Fenton's reagent. IV. Structure and reactivity relations in the reactions of hydroxyl radicals and the redox reactions of radicals

Journal Article · Tue Jan 01 04:00:00 EST 1974 · J. Amer. Chem. Soc., v. 96, no. 1, pp. 133-139

DOI:https://doi.org/10.1021/ja00808a022· OSTI ID:4370461

Walling, C; El-Taliawi, G M; Johnson, R A

Reactivities of a variety of alcohols, ethers, and amides toward hydroxyl radicals have been examined. Results are in encouraging agreement with radiation chemistry results. Reactivities of different C- H bonds have been dissected from the data and indicate that the hydroxyl radical is a strongly electrophilic species, so that electron supply is more important than C--H bond strength in determining reactivity. Comparison with gas-phase data shows similar reactivity patterns, but considerably faster reactions in H/sub 2/O. Radicals alpha to --OH, --OR, and amide N are readily oxidized by Fe/sup 3+/; tert-alkyl radicals are oxidized with more difficulty and allyl radicals hardly at all. In contrast, radicals RC (OH)CCl/sub 3/ are reduced by Fe/sup 2+/. Results are consistent with a fast oxidation of easily oxidized radicals by Fe/sup 3+/ via electron transfer, and a slower more general oxidation of radicals by Cu/sup 2+/ via a RCu(III) intermediate. (auth)

• Research Organization: Univ. of Utah, Salt Lake City
• Sponsoring Organization: USDOE
• NSA Number: NSA-29-012589
• OSTI ID: 4370461
• Journal Information: J. Amer. Chem. Soc., v. 96, no. 1, pp. 133-139, Journal Name: J. Amer. Chem. Soc., v. 96, no. 1, pp. 133-139; ISSN JACSA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

*HYDROXYL RADICALS-- CHEMICAL REACTIONS
ACETIC ACID
ACETONE
ALKYL RADICALS
ALLYL RADICALS
AMIDES
BUTANOLS
CATIONS
CHEMICAL BONDS
DIOXANE
ETHERS
IRON COMPOUNDS
METHANOL
N40300* --Chemistry--Radiation Chemistry
OXIDATION
PROPANOLS
REDUCTION
WATER