ChemInform Abstract: Autoxidation of γ‐Butyrolactone.

Perkel, A. L.; Freidin, B. G.; Ivko, E. V.

doi:10.1002/chin.198737127

Cited by 1 publication

(1 citation statement)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…8). 128 It can be supposed that a rather low rate of consumption of succinic anhydride can be attributed to that 4-hydroxybutanoic acid (58), which is formed from the pericyclic isomerization of peroxyester 57 (an alcohol component), undergoes a fast cyclization to γ-butyrolactone (Scheme 31), thus removing the active primary OH group from the reaction.…”

Section: Channels and Mechanisms Of Formation Of Products From Peroxide Intermediates Formed Due To The Ester Alkoxyl Moietiesmentioning

confidence: 99%

The specific features of the liquid-phase oxidation of saturated esters. Kinetics, reactivity and mechanisms of formation of destruction products

Perkel

Voronina

2020

Russ Chem Bull

View full text Add to dashboard Cite

Data on kinetics, reactivity, and mechanisms of formation of destruction products of the liquid-phase oxidation of saturated esters by molecular oxygen have been systematized and discussed. The ester group has both an activating and deactivating eff ects on the reactivity of the СН bonds of the alkoxyl (α´-, β´-, γ´-, and δ´-) and acyl (α-, β-, and γ-) groups. The activating eff ect in esters is weaker than in alcohols, ketones, and ethers and extends to the αand α´-CH bonds. The reactivity of the β-, β´-, and γ´-СН bonds is signifi cantly lower than that of the secondary СН bonds of hydrocarbons. Oxidation of the β-СН bonds of the acyl moieties of esters leads to НОО • radical, α,β-epoxy-, α,β-dihydroxy-, and α,β-unsaturated esters, but not to hydroperoxides. Upon the oxidation of esters, the highly active α-carboxyalkylperoxy-, α-acyloxyperoxy-, and НОО • -radicals are formed. The recombination reactions involving these radicals occur both with and without chain termination. The specifi city of the decomposition of ester hydroperoxides are due to intra-and intermolecular interactions of the hydroperoxide groups with the ester groups. Labile peroxide intermediates (α-hydroxyperoxyesters, peroxyesters, and peroxylactones) are formed through the corresponding tetrahedral intermediates and decay predominantly by the non-radical pathway. The recombination of the peroxyl radicals and the decay of labile peroxides result in the parallel accumulation of per oxide and non-peroxide products during the oxidation of esters.

show abstract

Section: Channels and Mechanisms Of Formation Of Products From Peroxide Intermediates Formed Due To The Ester Alkoxyl Moietiesmentioning

confidence: 99%