Kinetics and regioselectivity of the Autoxidation of o‐Substituted Isopropyl Aromatics

Heinze, Antje; Lauterbach, Gerlinde; Pritzkow, W.; Schmidt‐Renner, W.; Voerckel, V.; Zewegsuren, Nansadyn

doi:10.1002/prac.19873290309

Cited by 9 publications

(6 citation statements)

References 13 publications

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“…The obtained results reaffirmed the reported data which maintained that 1IPN undergoes a free-radical oxidation except that the reaction rate is much lower (10−12 times) than that of 2IPN. , …”

Section: Resultssupporting

confidence: 88%

“…The reported data on oxidation of 1IPN are controversial. Some investigators claim that 1IPN fails to undergo oxidation, , whereas others maintain that it is oxidized but at a lower rate, some 5−10 times lower than that of oxidation of 2IPN. , When 2IPN contaminated with the 1-isomer was used as a raw material, oxidation was found to yield the product which, in addition to major amounts of HP-2, contained minor amounts of 1-(1-hydroperoxy-1-methylethyl)naphthalene (HP-1)…”

Section: Introductionmentioning

confidence: 99%

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The Effect of 1- and 2-(1-Hydroperoxy-1-methylethyl)naphthalenes on the Liquid-Phase Oxidation of Alkylaromatic Hydrocarbons

Zawadiak

Stec

Orlińska

2002

Org. Process Res. Dev.

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The properties of 1-and 2-(1-hydroperoxy-1-methylethyl)naphthalenes as initiators were studied in the liquid-phase freeradical oxidation of hydrocarbons with oxygen. 2-(1-Hydroperoxy-1-methylethyl)naphthalene was found to initiate the reaction, whereas unexpectedly, 1-(1-hydroperoxy-1-methylethyl)naphthalene was found to inhibit the reaction. The products of decomposition of the studied hydroperoxides were found to exhibit essential differences. Thermal decomposition of 1-(1-hydroperoxy-1-methylethyl)naphthalene was found to yield hydroxyaromatic compounds active as oxidation inhibitors. This fact explains the oft-reported lack of reaction in longterm oxidation of 1-isopropylnaphthalene and its disfavourable effect on the oxidation of 2-isopropylnaphthalene.

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Section: Resultssupporting

confidence: 88%

Section: Introductionmentioning

confidence: 99%

The Effect of 1- and 2-(1-Hydroperoxy-1-methylethyl)naphthalenes on the Liquid-Phase Oxidation of Alkylaromatic Hydrocarbons

Zawadiak

Stec

Orlińska

2002

Org. Process Res. Dev.

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“…This coplanar adjustment is hindered by substituents in o-position, and the reactivities of the tertiary C-H bonds in o-cymene and in 2,Sdimethyl cumene are therefore far lower than reactivity of the tertiary C-H bonds in cumene. A n analogous situation exists in the case of aisopropyl naphthalene (Formula Scheme l l ) [53].…”

Section: Formula Scheme 3 Evaluation Of the Chain Termination Constanmentioning

confidence: 85%

“…Formula Scheme 10 shows kinetic data for omethyl-substituted cumenes [53]. It is clear that methyl groups in o-position decrease the reactivity of the tertiary C-H bond considerably.…”

Section: Formula Scheme 3 Evaluation Of the Chain Termination Constanmentioning

confidence: 99%

Kinetics and regioselectivity of the Autoxidation of Alkylaromatic Hydrocarbons

et al. 1992

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Conclusions concerning the reactivities of alkylaromatic hydrocarbons in autoxidations are possible neither on the basis of the oxidizabilities nor on the basis of the chain propagation constants kp. In order to compare different alkylaromatic hydrocarbons, their rate constants with a definite peroxy radical, for example with the cumylperoxy radical, must be determined. Another possibility is the evaluation of relative rate constants by competitive oxidations of binary mixtures of hydrocarbons. These constants are not related to a definite peroxy radical. Nevertheless, these relative rate constants are real measures of the reactivities. If one also determines the composition of the reaction mixtures, which is especially convenient after LiAlH4 reduction, then it is possible to evaluate relative reactivities of the single C‐H bonds, for example in relation to the tertiary C‐H bond of cumene. This was done in our studies, and a great number of single bond reactivities is given in this survey. It is therefore possible to evaluate the activating effect of phenyl groups on different types of α‐C‐H bonds, and steric effects are also perceptible. In o‐substituted isopropyl aromatics, a desactivation by steric hindrance of mesomerism takes place.

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“…The reported data on oxidation of 1IPN are controversial. Some investigators claim that 1IPN fails to undergo oxidation with oxygen, , whereas others maintain that it undergoes oxidation but at a rate about 5−10 times lower than that of the oxidation of 2IPN. , …”

Section: Introductionmentioning

confidence: 99%

Unusual Inhibition Effect of 1-(1-Naphthyl)-1-methylethylhydroperoxide on the Liquid-Phase Oxidation of Isopropylarenes. GC−MS and Theoretical Studies of the Thermal Decomposition of 1-Naphthyl- and 1-Anthryl-1-methylethylhydroperoxides

Mazurkiewicz

Zawadiak

Orlińska

et al. 2006

Org. Process Res. Dev.

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All five possible 1-aryl-1methylethylhydroperoxides derived from naphthalene and anthracene were synthesized and their thermal decomposition in GC−MS conditions was investigated to explain the unusual inhibition effect of 1-(1-naphthyl)-1-methylethylhydroperoxide on the liquid-phase oxidation of isopropylarenes. 2-(1-Aryloxy)propenes were identified as the main decomposition products of 1-(1-naphthyl)-1-methylethylhydroperoxide and 1-(1-anthryl)-1-methylethylhydroperoxide. The relatively unstable 2-aryloxypropenes have thus far never been described as thermal decomposition products of 1-aryl-1-methylethylhydroperoxides. The plausible mechanism of the formation of 2-(1-aryloxy)propenes was proposed on the basis of AM-1 calculations of the possible rearrangement paths of the alkoxy radicals derived from the investigated hydroperoxides. The mechanism explains the inhibition effect of 1-(1-naphthyl)-1-methylethylhydroperoxide on the oxidation of isopropylarenes.

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Kinetics and regioselectivity of the Autoxidation of o‐Substituted Isopropyl Aromatics

Cited by 9 publications

References 13 publications

The Effect of 1- and 2-(1-Hydroperoxy-1-methylethyl)naphthalenes on the Liquid-Phase Oxidation of Alkylaromatic Hydrocarbons

The Effect of 1- and 2-(1-Hydroperoxy-1-methylethyl)naphthalenes on the Liquid-Phase Oxidation of Alkylaromatic Hydrocarbons

Kinetics and regioselectivity of the Autoxidation of Alkylaromatic Hydrocarbons

Unusual Inhibition Effect of 1-(1-Naphthyl)-1-methylethylhydroperoxide on the Liquid-Phase Oxidation of Isopropylarenes. GC−MS and Theoretical Studies of the Thermal Decomposition of 1-Naphthyl- and 1-Anthryl-1-methylethylhydroperoxides

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