Peroxyacetic acid compounds

Oxidation. Acetaldehyde is readily oxidised with oxygen or air to acetic acid, acetic anhydride, and peracetic acid (see Acetic acid and derivatives). The principal product depends on the reaction conditions. Acetic acid [64-19-7] may be produced commercially by the Hquid-phase oxidation of acetaldehyde at 65°C using cobalt or manganese acetate dissolved in acetic acid as a catalyst (34). Liquid-phase oxidation in the presence of mixed acetates of copper and cobalt yields acetic anhydride [108-24-7] (35). Peroxyacetic acid or a perester is beheved to be the precursor in both syntheses. There are two commercial processes for the production of peracetic acid [79-21 -0]. Low temperature oxidation of acetaldehyde in the presence of metal salts, ultraviolet irradiation, or osone yields acetaldehyde monoperacetate, which can be decomposed to peracetic acid and acetaldehyde (36). Peracetic acid can also be formed directiy by Hquid-phase oxidation at 5—50°C with a cobalt salt catalyst (37) (see Peroxides and peroxy compounds). Nitric acid oxidation of acetaldehyde yields glyoxal [107-22-2] (38,39). Oxidations of /)-xylene to terephthaHc acid [100-21-0] and of ethanol to acetic acid are activated by acetaldehyde (40,41). 

Hydrolysis of Peroxycarboxylic Systems. Peroxyacetic acid [79-21-0] is produced commercially by the controlled autoxidation of acetaldehyde (qv). Under hydrolytic conditions, it forms an equiHbrium mixture with acetic acid and hydrogen peroxide. The hydrogen peroxide can be recovered from the mixture by extractive distillation (89) or by precipitating as the calcium salt followed by carbonating with carbon dioxide. These methods are not practiced on a commercial scale. Alternatively, the peroxycarboxyHc acid and alcohols can be treated with an estetifying catalyst to form H2O2 and the corresponding ester (90,91) (see Peroxides and peroxy compounds). 

Derivative Formation. Hydrogen peroxide is an important reagent in the manufacture of organic peroxides, including tert-huty hydroperoxide, benzoyl peroxide, peroxyacetic acid, esters such as tert-huty peroxyacetate, and ketone derivatives such as methyl ethyl ketone peroxide. These are used as polymerization catalysts, cross-linking agents, and oxidants (see Peroxides and peroxide compounds). 

Peroxomonosulfuric acid, 18 404—405 Peroxonitrite ion, 18 402 Peroxonitrous acid/salts, 18 402 Peroxophosphoric acids/salts, 18 402-404 Peroxopolyoxometallates, 18 415-416 Peroxosilicates, 18 402 Peroxosulfuric acids/salts, 18 404-405 Peroxotin compounds, 18 402 Peroxyacetic acid, 1 148 14 66, 67 Peroxyacetyl nitrate (PAN), 1 789, 795 Peroxyacids, 18 462 466... 

Nitroso compounds are formed during the addition of nitrous oxide," " dinitrogen trioxide, and nitrosyl halides to alkenes, and in some cases, from incomplete oxidation of amines with peroxyacids like peroxyacetic acid. Quenching of carbanions with nitrosyl halides is also a route to nitroso compounds. A full discussion on this subject is beyond the scope of this work and so the readers are directed to the work of Boyer. ... 

The reagent prepared from the reaction of 30 % hydrogen peroxide with glacial acetic acid also contains peroxyacetic acid but the main product of arylamine oxidation is usually the corresponding nitroso compound. On heating with an excess of this reagent the nitro compound is usually obtained. ... 

Azo and azoxy compounds are potential by-products of peroxyacetic acid oxidations, particularly when the rate of oxidation is slow. Competitive condensation reactions are usually avoided by using an excess of oxidant and also avoiding the presence of excess acid which retards amine oxidation. The latter is sometimes suppressed by using a sodium bicarbonate buffer.i i i ... 

Faust, B. C., K. Powell, C. J. Rao, and C. Anastasio, Aqueous-Phase Photolysis of Biacetyl (an a-Dicarbonyl Compound) A Sink for Biacetyl and a Source of Acetic Acid, Peroxyacetic Acid, Hydrogen Peroxide, and the Highly Oxidizing Acetylperoxyl Radical in Aqueous Aerosols, Fogs, and Clouds, Atmos. Environ., 31, 497-510 (1997). 

A-6. Write a structural formula, including stereochemistry, for the compound formed from ds-3-hexene on treatment with peroxyacetic acid. 

IIIA). The latter compounds were used for the synthesis of 6-acetyl- and 6-nitro-substituted ll-phenoxynaphthacene-5,12-quinone by acetylation with acetic anhydride in the presence of catalytic content of sulfuric acid and by oxidation with peroxyacetic acid, respectively. 

