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

Journal Article · · J. Amer. Chem. Soc., v. 96, no. 1, pp. 133-139
DOI:https://doi.org/10.1021/ja00808a022· OSTI ID:4370461

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, Other Information: Orig. Receipt Date: 30-JUN-74
Country of Publication:
Country unknown/Code not available
Language:
English