Fishing antioxidant 4-hydroxycoumarin derivatives: synthesis, characterization, and in vitro assessments

Can J Physiol Pharmacol. 2024 Jun 1;102(6):361-373. doi: 10.1139/cjpp-2023-0455. Epub 2024 Mar 6.

Abstract

Coumarins represent a diverse class of natural compounds whose importance in pharmaceutical and agri-food sectors has motivated multiple novel synthetic derivatives with broad applicability. The phenolic moiety in 4-hydroxycoumarins underscores their potential to modulate the equilibrium between free radicals and antioxidant species within biological systems. The aim of this work was to assess the antioxidant activity of 18 4-hydroxycoumarin coumarin derivatives, six of which are commercially available and the other 12 were synthesized and chemically characterized and described herein. The 4-hydroxycoumarins were prepared by a two steps synthetic strategy with satisfactory yields. Their antioxidant potential was evaluated through three in vitro methods, two free radical-scavenging assays (DPPH• and ABTS•+) and a metal chelating activity assay. Six synthetic coumarins (4a, 4g, 4h, 4i, 4k, 4l) had a scavenging capacity of DPPH• higher than butylated hydroxytoluene (BHT) (IC50 = 0.58 mmol/L) and compound 4a (4-hydroxy-6-methoxy-2 H-chromen-2-one) with an IC50 = 0.05 mmol/L outperformed both BHT and ascorbic acid (IC50 = 0.06 mmol/L). Nine hydroxycoumarins had a scavenging capacity against ABTS•+ greater (C3, 4a, 4c) or comparable (C1, C2, C4, C6, 4g, 4l) to Trolox (IC50 = 34.34 µmol/L). Meanwhile, the set had a modest ferrous chelation capacity, but most of them (C2, C5, C6, 4a, 4b, 4h, 4i, 4j, 4k, 4l) reached up to more than 20% chelating ability percentage. Collectively, this research work provides valuable structural insights that may determine the scavenging and metal chelating activity of 4-hydroxycoumarins. Notably, substitutions at the C6 position appeared to enhance scavenging potential, while the introduction of electron-withdrawing groups showed promise in augmenting chelation efficiency.

Keywords: ABTS; DPPH; antiradical; hydroxycoumarins; metal chelation; radical scavenger.

MeSH terms

  • 4-Hydroxycoumarins* / chemical synthesis
  • 4-Hydroxycoumarins* / chemistry
  • 4-Hydroxycoumarins* / pharmacology
  • Antioxidants* / chemical synthesis
  • Antioxidants* / chemistry
  • Antioxidants* / pharmacology
  • Benzothiazoles
  • Biphenyl Compounds / chemistry
  • Chelating Agents / chemical synthesis
  • Chelating Agents / chemistry
  • Chelating Agents / pharmacology
  • Free Radical Scavengers* / chemical synthesis
  • Free Radical Scavengers* / chemistry
  • Free Radical Scavengers* / pharmacology
  • Picrates / chemistry
  • Structure-Activity Relationship
  • Sulfonic Acids / chemistry

Substances

  • 4-Hydroxycoumarins
  • Antioxidants
  • Free Radical Scavengers
  • 1,1-diphenyl-2-picrylhydrazyl
  • Picrates
  • 2,2'-azino-di-(3-ethylbenzothiazoline)-6-sulfonic acid
  • Chelating Agents
  • Biphenyl Compounds
  • Sulfonic Acids
  • 4-hydroxycoumarin
  • Benzothiazoles