Reaction of hydrocarbons with tert.-butoxy radicals

Inhibition of the Autoxidation of Organic Substances in the Liquid Phase.

“…and therefore the relative ease of oxidation of different substrates can be correlated with the relative rates of reaction 18 (54,55). Peroxy radicals can also abstract a hydrogen atom, particularly one in the ,&position, by an intramolecular process (278) and can add to olefinic double bonds (187, 223, 224, 231, 272).…”

THE REACTION OF tert-BUTOXY RADICALS WITH 2,6-Di-tert-BUTYL-4-METHYLPHENOL AND 2,6-Di-tert-BUTYLPHENOL

“…They might be produced either by the deoxygenation of t-butoxy radicals or by an assymetric decomposition of the peroxide. The addition of BhIP or B P a t a comparable concentration to the peroxide greatly simplifies the products since reaction [2] now predominates over reaction [4] and the yield of methyl radicals is thereby greatly reduced. The decon~position of the peroxide is still a first-order reaction but the rate of decomposition is slightly increased by an excess of the phenol (see Fig.…”

“…The t-bu toxy radical is particularly suitable for studying the relative rates of reaction [2] with different substrates since it may either abstract a hydrogen to give t-butanol o r decdmpose t o give acetone and a methyl radical. The ratio, [t-butanol]/[acetone], produced in different substrates therefore gives a measure of the relative rates of hydrogen abstraction fro-m the substrates.…”

“…The ratio, [t-butanol]/[acetone], produced in different substrates therefore gives a measure of the relative rates of hydrogen abstraction fro-m the substrates. These radicals are readily prepared by the decomposition of di-t-butyl peroxide and the reactions can be represented by, This technique has been employed by a number of workers in recent years to measure the relative rates of hydrogen abstraction by t-butoxy radicals from a variety of substrates such as hydrocarbons (2)(3)(4)(5)(6)(7)(8)(9), ethers, (10, l l ) , alcohols (12), and amiiles (13,14). As a part of our general program for studying the inhibition of autoxidation by phenols (15)(16)(17) we considered that an examination of the reaction of t-butoxy radicals with phenols might throw considerable light on the overall mechanism of inhibition.…”

Catalyse Des Oxydations A Chaînes Ramifiées

“…Le reacteur est relie i# un reservoir(7) qui contient de I'oxygene sous une pression superieure a la pression totale existant dans le rkacteur. Celui-ci, ainsi que le reservoir(7) sont separks par un robinet V4 ii vis micrometrique normalement ferme. Lorsque, suite A I'oxydation, Poz tombe de 20 a 17 atm., on restaure Po, it 20 atm., en ouvrant momentanement le robinet V4.…”