Electrochemical transformations and antiradical activity of asymmetrical RS-substituted pyrocatechols

Journal Article · Mon Oct 15 04:00:00 EDT 2018 · Russian Chemical Bulletin

DOI:https://doi.org/10.1007/S11172-018-2299-9· OSTI ID:22943438

Pitikova, O. V. ^[1]; Poddel’sky, A. I. ^[2]; Berberova, N. T. ^[3]

---

1. Ingineering Centre LLC “Gazprom dobycha Astrakhan,” (Russian Federation)
2. Russian Academy of Sciences, G. A. Razuvaev Institute of Organometallic Chemistry (Russian Federation)
3. Astrakhan State Technical University (Russian Federation)

Redox transformations of sulfides 1–8 combining a fragment of sterically hindered pyrocatechol with alkyl, cycloalkyl, and aromatic substituents were studied. The first step of electrooxidation of thioethers affords o-benzoquinones. The introduction of the redox-active thioether group extends the range of redox properties of pyrocatechols. In the second step, the thioether fragment is involved in the quasi-reversible anodic process, and the number of electrons participating in the electrode reaction depends on the structure of the hydrocarbon group bonded to the sulfur atom. The reactivity of compounds 1–8 toward O{sub 2}{sup •–} was evaluated on the basis of the electrochemical data. Cyclopentyl, phenyl, or benzyl substituents in the thioether group exert a greater effect on the antiradical activity than the alkyl moieties. The formation of an o-semiquinolate radical anion in the reaction of pyrocatechol thioethers with KO{sub 2} was detected by the ESR method. It was shown using the reaction with the stable 2,2-diphenyl-1-picrylhydrazyl radical as an example that RS-functionalized pyrocatechols show a higher antiradical activity compared to 3,5-di-tert-butylpyrocatechol.

• OSTI ID: 22943438
• Journal Information: Russian Chemical Bulletin, Journal Name: Russian Chemical Bulletin Journal Issue: 10 Vol. 67; ISSN RCBUEY; ISSN 1066-5285
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANIONS
ATOMS
BENZOQUINONES
COMPARATIVE EVALUATIONS
ELECTROCHEMISTRY
ELECTRON SPIN RESONANCE
ORGANIC SULFUR COMPOUNDS
PYROCATECHOL
RADICALS
REACTIVITY
SULFIDES
SULFUR