13122-71-9Relevant articles and documents
Branching ratios for the reaction of selected carbonyl-containing peroxy radicals with hydroperoxy radicals
Hasson, Alam S.,Tyndall, Geoffrey S.,Orlando, John J.,Singh, Sukhdeep,Hernandez, Samuel Q.,Campbell, Sean,Ibarra, Yesenia
experimental part, p. 6264 - 6281 (2012/08/28)
An important chemical sink for organic peroxy radicals (RO2) in the troposphere is reaction with hydroperoxy radicals (HO2). Although this reaction is typically assumed to form hydroperoxides as the major products (R1a), acetyl peroxy radicals and acetonyl peroxy radicals have been shown to undergo other reactions (R1b) and (R1c) with substantial branching ratios: RO2 + HO2 → ROOH + O2 (R1a), RO 2 + HO2 → ROH + O3 (R1b), RO2 + HO2 → RO + OH + O2 (R1c). Theoretical work suggests that reactions (R1b) and (R1c) may be a general feature of acyl peroxy and α-carbonyl peroxy radicals. In this work, branching ratios for R1a-R1c were derived for six carbonyl-containing peroxy radicals: C2H 5C(O)O2, C3H7C(O)O2, CH3C(O)CH2O2, CH3C(O)CH(O 2)CH3, CH2ClCH(O2)C(O)CH 3, and CH2ClC(CH3)(O2)CHO. Branching ratios for reactions of Cl-atoms with butanal, butanone, methacrolein, and methyl vinyl ketone were also measured as a part of this work. Product yields were determined using a combination of long path Fourier transform infrared spectroscopy, high performance liquid chromatography with fluorescence detection, gas chromatography with flame ionization detection, and gas chromatography-mass spectrometry. The following branching ratios were determined: C2H5C(O)O2, YR1a = 0.35 ± 0.1, YR1b = 0.25 ± 0.1, and YR1c = 0.4 ± 0.1; C3H7C(O)O2, YR1a = 0.24 ± 0.15, YR1b = 0.29 ± 0.1, and YR1c = 0.47 ± 0.15; CH3C(O)CH2O2, Y R1a = 0.75 ± 0.13, YR1b = 0, and YR1c = 0.25 ± 0.13; CH3C(O)CH(O2)CH3, Y R1a = 0.42 ± 0.1, YR1b = 0, and YR1c = 0.58 ± 0.1; CH2ClC(CH3)(O2)CHO, Y R1a = 0.2 ± 0.2, YR1b = 0, and YR1c = 0.8 ± 0.2; and CH2ClCH(O2)C(O)CH3, YR1a = 0.2 ± 0.1, YR1b = 0, and YR1c = 0.8 ± 0.2. The results give insights into possible mechanisms for cycling of OH radicals in the atmosphere.
Oxidation of Butyraldehyde Initiated by Palladium (II) Ion-Pair Complexes
Onsager, Olav-T.,Swensen, Hanne C. A.,Johansen, Jon E.
, p. 567 - 572 (2007/10/02)
Ion-pair complexes comprising a combination of Bu4NCl/Pd(OAc)2 Bu4PCl/Pd(OAc)2 were found to be highly active catalysts for the O2-based autoxidation of butyraldehyde under mild conditions.Based on kinetic evidence, dimeric Pd complexes, Pd2(OAc)4Cl22-, are believed to be mainly responsible for the initiation process, although a catalytic contribution of monomeric species, e.g., Pd(OAc)2Cl22-, cannot entirely be excluded.The oxidation of aldehyde to carboxylic acid and peracid follows a free radical mechanism.
