Tert-butylperoxy Radical Research Articles

ChemInform Abstract: ON THE ACCURACY OF THE HYDROPEROXIDE METHOD OF DETERMINING ABSOLUTE RATE CONSTANTS FOR HYDROGEN ATOM ABSTRACTION BY THE TERT.‐BUTYLPEROXY RADICAL

Measurements of rates of oxygen absorption and steady-state peroxy radical concentrations for the autoxidation of tetralin in the presence of tert-butyl hydroperoxide have shown that the rate constant for reaction of the tert-butylperoxy radical with tetralin at 60°C is approximately 11.0 M−1s−1. This rate constant is about a factor of 4 larger than the value recently reported by Niki, Okayasu, and Kamiya for this reaction. The present work emphasizes that great care should be taken when the hydroperoxide method is used to estimate cross-propagation rate constants for a substrate as reactive as tetralin at a temperature as high as 60°C.

ChemInform Abstract: AN ELECTRON SPIN RESONANCE STUDY OF THE TERT.‐BUTYLSULFINYL RADICAL

The tert-butylsulfinyl radical, (CH3)3CSO•, can be prepared directly in the cavity of an e.p.r. spectrometer by photolysis of di-tert-butyl peroxide in a solution of tert-butylsulfenic acid in toluene or isopentane at low temperatures (−40° to−100°). The e.s.r. spectrum consists of a rather broad singlet (ΔHmis ∼ 1.9 G) with the field center at g = 2.0106.This radical undergoes self-reaction by a bimolecular process and a 2.5 × 10−7 M solution has a half-life of 0.07 s at −100 °C. It is, therefore, much shorter-lived than the iso-structural tert-butylperoxy radical, (CH3)3COO•.

ChemInform Abstract: ARRHENIUS PARAMETERS FOR REACTION OF TERT.‐BUTYLPEROXY RADICALS WITH SOME HINDERED PHENOLS AND AROMATIC AMINES

The reaction of tert-butylperoxy radicals with some 2,6-di-tert-butyl-4-substituted phenols, α-naphthol, α-naphthylamine, and N-phenyl-α-naphthylamine has been studied by following the change in radical concentration with time using an e.p.r. spectrometer. Rates of radical decay were first-order in both reactants and were not influenced by the presence of tert-butyl hydroperoxideAbsolute values of the second-order rate constants were measured from −35 to −100° and the preexponential factors and activation energies fell in the range 104–105 M−1 s−1 and 0.5–1.0 kcal mol−1. Rate constants for deuterated phenols (OD) and aromatic amines (ND) were an order of magnitude lower than for the corresponding light compoundsThere was no evidence for quantum mechanical tunneling in these hydrogen atom transfer reactions and it would appear that the activation parameters are low because reaction initially involves the formation of a hydrogen bonded peroxy radical – phenol (or aromatic amine) complex, followed by the tra...

An Electron Spin Resonance Study of the tert-Butylsulfinyl Radical

The tert-butylsulfinyl radical, (CH3)3CSO•, can be prepared directly in the cavity of an e.p.r. spectrometer by photolysis of di-tert-butyl peroxide in a solution of tert-butylsulfenic acid in toluene or isopentane at low temperatures (−40° to−100°). The e.s.r. spectrum consists of a rather broad singlet (ΔHmis ∼ 1.9 G) with the field center at g = 2.0106.This radical undergoes self-reaction by a bimolecular process and a 2.5 × 10−7 M solution has a half-life of 0.07 s at −100 °C. It is, therefore, much shorter-lived than the iso-structural tert-butylperoxy radical, (CH3)3COO•.

Arrhenius Parameters for Reaction of tert-Butylperoxy Radicals with some Hindered Phenols and Aromatic Amines

The reaction of tert-butylperoxy radicals with some 2,6-di-tert-butyl-4-substituted phenols, α-naphthol, α-naphthylamine, and N-phenyl-α-naphthylamine has been studied by following the change in radical concentration with time using an e.p.r. spectrometer. Rates of radical decay were first-order in both reactants and were not influenced by the presence of tert-butyl hydroperoxideAbsolute values of the second-order rate constants were measured from −35 to −100° and the preexponential factors and activation energies fell in the range 104–105 M−1 s−1 and 0.5–1.0 kcal mol−1. Rate constants for deuterated phenols (OD) and aromatic amines (ND) were an order of magnitude lower than for the corresponding light compoundsThere was no evidence for quantum mechanical tunneling in these hydrogen atom transfer reactions and it would appear that the activation parameters are low because reaction initially involves the formation of a hydrogen bonded peroxy radical – phenol (or aromatic amine) complex, followed by the transfer of a hydrogen atom within the complex

Absolute rate constants for the reaction of tert-butylperoxy radicals with some m- and p-substituted toluenes

Absolute rate constants for the reaction of tert-butylperoxy radicals with some m- and p-substituted toluenes

Absolute rate constants for the reaction of tert-butylperoxy radicals with trivalent phosphorus compounds

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAbsolute rate constants for the reaction of tert-butylperoxy radicals with trivalent phosphorus compoundsE. Furimsky and J. A. HowardCite this: J. Am. Chem. Soc. 1973, 95, 2, 369–374Publication Date (Print):January 1, 1973Publication History Published online1 May 2002Published inissue 1 January 1973https://doi.org/10.1021/ja00783a011RIGHTS & PERMISSIONSArticle Views131Altmetric-Citations37LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (586 KB) Get e-Alerts Get e-Alerts

Electron Spin Resonance Spectrum of the tert-Butylperoxy Radical, B16O17O•

A tert-butylperoxy radical specifically labelled with 17O on the terminal oxygen has been prepared by photolysis of di-tert-butyl peroxide in perdeuterocyclopentane containing 17O enriched oxygen. The value of the 17O hyperfine coupling constant is 23.45 G.

Antioxidants and stabilizers. XXIX. Reaction of 2,2'-methylenebis(4-methyl-6-tert-butyl phenol) with tert-butoxy and tert-butylperoxy radicals

Antioxidants and stabilizers. XXIX. Reaction of 2,2'-methylenebis(4-methyl-6-tert-butyl phenol) with tert-butoxy and tert-butylperoxy radicals

Radical reactions in the ligand field of metal complexes. II. Reactions of the tert-butylperoxy radical bound to cobalt(III)

Radical reactions in the ligand field of metal complexes. II. Reactions of the tert-butylperoxy radical bound to cobalt(III)