Oxidation of propylene by palladium chloride in acetic acid

Conclusions The oxidation of propylene by palladium chloride in glacial acetic acid leads to the formation of isopropenyl acetate, cis-n-propenyl acetate, trans-n-propenyl acetate, the corresponding alkylidene diacetate, and small amounts of allyl acetate.Translated from Izvestiya Akademii Nauk SSSR, Khimicheskaya, No. 12, pp. 2204–2206, December, 1965     

Oxidation of butene-1 by palladium chloride in acetic acid

Conclusions The oxidation of butene-1 by palladium chloride in glacial acetic acid leads to the formation of a mixture of complex alkenyl esters: butene-1-ol-3 acetate, butene-1-ol-2 acetate, the acetates of trans- and cis-butene-2-ols-2, and the acetates of trans- and cis-butene-2-ols-1.     

Regularities of formic acid oxidation in the presence of porous silicon nanocomposites with palladium

Nanocomposites demonstrating high catalytic activity in the oxidation of formic acid were obtained by depositing palladium on porous silicon support. The palladium samples on porous silicon are superior to commercial samples on carbon black in many characteristics. A decrease in the size of palladium nanoparticles favors an increase in the catalytic activity of the palladium/porous silicon nanocomposites.     

Photoactivation of alkene oxidation by molecular oxygen in the presence of palladium

A catalytic cycle which leads to α,-β ethylenic ketones and methyl ketones from terminal alkenes in the presence of palladium trifluoroacetate,oxygen and U.V. light is described.     

Adducts of tetraphenylstibium nitrate with nitric acid and of tetraphenylstibium acetate with acetic acid: Syntheses and structures

The reactions of tetraphenylstibium nitrate with nitric acid and of tetraphenylstibium acetate with acetic acid yield adducts Ph₄SbONO₂ · HNO₃ (I) and Ph₄SbOC(O)CH₃ · CHH₃COOH (II). According to X-ray diffraction data, the antimony atom in [Ph₄Sb]⁺[O₂N-O···H···O-NO₂]^? has a tetrahedral coordination. The CSbC bond angles and Sb-C bond lengths vary within 108.04(6)°–109.75(4)° and 2.096(1)–2.098(1) Å, respectively. The anion includes the intermolecular hydrogen bond O(1)–H(1)···O(1)″: the O(1)-H(1), H(1)···O(1)″, and O(1)···O(1)″ distances are 0.91(4), 1.56(4), and 2.460(2) Å, respectively; and the OHO angle is 169(5)°. The nitrate groups are usually planar. Complex II also contains the intermolecular hydrogen bond with the following parameters: O(3)-H(3), 0.92 Å; H(3)···O(2), 1.68 Å; and O(3)···O(2) 2.594 Å; the O(2)H(3)O(3) angle is 172.1°. This H-bond noticeable changes the coordination polyhedron of the antimony atom compared to that in tetraphenylstibium acetate.     

Melaminium acetate acetic acid solvate monohydrate

The crystals of the title new melaminium salt, 2,4,6‐tri­amino‐1,3,5‐triazin‐1‐ium acetate acetic acid solvate monohydrate, C₃H₇N₆⁺·CH₃COO^?·CH₃COOH·H₂O, are built up from singly protonated melaminium residues, acetate anions, and acetic acid and water mol­ecules. The melaminium residues are interconnected by N—H?N hydrogen bonds to form chains along the [010] direction. These chains of melaminium residues form stacks aligned along the a axis. The acetic acid mol­ecules interact with the acetate anions via the H atom of their carboxylic acid groups and, together with the water mol­ecules, form layers that are parallel to the (001) plane. The oppositely charged moieties interact via multiple N—H?O hydrogen bonds that stabilize a pseudo‐two‐dimensional stacking structure.     

Hydroacetoxylation of olefins with acetic acid genetated in situ from vinyl acetate in the presence of ruthenium complexes

Ruthenium complexes catalyze the decomposition of vinyl acetate releasing the acetic acid and its subsequent addition to linear and cyclic olefins.     

