2-diol (sorbitylfurfural, SF) leads, in the presence of controlled amounts of oxygen, to a permanent functional modification of the target molecule. The yield of conversion reaches 60% of the starting material. LC-MS analysis allowed the identification, as final products, of carboxylic acids, butenal and hydroxy-furan derivatives in which the sugar chain remains unbroken, while the furanic ring is attacked first by OH and then by oxygen, giving in succession an intra-/inter-molecular rearrangement of the allylperoxyl radicals thus formed. The proposed oxidation of the furanic ring envisages the peroxyl intermediates undergoing mono- and/or bi-molecular reactions; a reaction path has been outlined and is reported here. The presence of unsaturated bonds in the final products could provide a further site for radical scavenger activity. Therefore, the fast reaction with O-2 and the rearrangement of the produced peroxyl radicals to species, which are likely to be effective OH-capturers, reinforces the antioxidant ability of SF.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
