54009-71-1Relevant articles and documents
Mechanistic Insights into the Aerobic Oxidation of Aldehydes: Evidence of Multiple Reaction Pathways during the Liquid Phase Oxidation of 2-Ethylhexanal
Vanoye, Laurent,Favre-Réguillon, Alain
, p. 335 - 346 (2022/02/10)
The liquid-phase aldehyde oxidation by molecular oxygen (autoxidation) has been known for about 2 centuries and is a critical organic transformation in both industrial applications and academic research. However, the general reaction pathway proposed for the aerobic oxidation of aldehydes into the corresponding carboxylic acid exhibits some inconstancies, in particular, for β-substituted aliphatic aldehydes. Thus, the liquid-phase aerobic oxidation of 2-ethylhexanal was further studied in acetonitrile at 20 °C with O2 at atmospheric pressure. By precisely monitoring the primary intermediate (peracid), product (carboxylic acid), and byproducts as a function of time and catalysts used, we demonstrated the pivotal role of the acylperoxy radical. The direct formation of peracid and carboxylic acid from the latter was highlighted by analyzing the composition of the reaction mixture at low conversion. Peracid could be converted into carboxylic acid by metal catalysts or through reaction workup. Consequently, the commonly accepted pathway of aerobic oxidation of aldehyde via a Criegee intermediate can be overlooked under these conditions.
Oxidative degradation of fragrant aldehydes. Autoxidation by molecular oxygen
Marteau,Ruyffelaere,Aubry,Penverne,Favier,Nardello-Rataj
, p. 2268 - 2275 (2013/04/10)
The oxidative degradation of fragrant aldehydes by molecular oxygen has been investigated. The oxygen consumption was monitored and the bond dissociation energy (BDE) of the aldehyde C(O)-H bond were calculated by DFT method. The oxidation products were identified by GC/MS. The different pathways accounting for the oxidative degradation are discussed. The main product is the acid, beside the formate ester. Both oxidation products result from the Baeyer-Villiger reaction involving a peracid R(CO)OOH whereas minor products arise from the hydroperoxide ROOH intermediate derived either from the acyl peroxy radical, R(CO)OO or from the decarboxylation of the peracid RC(O)OOH.
Factors affecting the selectivity of air oxidation of 2-ethyhexanal, an α-branched aliphatic aldehyde
Lehtinen, Christel,Brunow, Goesta
, p. 544 - 549 (2013/08/07)
Various solvents and metal catalysts were tested in air oxidation of 2-ethylhexanal to elucidate the effects of different variables on the reaction path of the substrate. The primary goal was to determine the optimal conditions for maximising the yield of carboxylic acid and minimising the formation of other products. Solvents and catalysts both had a significant impact on the product distribution. The best selectivity of 2-ethylhexanal to 2-ethylhexanoic acid, 84%, was obtained with octanoic acid as solvent and manganese(II) acetate as catalyst. Addition of an aromatic aldehyde, benzaldehyde, or p-methoxybenzaldehyde retarded the oxidation rate of both 2-ethylhexanal and aromatic aldehyde dramatically.