CED [Conversion Extraction Desulfurization] A process for reducing the sulfur content of diesel fuel. Peroxyacetic acid oxidizes the organic sulfur compounds to sulfones, which are removed by solvent extraction. Developed in 2000 by Petro Star. 

Oxidation of julolidine with peroxyacetic acid (at pH 4.8) has been reported124 to give bis-9,9 -julolidyl (105) by oxidative coupling of the benzene ring. A similar oxidative dimer was formed125 when the isolable 4-bromomethylene compound, produced by bromination of 2,2,4-trimethyl- 1,2-dihydroquinoline in chloroform, was allowed to react with bromine in the same solvent. 

The most important applications of peroxyacetic acid are the epoxi-dation [250, 251, 252, 254, 257, 258] and anti hydroxylation of double bonds [241, 252, the Dakin reaction of aldehydes [259, the Baeyer-Villiger reaction of ketones [148, 254, 258, 260, 261, 262] the oxidation of primary amines to nitroso [iJi] or nitrocompounds [253], of tertiary amines to amine oxides [i58, 263], of sulfides to sulfoxides and sulfones [264, 265], and of iodo compounds to iodoso or iodoxy compounds [266, 267] the degradation of alkynes [268] and diketones [269, 270, 271] to carboxylic acids and the oxidative opening of aromatic rings to aromatic dicarboxylic acids [256, 272, 271, 272,273, 274]. Occasionally, peroxyacetic acid is used for the dehydrogenation [275] and oxidation of aromatic compounds to quinones [249], of alcohols to ketones [276], of aldehyde acetals to carboxylic acids [277], and of lactams to imides [225,255]. The last two reactions are carried out in the presence of manganese salts. The oxidation of alcohols to ketones is catalyzed by chromium trioxide, and the role of peroxyacetic acid is to reoxidize the trivalent chromium [276]. 

Oxidants suitable for the partial oxidation of amines to nitroso compounds are peroxy acids Caro acid, which is prepared in situ from potassium persulfate and sulfuric acid [195, 199 potassium peroxysulfate (Oxone) [295] peroxyacetic acid [i53], and peroxybenzoic add [1186], 3-Nitro-o-toluidine [195] and 5-nitro-o-toluidine [199] in aqueous-alcoholic solutions, when treated with a mixture of potassium persulfate and concentrated sulfuric acid, give 3-nitro-2-nitrosotoluene and 5-nitro-2-nitrosotoluene in respective yields of 60 and 55-66%. Organic peroxy acids convert 2,6-dihaloanilines into 2,6-dihalonitrosobenzenes (equation 497) [753, 1186]. p-Phenylenediamine (1,4-diaminobenzene) is oxidized by Oxone (2KHS05 KHS04 K2S04) in an aqueous suspension at room temperature to p-dinitrosobenzene in a quantitative yield [205]. 

The oxidation of some aliphatic amines is a good route to aliphatic nitro compounds. tert-Butylamine is oxidized in 83% yield to 2-methyl-2-nitropropane by potassium permanganate in water at 45 °C for 8 h and at 55 °C for 8 h [738, 892], Under similar conditions, 4-amino-2,2,4-tri-methylpentane is converted into 4-nitro-2,2,4-trimethylpentane in 69-82% yields [859]. Refluxing 3a-acetoxy-20a-amino-5p-pregnane with a chloroform solution of m-chloroperoxybenzoic acid for 40 min furnishes 3a-acetoxy-20a-nitro-5p-pregnane in 66% yield [379]. 2-Aminobutane is converted into 2-nitrobutane by peroxyacetic acid [253] or dimeth yldioxirane [277] (equation 498). 

Primary aromatic amines are oxidized to nitro compounds by peroxy adds perboric acid [194], peroxysulfuric acid [203], peroxyacetic acid [253],... 

Whereas peroxyacetic acid oxidizes 2,6-dichloroaniline to 2,6-dichlo-ronitrosobenzene [/5J], peroxytrifluoroacetic acid carries the oxidation to the nitro compound. Refluxing 2,6-dichloroaniline with peroxytrifluoroacetic acid, which is prepared in situ from 90% hydrogen peroxide and trifluoroacetic anhydride in dichioromethane, gives 2,6-dichloronitroben-zene in 89-92% crude yields and 59-73% pure yields [290. 2-Amino-4-methylpyridine treated with 30% hydrogen peroxide in fuming sulfuric acid at 10-25 °C for 50 h yields 68% of 4-methyl-2-nitropyridine [203]. 

The oxidation of tertiary amines to amine oxides is carried out by peroxy compounds, most often hydrogen peroxide and peroxyacetic acid. 

Oxidation of Primary Aromatic Amines to Nitroso Compounds with Peroxyacetic Acid [753] ... 

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