Catalytic oxidation of hydrocarbons of natural and oil gas
Alkane oxidation by O2 and CO in the presence of Rh-, Pd-, and Pt-containing catalytic systems leads to the product of C-H bond oxidation and the products of C-C bond oxidative destruction. A deuterated methyl group in acetic acid is observed in the oxidation of n-propane in a deuterium-donor medium. The possible mechanisms of alkane C2-C4 conversion are proposed.
Chepaikin,Bezruchenko,Menchikova,Moiseeva,Gekhman
experimental part
p. 332 - 337
(2011/04/26)
Homogeneous catalytic oxidation of light alkanes: C-C bond cleavage under mild conditions
The combined oxidation of CO and C2-C4 alkanes (associated petroleum gas and natural gas components) under the action of oxygen in trifluoroacetic acid solutions in the presence of rhodium and copper chlorides was accompanied by the oxidative degradation of C-C bonds in a hydrocarbon chain with the formation of carbonyl compounds, alcohols, and esters. For butane and isobutane, the reaction path with C-C bond cleavage was predominant. The buildup curves of isobutane oxidation products (both with the retention and with the degradation of the chain) were S-shaped and characterized by the same induction period; they did not pass through a maximum. A reaction scheme was proposed to reflect the main special features of the mechanism of transformations occurring in the O2/Rh/Cu/Cl- oxidation system.
Chepaikin,Bezruchenko,Menchikova,Moiseeva,Gekhman
experimental part
p. 666 - 671
(2011/02/16)
Toluene-p-sulfonic Acid-catalysed Reaction of But-1-ene with Trifluoroacetic Acid: Return and Elimination from the Intimate Ion Pair
At short times, reaction of but-1-ene with toluene-p-sulfonic acid in trifluoroacetic acid gives 2-butyl tosylate 1, 2-butyl trifluoroacetate 2 and but-2-ene 3 in ratios of (>=)2.3:1:(>=)0.41; thus internal return is the major pathway and elimination is important for the tight 2-butyl cation-tosylate anion pair.
Farcasiu, Dan
p. 2611 - 2612
(2007/10/02)
Stereochemistry of Trifluoroacetolysis of Optically Active 2-Butyl Tosylate. A Test for Hydrogen Bridging
Trifluoroacetolysis of (R)-(-)-2-butyl tosylate at 25 deg C gives 2-butyl trifluoroacetate with 7 +/- 1percent net inversion.The ratio of the polarimetric and spectrophotometric rate constants is 1.55, and this decreases to 1.05 in the presence of 0.125 M NaO2CCF3.These results are most simply and plausibly interpreted in terms of formation of an ion pair consisting of an open 2-butyl cation and a tosylate anion which gives racemized tosylate by ion-pair return and by elimination/readdition, with competitive nucleophilic solvent attack with a small overall preference for substitution on the side opposite the anion.A published proposal based on deuterium labeling studies that a hydrogen-bridged butyl cation is the predominant intermediate in this reaction does not give a simple prediction of these results.
Allen, Annette D.,Ambidge, Christopher,Tidwell, Thomas T.
p. 4527 - 4530
(2007/10/02)
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