The reactivities of novel heterocyclic diarylamine radical-trapping antioxidants (RTAs) are profiled in a heavy hydrocarbon at 160 °C, conditions representative of those at which diphenylamine RTAs are used industrially. While carboxylic acids produced during the autoxidation are shown to deactivate these more basic RTAs, the addition of a sacrificial base leads to efficacies that are unprecedented in the decades of academic and industrial research in this area.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/ja5124144 | DOI Listing |
J Org Chem
December 2023
Department of Chemistry and Biomolecular Sciences, University of Ottawa, 10 Marie Curie Pvt., Ottawa K1N 6N5, Ontario, Canada.
Molybdenum dithiocarbamates (MDTCs) are indispensable lubricant additives. Although their role as antiwear agents is well established, they have also been attributed antioxidant properties that are not understood. MDTCs do not inhibit autoxidation, but they markedly enhance the capacity of diphenylamines (DPAs)─ubiquitous radical-trapping antioxidants (RTAs)─to do so.
View Article and Find Full Text PDFChem Sci
August 2021
Department of Chemistry and Biomolecular Sciences, University of Ottawa 10 Marie Curie Pvt. Ottawa Ontario K1N 6N5 Canada
The prediction and/or rationalization of diarylamine radical-trapping antioxidant (RTA) activity at the elevated temperatures where they are most useful presents a significant challenge, precluding the development of new technology. Whilst structure-activity relationships at ambient temperatures are well established, their predictive capacity at elevated temperatures is poor due to competing reactions. A striking example involves phenoxazine, which is a superior RTA relative to its sulfur analog phenothiazine at ambient temperature ( = 3.
View Article and Find Full Text PDFJ Org Chem
May 2021
Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario, Canada K1N 6N5.
Alkylated diphenylamines are among the most efficacious radical-trapping antioxidants (RTAs) for applications at elevated temperatures since they are able to trap multiple radical equivalents due to catalytic cycles involving persistent diphenylnitroxide and diphenylaminyl radical intermediates. We have previously shown that some heterocyclic diarylamine RTAs possess markedly greater efficacy than typical alkylated diphenylamines, and herein, report on our efforts to identify optimal alkyl substitution of the scaffold, which we had found to be the ideal compromise between reactivity and stability. Interestingly, the structure-activity relationships differ dramatically with temperature: -alkyl substitution slightly increased reactivity and stoichiometry at 37 and 100 °C due to more favorable (stereo)electronic effects and corresponding diarylaminyl/diarylnitroxide formation, while -alkyl substitution slightly decreased both reactivity and stoichiometry.
View Article and Find Full Text PDFJ Am Chem Soc
August 2020
Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON K1N 6N5, Canada.
Nitroxides were recently shown to catalyze the cross-dismutation of alkylperoxyl and hydroperoxyl radicals, making them uniquely effective radical-trapping antioxidants (RTAs) in unsaturated hydrocarbons where both species are formed. Given the abundance of unsaturated lipids in biological membranes, the continuous generation of hydroperoxyl (superoxide) as a byproduct of aerobic respiration, and the demonstrated cytoprotective properties of some nitroxides, we probed if cross-dismutation operates in phospholipid bilayers and cell culture. Interestingly, only nitroxides that were efficiently converted to amines in situ were effective, with their activity paralleling the stability of the incipient aminyl radicals.
View Article and Find Full Text PDFAcc Chem Res
September 2018
Department of Chemistry and Biomolecular Sciences , University of Ottawa, 10 Marie Curie Pvt. Ottawa , ON K1N 6N5 , Canada.
Autoxidation, the free radical chain reaction that nominally inserts O into hydrocarbons to give peroxides, is primarily responsible for the degradation of all organic materials. Peroxyl radicals propagate autoxidation mainly by abstraction of labile H-atoms from the hydrocarbons, whereas radical-trapping antioxidants (RTAs) inhibit autoxidation by donating an H-atom to the peroxyl radical to give a nonpropagating radical. As such, a detailed understanding of the kinetics and thermodynamics of H-atom transfer (HAT) reactions to peroxyl radicals, and the effects of sterics, electronics, and medium thereupon, is key to understanding the mechanisms and products of autoxidation and the ability of RTAs to inhibit it.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!