Mechanism silver carbonate oxidation

Silver carbonate, alone or on CeHte, has been used as a catalyst for the oxidation of methyl esters of D-fmctose (63), ethylene (64), propylene (65), trioses (66), and a-diols (67). The mechanism of the catalysis of alcohol oxidation by silver carbonate on CeHte has been studied (68). 

The first thorough investigation of the mechanism of ethylene oxidation on silver surfaces was undertaken by Twigg,1171 who passed a mixture of air and ethylene at 200-350° over fine glasB wool ooated with metallic silver and obtained ethylene oxide, carbon dioxide, and water vapor. The reaction appeared to oonsist of two independent overall processes, which could be depicted separately as shown in Eq. (09) and (100). Of the two reactants, only oxygen was actually o... 

The available experimental data4 are consistent with the following mechanism for the oxidation of alcohols with silver carbonate on Celite ... 

Mechanism. Fetizon et al. have proposed a concerted mechanism for oxidations with silver carbonate on Celite in which the first step is a reversible absorption of the... 

Oxidation of 3-acyl-4-hydroxy-2H-l,2-benzothiazine 1,1-dioxide (9) in methanol by silver carbonate or terf-butyl hypochlorite produced 3-methoxy-4H-l,2-benzothiazin-4-one 1,1-dioxide (35),32 apparently by a free radical mechanism with participation of solvent. 

Polar solvents inhibit the reaction, presumably by interfering with the adsorption process as noted in the mechanism proposed for manganese dioxide oxidations. Oxidation of 1-heptanol to heptanal with Fetizon s reagent was quantitative when the solvent was 35% hexanes. When benzene was used as a solvent, the yield of heptanal dropped to 90% and was < 1% in ethyl acetate, methyl ethyl ketone, or acetonitrile. 69 Since the oxidation is a heterogeneous reaction, requiring adsorption of the alcohol substrate, as the surface area of the reagent increases (increased by precipitation on Celite), the rate of oxidation increases. An optimum ratio is reached beyond which increasing the silver carbonate/Celite ratio slows the oxidation. 69... 

A study518 of the mechanism of oxidation of alcohols by the reagent suggested that a reversible, oriented adsorption of the alcohol onto the surface of the oxidant occurs, with the oxygen atom of the alcohol forming a coordinate bond to a silver ion, followed by a concerted, irreversible, homolytic shift of electrons to generate silver atoms, carbon dioxide, water, and the carbonyl compound. The reactivity of a polyhydroxy compound may not, it appears, be deduced from the relative reactivity of its component functions, as the geometry of the adsorbed state, itself affected by solvent polarity, exerts an important influence on the selectivity observed.519... 

Aromatic cation-radicals can also react with NOj", giving nitro compounds. Such reactions proceed either with a preliminary prepared cation-radical or starting from nncharged componnd if iodine and silver nitrite are added. As for mechanisms, two of them seem feasible—first, single electron transfer from the nitrite ion to a cation-radical and second, nitration of ArH with the NOj radical. This radical is quantitatively formed when iodine oxidizes silver nitrite in carbon tetrachloride (Neelmeyer 1904). 

The application of surface-enhanced Raman spectroscopy (SERS) for monitoring redox and other processes at metal-solution interfaces is illustrated by means of some recent results obtained in our laboratory. The detection of adsorbed species present at outer- as well as inner-sphere reaction sites is noted. The influence of surface interaction effects on the SER spectra of adsorbed redox couples is discussed with a view towards utilizing the frequency-potential dependence of oxidation-state sensitive vibrational modes as a criterion of reactant-surface electronic coupling effects. Illustrative data are presented for Ru(NH3)63+/2+ adsorbed electrostatically to chloride-coated silver, and Fe(CN)63 /" bound to gold electrodes the latter couple appears to be valence delocalized under some conditions. The use of coupled SERS-rotating disk voltammetry measurements to examine the kinetics and mechanisms of irreversible and multistep electrochemical reactions is also discussed. Examples given are the outer- and inner-sphere one-electron reductions of Co(III) and Cr(III) complexes at silver, and the oxidation of carbon monoxide and iodide at gold electrodes. 

The synthesis of 4,5-dicyano-l,2,3-trithiole 2-oxide (172) starts from sodium cyanide and carbon disulfide which via (170) gave the disodium salt of 2,3-mercaptomaleonitrile (171 M = Na). Treatment of the corresponding silver salt (171 M = Ag) with thionyl chloride yielded (172) <66HC(2l-l)l). Phenylsulfine (174), prepared in situ by dehy-drohalogenation of phenylmethanesulfinyl chloride (173), slowly decomposed in ether solution at room temperature to give cis- and trans-stilbenes, mms-4,5-diphenyl-l,2,3-trithiolane 1,1-dioxide (36) and a 5,6-diphenyl-l,2,3,4-tetrathiane dioxide (68JCS(C)1612). The mechanisms of formation of these heterocycles are obscure. 

A few examples of oxidation reactions of 1,1-enediamines are known31,181-183. An oxidative coupling reaction of simple 1,1-enediamines with silver ion181 or carbon tetrabromide182 has been reported. Oxidation of dienetetramines 231 leads to the dication-substituted carbocyclic products 232 (equation 96). The most plausible mechanism involves dimerization of two radical cations181. 

The oxidation of acetate by peroxodisulphate is much slower than that of formate. Glasstone and Hickling showed that the products, which include carbon dioxide, methane, ethane, and ethylene, are similar to those produced by the anodic oxidation of acetate ions (Kolbe electrolysis), and they inferred that the same organic radicals are formed as intermediates. Similar results are reported by Eberson et al. for the oxidations of ethyl terf.-butyl-malonate, tert.-butyl-cyanoacetate, and ferl.-butyl-malonamate ions. The oxidations of these ions and of acetate by peroxodisulphate are first order with respect to peroxodisulphate and zero order with respect to the substrate. Mechanisms involving hydroxyl radicals are excluded because the replacement of peroxodisulphate by Fenton s reagent leads to different products, so Eberson et al. infer that the initial attack on the substrate is by sulphate radical-ions. Sengar and Pandey report that the rate of the silver ion-catalysed oxidation of acetate is independent of the peroxodisulphate concentration. 

The oxidations of lactic, malic, and tartaric acids have been studied. In each case carbon dioxide is produced, and in addition lactic acid gives acetaldehyde, and malic acid gives malonic acid. The kinetics are not well defined, and most of the studies show changes of order during a run. In general, the observations are in accord with chain mechanisms. Kumar and Saxena found that the oxidation of lactic acid is first-order with respect to peroxodisulphate and zero-order with respect to the acid. Bakore and Joshi studied the silver ion-catalysed oxidation, and found approximately first-order kinetics with respect to both... 

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