Peroxyacetic acid derivatives

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). 

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). 

Cycloaddition reactions of pyrazolo[4,3-c]pyrazoles (63) have not been reported. Oxidation of the tetraaryl derivative (63 R1=p-C1C6H4, R2 = Ph) with potassium permanganate or peroxyacetic acid gives the 3-aroyl-4-arylazopyrazole (64 R1 = p-ClC6H4,... 

The configuration of NADH at the 4 position was determined by a chemical transformation to succinic acid [98]. A sample of NADH containing 2H in the A position, 92, was converted to a 6-methoxy derivative, 95 succinic acid was obtained from this derivative by treatment with ozone and then peroxyacetic acid. 

Examples of the primary stereoelectronic effect have been demonstrated in the literature. Chandrasekhar and Roy showed that rearrangement of 2-oxo-cyclohexyl-peroxyacetic acid 35, derived from acid 34, proceeded via intermediates 36 and 37 to 38 in 62% overall yield.17 Migration of bond a was the only bond which migrated being antiperiplanar to the peroxide no product of migration of bond b was observed. 

Peroxyacetic acid hydrogen chloride Ketones from ethylene derivatives... 

Peroxyacetic acid sodium carbonate Aldehydes from ethylene derivatives with rearrangement s. 18,187... 

As a rule, alkenes do not react with 78-80 unless there is another reagent present—specifically, a transition metal. This reaction will not be discussed further. In sharp contrast, peroxycarboxylic acids such as 81 react directly with alkenes. Peroxycarboxylic acids 81 are named by adding the term peroxy to the name of the carboxylic acid (see Chapter 5, Section 5.9.3 and Chapter 16, Section 16.4). Using the common names, the peroxy analog of formic acid is peroxyformic acid (82), and others include peroxyacetic acid (83), peroxytrifiuo-roacetic acid (84), peroxybenzoic acid (85), and me a-chloroperoxybenzoic acid (abbreviated mCPBA, 86). Peroxycarboxylic acid 85 is a derivative of the aromatic carboxylic acid benzoic acid (PhCOOH), and the carboxylic acid precursor to 86 is clearly another aromatic carboxylic acid. (The nomenclature and structural features of benzoic acid and other aromatic carboxylic acid derivatives will be discussed in detail in Chapter 21, Section 21.2.) The salient feature of peroxyacids 82-86 is the presence of the electrophihc oxygen atom mentioned previously, which will react with an alkene. 

Sulfuric acid peroxyacetic acid Glycol esters from ethylene derivs. 

In a study of the oxidation of various heterocyclic thiones with peroxyacetic acid, l,2-dithiole-3-thiones (10) carrying electron-withdrawing substituents have been found to give l,2-dithiole-3-ones rather than dithiolium salts. Experimental details have been published for addition reactions of l,2-dithiole-3-thiones with acetylenes, and with benzyne. Reactions with enamines, leading to thiopyran derivatives (11), have been described. ... 

Peroxyacetic acid is a better oxidizing agent for hydrazine derivatives than yellow mercuric oxide and can be used in solvents in which the reactants are sufficiently soluble. F. e. and reactions such as cleavage of semicarbazones, formation of diacylhydrazines from carboxylic acid hydrazides, s. L. Horner and H. Fernekess, B. 9A, 712 (1961) s. a. Synth. Meth. 16, 58, 254, 359. 

Hydrazidines s. Amidrazones Hydrazine (s. a. Wolff-Kishner reduction) 16, 104, 109 Hydrazine derivatives —, reactions with peroxyacetic acid 16, 58, 254, 356, 359 1,2-Hydrazinedicarboxamidine... 

A wide range of aromatic nitro and nitroso compounds are rapidly and smoothly reduced to the corresponding amines by sodium boron hydride in the presence of palladized charcoal . Selective and stereospecific reductions can be performed with di-imide, an unstable reagent prepared in situ from a number of precursors . Peroxyacetic acid is an excellent oxidizing agent for a variety of hydrazine derivatives... 

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