Hydrogen peroxide in oxidation

Penkett, S. A., B. M. R. Jones, K. A. Brice, and A. E. J. Eggleton, The Importance of Atmospheric Ozone and Hydrogen Peroxide in Oxidizing Sulphur Dioxide in Cloud and Rain Water, Atmos. Environ., 13, 123-137 (1979). 

The editors emphasise the CAUTIONARY notes relating to the handling of hydrogen peroxide (p. 439), and to the distillation of extracts following the use of tetrahydrofuran/hydrogen peroxide in oxidation procedures (p. 552). 

Molecular complexes can be prepared from some tertiary amines and 90 or 30% solutions of hydrogen peroxide. 1,4-Diazabicyclooctane (Dabco) forms an adduct with two molecules of hydrogen peroxide. The adduct consists of hygroscopic crystals melting at 112 °C (dec), is stable for a limited time at room temperature, and can be used as a source of hydrogen peroxide in oxidations [727]. 

While determining the scope of the synthetic utility of urea-hydrogen peroxide in oxidation reactions, it was observed that aniline can be converted to azobenzene and azoxybenzene in good yield, as shown in Fig. 2.8. 

Hydrogen peroxide, in oxidation of pi-valonitrUe to a, [/ , a -tetramethyl-adiponitrile, 92... 

Hydrogen peroxide in aqueous solution has many uses, because the products from its reaction are either water or oxygen, which are generally innocuous. The chief use is bleaching of textiles, both natural and synthetic, and of wood pulp for paper. Other uses are the oxidation of dyestuffs, in photography and in the production of... 

Oxidation of diphenylcarbazide (Section VII,3) with hydrogen peroxide in the presence of alcohoUo potassium hydroxide affords diphenylcarbazone ... 

Thiazole-N-oxides are prepared by the action at low temperature (-10°C) of hydrogen peroxide in acetic acid (474). 4-MethyIthiazole and 2,4-dimethylthiazole afforded the corresponding N-oxides with yields of 27 and 58%, respectively (Scheme 88). Thiazole-N-oxides without a methyl group in the 2-position are so unstable that they have a tendency to form 2-hydroxythiazoles and are decomposed by oxidation, whereas a 2-methyl group would prevent such rearrangement (474). 

Inorganic Methods. Before the development of electrolytic processes, hydrogen peroxide was manufactured solely from metal peroxides. Eady methods based on barium peroxide, obtained by air-roasting barium oxide, used dilute sulfuric or phosphoric acid to form hydrogen peroxide in 3—8% concentration and the corresponding insoluble barium salt. Mote recent patents propose acidification with carbon dioxide and calcination of the by-product barium carbonate to the oxide for recycle. 

Oxidation. Oxidation of hydroxybenzaldehydes can result in the formation of a variety of compounds, depending on the reagents and conditions used. Replacement of the aldehyde function by a hydroxyl group results when 2- or 4-hydroxybenzaldehydes are treated with hydrogen peroxide in acidic (42) or basic (43) media pyrocatechol or hydroquinone are obtained, respectively. 

C. HIO is prepared by oxidation of iodine with perchloric acid, nitric acid, or hydrogen peroxide or oxidation of iodine in aqueous suspension to iodic acid by silver nitrate. Iodic acid is also formed by anodic oxidation at a platinum electrode of iodine dissolved in hydrochloric acid (113,114). 

Weak to moderate chemiluminescence has been reported from a large number of other Hquid-phase oxidation reactions (1,128,136). The Hst includes reactions of carbenes with oxygen (137), phenanthrene quinone with oxygen in alkaline ethanol (138), coumarin derivatives with hydrogen peroxide in acetic acid (139), nitriles with alkaline hydrogen peroxide (140), and reactions that produce electron-accepting radicals such as HO in the presence of carbonate ions (141). In the latter, exemplified by the reaction of h on(II) with H2O2 and KHCO, the carbonate radical anion is probably a key intermediate and may account for many observations of weak chemiluminescence in oxidation reactions. 

Oxidation. Maleic and fumaric acids are oxidized in aqueous solution by ozone [10028-15-6] (qv) (85). Products of the reaction include glyoxyhc acid [298-12-4], oxalic acid [144-62-7], and formic acid [64-18-6], Catalytic oxidation of aqueous maleic acid occurs with hydrogen peroxide [7722-84-1] in the presence of sodium tungstate(VI) [13472-45-2] (86) and sodium molybdate(VI) [7631-95-0] (87). Both catalyst systems avoid formation of tartaric acid [133-37-9] and produce i j -epoxysuccinic acid [16533-72-5] at pH values above 5. The reaction of maleic anhydride and hydrogen peroxide in an inert solvent (methylene chloride [75-09-2]) gives permaleic acid [4565-24-6], HOOC—CH=CH—CO H (88) which is useful in Baeyer-ViUiger reactions. Both maleate and fumarate [142-42-7] are hydroxylated to tartaric acid using an osmium tetroxide [20816-12-0]/io 2LX.e [15454-31 -6] catalyst system (89). 

Petoxycatboxyhc acids have been obtained from the hydrolysis of stable o2onides with catboxyhc acids, pethydtolysis of acyhinida2ohdes, reaction of ketenes with hydrogen peroxide, electrochemical oxidation of alcohols and catboxyhc acids, and oxidation of catboxyhc acids with oxygen in the presence of o2one (181). 

Nitroxyl radicals of diarylamines can also be obtained on oxidation with hydrogen peroxide in the presence of vanadium ions. Resonance helps stabili2e these radicals. Eor example, the nitroxide from 4,4 -dimethoxydiphenylainine [63619-50-1] is stable for years, whereas the radical from the unsubstituted diphenylamine caimot be isolated. Substitution in the ortho and para positions also increases the stabiUties of these nitroxides by inhibiting coupling reactions at these sites. However, they are not as stable as the stericaHy hindered tetramethylpiperidyl radical. 

In many instances, beginning a synthesis with quinoline N-oxide [1613-37-2] faciHtates the preparation of difficult compounds. Quinoline is converted to the N-oxide using hydrogen peroxide in acetic acid, and later reduced to the substituted quinoline. Warm mixed acid gives 4-rutroquinoline... 

Analytical Methods. A classical and stiU widely employed analytical method is iodimetric titration. This is suitable for determination of sodium sulfite, for example, in boiler water. Standard potassium iodate—potassium iodide solution is commonly used as the titrant with a starch or starch-substitute indicator. Sodium bisulfite occurring as an impurity in sodium sulfite can be determined by addition of hydrogen peroxide to oxidize the bisulfite to bisulfate, followed by titration with standard sodium hydroxide (279). 

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