Atmospheric oxidation pathways of acetic acid

One of the most abundant carboxylic acids measured in the atmosphere is acetic acid (CH(3)C(O)OH), present in rural, urban, and remote marine environments in the low-ppb range. Acetic acid concentrations are not well reproduced in global 3-D atmospheric models because of the poor inventory of sources and sinks to model its global distribution. To understand the complete oxidation of acetic acid in the atmosphere initiated by OH radicals, ab initio calculations are performed to describe in detail the energetics of the reaction potential energy surface (PES). The proposed reaction mechanism suggests that the CH(3)C(O)OH + OH reaction takes place via three pathways: the addition of OH to the central carbon, the abstraction of a methyl hydrogen, and the abstraction of an acidic hydrogen. The PES is characterized by prereactive H-complexes, transition states, and more interestingly unique radical-mediated isomerization reactions. From the analysis of the energetics, acetic acid atmospheric oxidation will proceed mainly via the abstraction of the acidic hydrogen, consistent with previous experimental and theoretical studies. The major byproducts from each pathway are identified. Glyoxylic acid is suggested to be a major byproduct of the atmospheric oxidation of acetic acid. The atmospheric fate of glyoxylic acid is discussed.     

Chitosan-cellulose sulfate acetate complexation in acetic acid solutions

Colloidal and optical properties of dispersions of chitosan-cellulose sulfate acetate interpolyelectrolyte complexes resultant from mixing dilute solutions of the polymers in acetic acid and in acetic acid-based buffer mixtures are investigated. It is established that, in acetic acid, an insoluble complex is formed whose composition corresponds to the unit ratio [chitosan]: [cellulose sulfate acetate] = 1: 1.5, mol/mol. Particle size and concentration are independent of the order of mixing of the solutions of the polymers. In buffer solvents, the particle size is larger and the particle concentration is lower than those in acetic acid. Excess chitosan causes the dissolution of the complex. The addition of low-molecular-weight electrolytes to ionic strengths of 0.2–0.3 also promotes the dissolution of the interpolyelectrolyte complex. The complex becomes completely soluble at ionic strengths of 1.5–2.0.     

Catalytic oxidation of toluene by ozone in the acetic acid-sulfuric acid system

Oxidation of toluene by ozone was studied in the system constituted by acetic and sulfuric acids in the presence of manganese(II) acetate and sodium bromide. The effect of sulfuric acid and the catalyst on the yield of benzoic acid and on the oxidation rate was considered. The optimal ozonization conditions were determined. A scheme of redox catalysis that accounts for experimental data was suggested.     

Coulometric generation of acetylions by oxidation of mercury in acetic anhydride and in acetic acid/acetic anhydride mixture

Coulometric generation of acetyl (CH₃CO⁺) ions by oxidation of mercury in acetic anhydride and in acetic acid/acetic anhydride (5:95, v/v) is described. Current/potential curves for solvents, titrated bases, indicator and mercury showed that in both these solvents mercury is oxidized at potentials which are much more negative than those for the titrated bases and other components present in the solution. Quinoline, triethanolamine, triethylamine, pyridine and quinolin-8-ol in acetic anhydride, as well as triethylamine, 2,2′-bipyridine, 2,4,6-collidine, pyridine and sodium acetate in acetic acid/acetic anhydride were titrated with acetyl ions generated by the oxidation of mercury. In this way, it was established that the oxidation of mercury to mercury (I) ions proceeds quantitatively with 100% current efficiency.     

Escherichia coli-catalyzed bioelectrochemical oxidation of acetate in the presence of mediators

Bioelectrocatalytic oxidation of acetate was investigated under anaerobic conditions by using Escherichia coli K-12 (IFO 3301) cells cultured on aerobic media containing poly-peptone, glucose or acetate as the sole carbon source. It was found that all E. coli cells cultured on the three media work as good catalysts of the electrochemical oxidation of acetate as well as glucose with Fe(CN)6(3-), 2,3-dimethoxy-5-methyl-1,4-benzo-quinone (Q0), 2,6-dichloro-indophenol, or 2-methyl-1,4-naphthoquinone as artificial electron acceptors (mediators). Acetate-grown E. coli cells exhibited the highest relative activity of the acetate oxidation against the glucose oxidation. On the other hand, all the artificial electron acceptors used work as inhibitors for the catalytic oxidation of acetate at increased concentrations. The inhibition phenomenon can be interpreted in terms of competitive substrate inhibition as a whole. Apparent values of Michaelis constant, catalytic constant, and inhibition constant were evaluated by amperometric methods. Q0 is an effective artificial mediator as evidenced by a large reaction rate constant between the cell and Q0 at least at low concentrations (<50 microM). However, Fe(CN)6(3-) is a promising mediator in biosensor applications because the inhibition constant is very large and it works as an electron acceptor even under aerobic conditions.     

Direct oxidation of methane to acetic acid catalyzed by Pd2+ and Cu2+ in the presence of molecular oxygen

Methane is catalytically converted primarily to acetic acid in concentrated sulfuric acid using a combination of Pd(2+) and Cu(2+) in the presence of oxygen.