Decomposition reactions of cumyl hydroperoxide with sulfur-containing metal complexes.

Ohkatsu, Yasukazu; Kikkawa, Kazumi; Osa, Tetsuo

doi:10.1627/jpi1958.23.16

Cited by 1 publication

(1 citation statement)

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“…This implies that there was a competition between 2 and Zn[(iPrO),PS,], for t-BuO' produced by decomposition of t-BuON,OBu-t and that the products of the reaction of Zn[(i-PrO),PS,], with t-BuO' did not react rapidly with 2. This system can probably be described by the elementary reactions [l] to [3].…”

Section: Preliminary Experimentsmentioning

confidence: 99%

Metal complexes as antioxidants. 9. Application of the spin scavenging technique to the reaction of transition metal dialkyldithiophosphates and dialkyldithiocarbamates with tertiary alkyl hydroperoxides

Howard¹,

Yamada²

1982

Can. J. Chem.

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Can. J . Chem. 60, 224 (1982). The spin scavenging technique has been applied to the initial homolytic reaction between tertiary alkyl hydroperoxides and zinc and nickel complexes of dialkyldithiophosphoric acids and dialkyldithiocarbamic acids using low concentrations of Galvinoxyl and 2,2,6,6-tetramethyl-4-0x0-I-piperidinyloxyl as radical scavengers. This method has demonstrated that these transition metal complexes react with hydroperoxides at 303 K to generate free-radicals. Quantitative kinetic data have been obtained from zeroorder scavenger decays and the efficiency with which the transition metal complexes generate free-radicals increases in the orderDeviations from zero-order scavenger decay have been observed, particularly at high complex concentrations, and have been attributed to reaction of the complex with transient radicals to give products which do not react rapidly with the scavenger. Chem. 60, 224 (1982). Utilisant de faibles concentrations de galvinoxyle et de tretramethyl-2,2,6,6-0x0-4 piperidinyloxy-1 comme pieges a radicaux, on a applique la technique de piegeage de spin a la reaction homolytique initiale entre les hydroperoxydes d'alkyles tertiaires et les acides dialkyldithiocarbamiques. Cette methode a demontre que ces complexes de metaux de transition reagissent avec les hydroperoxydes a 303K en produisant des radicaux libres. On a obtenu des donnees cinetiques quantitatives a partir de la desintegration d'ordre zero des capteurs; I'efficacite avec laquelle les complexes de metaux de transition engendrent les radicaux libres augmente dans I'ordre suivant, Zn [R,NCS]Toutes les desintegrations du capteur ne sont pas rigoureusement d'ordre zero, particulierement aux fortes concentrations du complexe. On a attribue ces deviations a la reaction du complexe avec les radicaux intermediaires pour donner des produits qui ne reagissent pas rapidement avec le capteur.[Traduit par le journal]

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Section: Preliminary Experimentsmentioning

confidence: 99%