Oxidation of Unsaturated Aldehydes by Organic Peracids

Pikh, Zorian; Nebesnyi, Roman; Ivasiv, Volodymyr; Pich, Andrij; Vynnytska, Sofia

doi:10.23939/chcht10.04.401

Cited by 15 publications

(17 citation statements)

References 3 publications

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“…Consequently, the greater the contribution of mechanism 2, the lower is the selectivity of the reaction. These data are in good agreement with the results of the study of the reaction of unsaturated aldehydes with peracids [14].…”

Section: Kinetics Of the Reaction Of Unsaturated Aldehydes With Hydrosupporting

confidence: 91%

“…The content of H 2 O 2 was determined by the iodometric method. The content of unsaturated acid was determined according to the procedure described elsewhere [12].…”

Section: Methodsmentioning

confidence: 99%

“…The analysis of Eq. (14) shows that the expression (K-1)/t0 is valid for K1. Then, the kinetic equation simply transforms into a second order equation:…”

Section: Calculation Of the Kinetic Parameters Of The Reaction Betweementioning

confidence: 96%

“…The above data [10][11][12] on the participation of selenium compounds in oxidative processes, as well as numerical data on the formation of inorganic peracids in the interaction of the corresponding oxides with H 2 O 2 indicate that the oxidation of aldehydes by the system SeO 2 -H 2 O 2 occurs according to the following scheme (Scheme IV).…”

Section: Sementioning

confidence: 99%

“…8 show that in terms of the rate of the reaction with H 2 O 2 in the presence of selenium catalyst, aldehydes can be arranged in the following sequence: cinnamic a l d e h y d e > b e n z a l d e h y d e > 2 -a l k y l p r o p e n a l > >2-bute nal>2-,3-alkyl prope nals >sat urat ed aldehydes. Thus, as opposite to the oxidation of aldehydes by organic peroxy acids [14], the oxidation of saturated aldehydes by H 2 O 2 proceeds much more slowly than that of unsaturated ones [15].…”

Section: T a B L Ementioning

confidence: 99%

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Mechanism and kinetics of the reaction of unsaturated aldehydes with hydrogen peroxide in the presence of selenium compounds

2019

VKhKhT

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We studied the mechanism of aldehydes oxidation by the system selenium-containing catalyst-hydrogen peroxide. On the basis of literature data analysis, our experimental results and developed kinetic model of the reaction, we stated that the oxidation of unsaturated aldehydes by Se-containing compounds and hydrogen peroxide occurs through the formation of intermediate active compound of peroxide nature, selenium peracid. Study of the kinetics of reaction with Se-containing catalysts in different oxidation state (0, +4, and +6) showed that the highest reaction rate was observed when selenium oxidation level was +4. It was also found that the nature of solvent significantly affects the reaction rate and solvents can be ranged by their positive effect as follows: formic acid>tertiary alcohols>acetic acid>dioxane>acetone. It was shown that the oxidation reaction in acetic acid occurs even without catalyst but proceeds in several directions that causes low selectivity towards the target products. As a result of kinetic study, we determined that the concentration of hydrogen peroxide had no effect on the reaction rate; however, an increase in water concentration in the reaction mixture (which is introduced into the reaction mixture together with hydrogen peroxide solution) decreases the reaction rate. On the basis of the results of kinetic simulation, we showed that the oxidation of unsaturated and saturated aldehydes occurs through two following ways: it chiefly proceeds through the step of noncatalytic interaction of aldehyde with hydrogen peroxide in the case of saturated aldehydes, whereas this route occurs only to a small extent in the case of unsaturated aldehydes.

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Section: Kinetics Of the Reaction Of Unsaturated Aldehydes With Hydrosupporting

confidence: 91%

“…The content of H 2 O 2 was determined by the iodometric method. The content of unsaturated acid was determined according to the procedure described elsewhere [12].…”

Section: Methodsmentioning

confidence: 99%

“…The analysis of Eq. (14) shows that the expression (K-1)/t0 is valid for K1. Then, the kinetic equation simply transforms into a second order equation:…”

Section: Calculation Of the Kinetic Parameters Of The Reaction Betweementioning

confidence: 96%

Section: Sementioning

confidence: 99%

Section: T a B L Ementioning

confidence: 99%

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Mechanism and kinetics of the reaction of unsaturated aldehydes with hydrogen peroxide in the presence of selenium compounds

2019

VKhKhT

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Ester formation during fatty acid methyl esters oxidation

Savel'ev,

Cherepanova,

Sapunov

2024

J Americ Oil Chem Soc

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The oxidation processes of unsaturated fatty acid methyl esters (FAMEs) and vegetable oils with molecular oxygen, proceeding through a radical mechanism, lead to the formation of a wide range of compounds. The primary oxidation products, hydroperoxides, undergo further decomposition to form products with a lower molecular weight or participate in cross‐linking reactions leading to the accumulation of products with a higher molecular weight than the raw material. A number of researches note an increase concentration of oligomeric products and esters during the oxidation of FAME. The study of literary sources made it possible to establish that the accumulation of these substances correlates with each other. The mechanisms of ester formation described in the literature suggest the direct participation of either acids or hydroperoxides in these reactions. The work examines the main ways of accumulation of heavy products and “new” esters during the oxidation of FAMEs.

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