Absolute rate constants for hydrocarbon autoxidation. 33. A product study of the self-reaction of α-tetralylperoxyls in solution

Baignée, A.; Chenier, J. H. B.; Howard, J. A.

doi:10.1139/v83-352

Cited by 11 publications

(2 citation statements)

References 25 publications

(31 reference statements)

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“…The product analysis (Table I) for induced decomposition of TOOH showed an excess of T=0 over TOH, in agreement with similar studies with chlorobenzene as solvent. 19 This excess can be ascribed to induced decomposition of TOOH19,20 or to oxidation of the alcohol to the ketone by TOO* or other radicals. The latter process can be represented by eq 9 and 10. ro2* + r,r2choh -ro2h + R,R2*COH (9) RiR2*COH + X* -* R,R2C=0 + XH (X* = R02', 02, H02•, etc.)…”

Section: Resultsmentioning

confidence: 99%

Relative yields of excited ketones from self-reactions of alkoxyl and alkylperoxyl radical pairs

Lee¹,

Mendenhall²

1988

J. Am. Chem. Soc.

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Section: Resultsmentioning

confidence: 99%

Relative yields of excited ketones from self-reactions of alkoxyl and alkylperoxyl radical pairs

Lee¹,

Mendenhall²

1988

J. Am. Chem. Soc.

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“…ke radical with oxygen. This reaction is nearly diffusion controlled, and the equilibrium lies toward the peroxy radical (23)(24)(25)(26)(27). Competition kinetic experiments have yielded values from 25 to 400 s"1 (30 °C) for ß (27).…”

Section: Introductionmentioning

confidence: 99%

A phospholipase C protocol for phospholipid peroxidation analysis

Wagner

Porter

1988

Chem. Res. Toxicol.

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A new method has been developed to analyze the primary products of phospholipid peroxidation. The procedure utilizes the ability of phospholipase C to hydrolyze phospholipid hydroperoxides to their corresponding diacylglycerol derivatives. 1-Palmitoyl-2-linoleoylphosphatidylcholine (1P,2L-GPC), 1-stearoyl-2-linoleoylphosphatidylcholine (1S,2L-GPC), and 1-stearoyl-2-arachidonylphosphatidylcholine (1S,2A-GPC) were autoxidized. The diacylglycerol hydroxides derived from the phosphatidylcholine hydroperoxides were separated by reverse-phase high-pressure liquid chromatography (RP-HPLC) and normal-phase high-pressure liquid chromatography (NP-HPLC). 1P,2L-diglyceride (1P,2L-DG) and 1P,2A-DG products were easily separated from 1S,2L-DG and 1S,2A-DG products by RP-HPLC. The linoleate diglyceride oxidation mixture was separated into the 13-trans/cis, 13-trans/trans, 9-trans/cis, and 9-trans/trans isomers by NP-HPLC. Likewise, 1P,2A-DG and 1S,2A-DG oxidation products were resolved into the 15-trans/cis, 15-trans/trans, 12-trans/cis, 11-trans/cis, 9-trans/cis, 8-trans/cis, and 5-trans/cis isomers. In both of the above cases, the 1,2-diacylglycerol isomers could be separated from the 1,3 isomers. Moreover, the diastereomers of the 9-, 8-, and 5-hydroxides could be separated. Each of the diacylglycerol oxidation products was characterized by (1) proton nuclear magnetic resonance (proton NMR), (2) electron ionization-mass spectrometry (EI-MS), and (3) NP-HPLC of the corresponding fatty acids. The diacylglycerol analysis provided the same results for the autoxidation of 1P,2L-GPC as the fatty acid methyl ester analysis. In addition, when 1S,2A-GPC was autoxidized in the presence of 5% alpha-tocopherol, both diastereomers of the 5-hydroxide were observed in the same proportions as the other hydroxides.

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Organic tetroxides and mechanism of peroxy radical recombination

Khursan

2014

Patai's Chemistry of Functional Groups

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The chemical properties of organic tetroxides, that is, compounds of a general formula ROOOOR (R = H or organic radical) are discussed. The following tetroxides are considered: hydrogen tetroxide HOOOOH, dialkyl tetroxides ROOOOR, hydrotetroxides ROOOOH, and five‐membered cyclic tetroxides—tetroxolanes. Hydrogen tetroxide is formed via self‐reaction of HOO · radicals on singlet PES; hydroperoxy radical interaction plays an important role in the chemistry of atmosphere. The formation and subsequent decay of tetroxides are discussed in detail. Similar self‐reaction of alkylperoxy radicals leads to organic tetroxides. Its irreversible transformation occurs in two directions depending on the tetroxide structure: the facile homolysis of ROOOOR bond or the induced by αCH bond radical decomposition of tetroxide into hydroperoxy, alkoxy radicals, and carbonyl compound. The latter interaction is the key step in the new mechanism of peroxy radical recombination suggested on the base of extensive analysis of available literature. Hydrotetroxides show properties similar to both HOOOOH and dialkyl tetroxides. A possibility of tetroxolane generation in the reaction of ozone with carbonyl compounds is discussed.

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Absolute rate constants for hydrocarbon autoxidation. 33. A product study of the self-reaction of α-tetralylperoxyls in solution

Cited by 11 publications

References 25 publications

Relative yields of excited ketones from self-reactions of alkoxyl and alkylperoxyl radical pairs

Relative yields of excited ketones from self-reactions of alkoxyl and alkylperoxyl radical pairs

A phospholipase C protocol for phospholipid peroxidation analysis

Organic tetroxides and mechanism of peroxy radical recombination

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