- Oxidative degradation of fragrant aldehydes. Autoxidation by molecular oxygen
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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.
- Marteau,Ruyffelaere,Aubry,Penverne,Favier,Nardello-Rataj
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p. 2268 - 2275
(2013/04/10)
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- Selective Oxidation of Alcohols and Aldehydes with Hydrogen Peroxide Catalyzed by Methyltrioctylammonium Tetrakis(oxodiperoxotungsto)phosphate(3-) under Two-Phase Conditions
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The use of methyltrioctylammonium tetrakis(oxodiperoxotungsto)phosphate(3-) (1c) in combination with hydrogen peroxide as the primary oxidant in an aqueous/organic biphase system provides a cheap, efficient, and versatile catalytic method for alcohol and aldehyde oxidation.By this method, a variety of water-insoluble primary and secondary alcohols and aldehydes were oxidized to carboxylic acids and ketones in good yields under mild conditions and after relatively short reaction times.
- Venturello, Carlo,Gambaro, Mario
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p. 5924 - 5931
(2007/10/02)
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- α,α-DICHLOROALDEHYDES AND α,α-DICHLOROCARBOXYLIC ACIDS FROM LONG CHAIN 1-ALKANOLS. IMPROVED CHLORINATION IN THE SYSTEM DMF-CHCl3-MgCl2
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Production of α,α-dichloroaldehydes by direct chlorination of 1-alkanols with chlorine gas, catalyzed by DMF and DMF*HCl, was extended to long chain compounds (CnH2n+1OH; n = 5, 6, 8, 10, 12, 14, 16, 18).Two problems specific to the longer chains were solved to obtain isolated yields in the range 70-85 percent; a) parasitic radical chlorination was largely controlled by shielding from light; b) alkyl alkanoate side product (8 percent for n = 8 but 25 percent for n = 16 or 18) was decreased to 0-2 percent in the presence of MgCl2*H2O.Homogeneity of the reaction medium was improved with chloroform as a cosolvent.Oxidation of the aldehydes to dichlorocarboxylic acids proceeded smoothly with aqueous KMnO4 up to the tetradecanal.For the longer chains 30 percent hydrogen peroxide-NaHCO3 in acetone (overnight at 48-52 deg C) was the preferred oxidant.
- Buyck, L. De,Casaert, F.,Lepeleire, C. De,Schamp, N.
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p. 525 - 534
(2007/10/02)
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