Structural analysis of oxidation products of urofuran acid by hypochlorous acid

The oxidation of urofuran acid derivatives (1-2) by hypochlorous acid (HOCl) was investigated with the goal to possibly simplify the detection of their metabolites in biological materials. The oxidation products of 3-carboxy-4-methyl-5-propyl-2-furanpropionic acid (1) were obtained as an isomeric mixture and confirmed to exist as cis (3a) and trans (3b) isomers, based on their 13C nuclear magnetic resonance (NMR) spectra. Similarly, the products of 5-H substituted acid 2 obtained by oxidation with HOCl were identified as 4a and 4b by 13C and 1H NMR which indicated the presence of cis and trans hemiacetal hydrogens at C-5 in a ratio of 2.11:1. The oxidation was found to proceed in a manner different from that of the F-acid, because of the presence of the electron withdrawing COOCH3 group at C-3 which favored the nucleophilic attack on the carbonyl group to afford cis- and trans-2,5-dihydroxy-2,5-dihydrofurans (3a-b, 4a-b).