Oxidants organic peroxides and

D. Hazard Information on Oxidizers, Organic Peroxides and Self Reacting Materials... 

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). 

The second catalyst paste of the two-paste product is a curing agent. A wide variety of materials convert the Hquid polysulfide polymers to elastomeric products. Alkalies, sulfur, metallic oxides, metallic peroxides, organic peroxides, and many metal—organic salts, ie, paint driers, are all potential curing agents. 

NA Prilezhaev. Organic Peroxides and their Application for Oxidation of Unsaturated Compounds. Warsaw, 1912 [in Russian]. 

The peroxyacids were until relatively recently the most powerful oxidants of all organic peroxides, and it is often unnecessary to isolate them from the mixture of carboxylic acid and hydrogen peroxide used to generate them. The pine lower aliphatic members are explosive (performic, particularly) at high, but not low concentrations, being sensitive to heat but not usually to shock. Dipicolinic acid or phosphates have been used to stabilise these solutions. The detonable limits of peroxyacid solutions can be plotted by extrapolation from known data. Aromatic peroxyacids are generally more stable, particularly if ring substituents are present [1],... 

In this review, we focus mainly on the preparative utility of organic peroxides, and only few mechanistic investigations are discussed. This review covers synthetic methodologies for the preparation of alkyl hydroperoxides and dialkyl peroxides (Section II) and the synthetic use of these peroxides in organic chemistry (Section III). In Section II, general methods for the synthesis of organic hydroperoxides and dialkyl peroxides are discussed, as well as the preparation of enantiomerically pure chiral hydroperoxides. The latter have attracted considerable interest for asymmetric oxidation reactions during the last years. 

Palladium(0)-catalyzed cross-coupling of aryl halides and alkenes (i.e., the Heck reaction) is widely used in organic chemistry. Oxidative Heck reactions can be achieved by forming the Pd -aryl intermediate via direct palladation of an arene C - H bond. Intramolecular reactions of this type were described in Sect. 4.1.2, but considerable effort has also been directed toward the development of intermolecular reactions. Early examples by Fu-jiwara and others used organic peroxides and related oxidants to promote catalytic turnover [182-184]. This section will highlight several recent examples that use BQ or dioxygen as the stoichiometric oxidant. 

While such oxidizing agents as chromic acid and nitric acid have been used to convert azo compounds into azoxy compounds, the more recent techniques have involved perbenzoic acid [7, 21-24], peracetic acid or hydrogen peroxide in glacial acetic acid [3, 25-28], and hydrogen peroxide in trifluoroacetic acid [29], Use of the various organic peroxides and hydroperoxides does not appear to have been studied. 

The oxygen atom O will then react with most organic molecules to form oxidation products peroxides and carbonyl derivatives in particular. With molecular oxygen it leads to formation of ozone 03... 

Many organic peroxides and hydroperoxides are known.30 Peroxo carboxylic acids (e.g., peroxoacetic acid, CH3CO OOH) can be obtained by the action of H202 on acid anhydrides. Peroxoacetic acid is made as 10 to 55% aqueous solutions containing some acetic acid by interaction of 50% H202 and acetic acid, with H2S04 as catalyst at 45 to 60°C the dilute acid is distilled under reduced pressure. It is also made by air oxidation of acetaldehyde. The peroxo acids are useful oxidants and sources of free radicals [e.g., by treatment with Fe2+(aq)]. Dibenzoyl peroxide, di-r-butyl peroxide, and cumyl hydroperoxide are moderately stable and widely used as polymerization initiators and for other purposes where free-radical initiation is required. 

This product must be purified from phosphorus before it can be used as an adhesion promoter for electronic devices. This is done by oxidising the phosphine to phosphine oxide with hydrogen peroxide or organic peroxides and by separating the products chromatographically. 

By organic oxides, hydrogen peroxide and organic peroxy acids... 

This ester oxidizes very easily [95], reaction being perceptible even below 140 °C. Above about 300 °C, pyrolysis to propene and acetic acid also takes place. It too, gives cool flames [47]. Fish and Waris [95] detected only acetone, organic peroxides and peroxyacids in the products. Between 280 and 360 °C, Hoare and Kamil [97] found a wider range of products including hydrogen peroxide, formaldehyde, methanol, isopropanol, acetic acid and at 320 °C and below, acetaldehyde. Propene and acetone were found at 360 °C but organic peroxides and peroxyacids were always absent. 

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