DPPH (= 2,2-Diphenyl-1-picrylhydrazyl) Radical-Scavenging Reaction of Protocatechuic Acid (= 3,4-Dihydroxybenzoic Acid): Difference in Reactivity between Acids and Their Esters

• Published in: Helvetica chimica acta 2006-07, Vol.89 (7), p.1395-1407
• Main Authors: Saito, Shizuka, Kawabata, Jun
• Format: Article
• Language: English
• Subjects: Antioxidants; DPPH Radical; Protocatechuic acid; Radical-scavenging mechanism
• ISSN: 0018-019X; 1522-2675
• DOI: 10.1002/hlca.200690139

Protocatechuic acid (= 3,4‐dihydroxybenzoic acid; 1) exhibits a significantly slow DPPH (= 2,2‐diphenyl‐1‐picrylhydrazyl) radical‐scavenging reaction compared to its esters in alcoholic solvents. The present study is aimed at the elucidation of the difference between the radical‐scavenging mechanisms of protocatechuic acid and its esters in alcohol. Both protocatechuic acid (1) and its methyl ester 2 rapidly scavenged 2 equiv. of radical and were converted to the corresponding o‐quinone structures 1a and 2a, respectively (Scheme). Then, a regeneration of catechol (= benzene‐1,2‐diol) structures occurred via a nucleophilic addition of a MeOH molecule to the o‐quinones to yield alcohol adducts 1f and 2c, respectively, which can scavenge additional 2 equiv. of radical. However, the reaction of protocatechuic acid (1) beyond the formation of the o‐quinone was much slower than that of its methyl ester 2. The results suggest that the slower radical‐scavenging reaction of 1 compared to its esters is due to a dissociation of the electron‐withdrawing carboxylic acid function to the electron‐donating carboxylate ion, which decreases the electrophilicity of the o‐quinone, leading to a lower susceptibility towards a nucleophilic attack by an alcohol molecule.