Formation of 4-Hydroxy-2,5-dimethyl-3(2H)-furanone and 4-Hydroxy-2(or 5)-ethyl-5(or 2)-methyl-3(2H)-furanone through Maillard Reaction Based on Pentose Sugars

The caramel-like smelling compounds 4-hydroxy-2,5-dimethyl-3(2 H )-furanone (HDMF) and 4-hydroxy-2(or 5)-ethyl-5(or 2)-methyl-3(2 H )-furanone (HEMF) were identified by GC−MS and GC−MS/MS in Maillard reaction systems based on pentoses. The reaction was performed in a phosphate buffer by heating xylose, ribose, or arabinose with glycine or l -alanine at 90 °C for 1 h. HEMF was detected in the system pentose/alanine. HDMF was formed in both pentose/glycine and pentose/alanine systems as well as directly from pentoses. Experiments using 13 C-labeled glycine and alanine suggest the incorporation of the Strecker degradation products formaldehyde and acetaldehyde into the pentose moiety, forming the furanones HDMF and HEMF, respectively. The presence of 12 C-HDMF, which was approximately 30% of the total HDMF amount found in xylose/glycine, indicates that HDMF is partly formed by sugar fragmentation. The proposed mechanism for the formation of the furanones is based on decomposition of the Amadori compound via 2,3-enolization, chain elongation by the Strecker aldehydes, and reduction of the resulting acetylformoin-type intermediates to the target molecules.