Ammoxidation of Lignocellulosic Materials: Formation of Nonheterocyclic Nitrogenous Compounds from Monosaccharides

Ammoxidized technical lignins are valuable soil-improving materials that share many similarities with native terrestrial humic substances. In contrast to lignins, the chemical fate of carbohydrates as typical minor constituents of technical lignins during the ammoxidation processes has not been thoroughly investigated. Recently, we reported the formation of N-heterocyclic, ecotoxic compounds (OECD test 201) from both monosaccharides (D-glucose, D-xylose) and polysaccharides (cellulose, xylan) under ammoxidation conditions and showed that monosaccharides are a source more critical than polysaccharides in this respect. GC/MS-derivatization analysis of the crude product mixtures revealed that ammoxidation of carbohydrates which resembles the conditions encountered in nonenzymatical browning of foodstuff affords also a multitude of nonheterocyclic nitrogenous compounds such as aminosugars, glycosylamines, ammonium salts of aldonic, deoxyaldonic oxalic and carbaminic acids, urea, acetamide, alpha-hydroxyamides, and even minor amounts of alpha-amino acids. D-Glucose and D-xylose afforded largely similar product patterns which differed from each other only for those products that were formed under preservation of the chain integrity and stereoconfiguration of the respective monosaccharide. The kinetics and reaction pathways involved in the formation of the different classes of nitrogenous compounds under ammoxidation conditions are discussed.