Formation of phenazines, phenoxazines, and benzoxazoles in the browning reactions of o-quinones

Abstract

Quinone-induced browning is widely produced in foods and is mostly considered a consequence of quinone/nucleophile reactions. However, even in the absence of amino acids or proteins, o-quinones develop browning. In an attempt to better understand the reaction pathways involved in this browning development, this study describes the reactions of 4-methyl-1,2-benzoquinone with alcohols, ammonia, and short chain aldehydes. These reaction mixtures developed browning at 37 °C and the main produced compounds were isolated by semipreparative HPLC and characterized by NMR and MS as phenazines, phenoxazines, and benzoxazoles. A reaction pathway that explains the formation of all these compounds is proposed. The formation of phenazines is responsible, at least partially, for the produced browning, and the formation of benzoxazoles inhibits such browning. Browning development seems to be a consequence of a competition among the reactions of formation of phenazines, phenoxazines, and benzoxazoles, which appear to be produced from a single intermediate.

Keywords: 4-Methyl-1,2-benzoquinone (PubChem ID: 123180); 4-Methylcatechol (PubChem ID: 9958); Benzaldehyde (PubChem ID: 240); Browning; Carbonyl-amine reactions; Carbonyl-phenol reactions; Crotonaldehyde (PubChem ID: 447466); Food carbonylome; Maillard reaction; Propanal (PubChem ID: 527); Reactive carbonyls.