Peroxydisulfate oxidation

Peroxydisulfate oxidations have also been used to prepare a variety of pyridine mono- and di-carboxylic add silver(II) complexes.496 All these compounds were orange-red in colour and sparingly soluble to insoluble in most solvents, including water. 

A dark red-brown precipitate of Ag(pyrazine)2S208 was obtained by peroxydisulfate oxidation of Ag1 solutions containing pyrazine at 0-5 °C, In a related experiment, the 2-carboxylate derivative was obtained. Both reactions proceeded via the oxidation of white... 

Goulden, P. and D. Anthony (1978). Kinetics of uncatalyzed peroxydisulfate oxidation of organic materials in fresh water. Anal. Chem. 50, 953-958. 

Toluene has been oxidized by the silver ion catalysed reaction with peroxy-disulfate. The reaction produces a mixture of bibenzyl, benzaldehyde and benzoic acids.299 Russian workers have described the conversion of 4-methoxy-toluene to the benzaldehyde by oxidation with peroxydisulfate in the presence of silver or copper ions and oxalic acid.300 The presence of copper salts in iron or copper catalysed peroxydisulfate oxidation is believed to suppress side-reactions.301 Phillips have patented a palladium(II)/tin(IV)/persulfate system for the oxidation of toluene derivatives.302 The reactions are carried out in carboxylic acid solvents (Figure 3.78). 

Figure 3.78 Metal catalysed peroxydisulfate oxidation of toluenes.

A procedure was developed for the determination of total and labile Cu and Fe in river surface water. It involved simultaneous solvent extraction of the metals as diethyldithio-carbamates (ddc) and tfac complexes. The complexes were extracted by isobutyl methyl ketone (ibmk) and the solution subjected to flame atomic absorption spectrometry. Variables such as pH, metal complex concentration, reaction time, ibmk volume and extraction time were optimized. Prior to the solvent extraction a microwave-assisted peroxydisulfate oxidation was used to break down the metallorganic matter complexes in the river surface waters . Trifluoroacetylacetone was used as a chelation agent for the extraction and quantitative determination of total Cr in sea water. The chelation reaction was conducted in a single aqueous phase medium. Both headspace and liquid phase extractions were studied and various detection techniques, such as capillary GC-ECD, EI-MS (electron-impact MS) and ICP-MS, were tested and compared. The LOD was 11-15 ngL Cr for all the systems examined. The method provided accurate results with EI-MS and ICP-MS, while significant bias was experienced with ECD °. ... 

Solid oxidants Sodium bismuthate is such a strong oxidant that it wiU oxidize Mn(II) to permanganate at room temperature. Ce(III) is oxidized quantitatively to Ce(rV) in sulfuric acid solution, and the excess bismuthate removed by filtration. Silver-catalyzed peroxydisulfate oxidation has largely supplanted the bismuthate method, thus avoiding the inconvenient filtration stq> required with solid oxidants. 

Compounds in which nickel is present in a higher oxidation state than 2+ are uncommon and often relatively unstable. Exceptions are found in sodium and potassium nickel(IY) paraperiodates, which have been described by R y and Sarma1 and which correspond to the formulation Na(K)NiI06-xH20. These compounds are readily prepared by peroxydisulfate oxidation of nickel(II) in the presence of periodate. 

Behrman and Pitt306 have applied the Elbs peroxydisulfate oxidation to the pyridine series, obtaining, for instance, 2,5-pyridinediol in 42% yield from 2-pyridinol. 

The perfection of this strategy makes use of the L-threonine-derived 2S,ZR acid 61 and tert-h xiy iV-(p-methoxybenzyl)glycinate as the active methylene partner [28d]. After condensation to amide 62, base treatment (LHMDS) induced epoxydation (at 0 °C) and then (25 °C) cyclization. This double inversion mechanism produced a single epimer, 63a, which, through acid 63b, was converted to target 11 by silylation, ester hydrolysis, lead tetraacetate and CAN (or peroxydisulfate) oxidation. 

Pyridone, 4-pyridone, and 3-pyridinol undergo the Elbs peroxydisulfate oxidation, a reaction characteristic of phenols and aromatic amines. A bimolecular ionic reaction in which the 2-pyridyloxy ion attacks the peroxy-bond of the persulfate ion with displacement of sulfate ion to give 2-pyridone-5-sulfate is consistent with the observations. ... 

A study involving the peroxydisulfate oxidation products of the antimalarial drug primaquine (e.g., 6-methoxy-5,8-di-[4-amino-r-methylbuylamino]quinoline, N -tri-[4-amino-l-methylbutyl]amine) utilized a C,g colunrn (A = 254nm) and a 95/30/7/1 water/acetonitrile/methanol/water (IM perchloric acid) mobile phase [1497]. Primaquine dimers were also studied. The study followed the reaction of 250 pg/mL primaquine. All products were easily detectable. 

Ozone or peroxydisulfate oxidation of either Am(iii) or Am(v) in aqueous sodium carbonate or bicarbonate yields an intensely colored red-brown solution thought to contain a carbonate complex of Am(vi) [114]. This same complex is also obtained by dissolution of solid sodium americyl acetate in sodium carbonate solutions. Nugent [238] speculates that an Am(vii)-carbonate complex may actually be present in such solutions. Americium(vi) in 0.1-0.5 M NaHC03... 

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