Formation of N-Substituted Pyrrole-2-Aldehydes in the Browning Reaction Between D-Xylose and Amino Compounds

SUMMARY– The formation of N -substituted pyrrole-2-aldehydes in the browning reaction between D-xylose and selected amino acids was investigated.
In order to facilitate the separation of the reaction products, the carbonyl compounds formed in the browning solution were converted into 2,4-dinitrophenylhydrazones (2,4-DNPs) and then esterified with diazomethane. Isolation of the esterified 2,4-DNP was accomplished by column chromatography with alumina. Chemical structures of the isolated 2,4-DNPs were confirmed by elementary analyses, ultraviolet and visible absorption spectra, and nuclear magnetic resonance spectra.
The following N -substituted pyrrole-2-aldehydes were isolated as methyl ester of 2,4-DNP, respectively: (2-formylpyrrol-I-ybacetic acid from the reaction mixture of D-xylose and glycine, 3-(2-formylpyrrol-1-y1)propionic acid from β-alanine, and 2-(2-formylpyrrol-1-y1)-4-methyl-valeric acid from L-leucine.
The extent of pyrrolealdehyde formation from D-xylose and selected alkylamine or amino acid was in the following order which corresponded to the extent of melanoidin formation: n-butylamine > methylamine, β-alanine > glycine > DL-alanine. N-substituted pyrrole-2-aldehyde was rather stable and was not considered to be an important intermediate of melanoidins. However, some correlationships between the formation of pyrrolealdehyde and that of melanoidins were demonstrated and discussed.