Peroxyacetic acids

Peroxyformic acid is nontoxic. It is a skin and eye irritant. Its irritant action is less severe than that of peroxyacetic acid. There are no reports on its tumorigenic properties. 

Peroxyformic acid is the only oxygen-balanced organic peroxide. Its active oxygen content (25.8%) is greater than that of other peroxy compounds. It is therefore expected to undergo extremely violent decomposition. However, in practice, this compound forms only in situ and the commercial formulations contain its aqueous or dilute solutions in organic solvents. 

The solutions of peroxyformic acid are shock and heat sensitive and highly reactive and decompose violently when exposed to heat. Dilution with water increases the sensitivity to shock and heat. It is a strong oxidizer and may react violently with readily 

Water from a sprinkler system may be used from an explosion-resistant location to fight fire and keep the containers cool. 

The spilled solution of peroxyformic acid should be absorbed by vermiculite or other noncombustible absorbent and disposed of immediately. Do not use paper, wood, or spark-generating metals for sweeping and handling. It is destroyed by burning on the ground in a remote place using a long torch. Concentrated aqueous solutions in a small quantity may be diluted with copious quantities of water and flushed down the drain. 

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A commonly used peroxy acid is peroxyacetic acid (CH3CO2OH) Peroxyacetic acid is normally used m acetic acid as the solvent but epoxidation reactions tolerate a variety of solvents and are often earned out m dichloromethane or chloroform... 

Relative Rates of Epoxidation of Some Representative Alkenes with Peroxyacetic Acid... 

Figure 7 7 shows why equal amounts of (R) and (5) 1 2 epoxypropane are formed m the epoxidation of propene There is no difference between the top face of the dou ble bond and the bottom face Peroxyacetic acid can transfer oxygen to either face with equal facility the rates of formation of the R and S enantiomers of the product are the same and the product is racemic... 

Epoxidation of alkenes is a stereospecific syn addition Which stereoisomer of 2 butene reacts with peroxyacetic acid to give meso 2 3 epoxybu tane Which one gives a racemic mixture of (2/ 3/ ) and (25 35) 2 3 epoxybutane ... 

Peroxyacetic acid (CH3COOH) is a weaker acid than acetic acid... 

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). 

Acetaldehyde oxidation generates peroxyacetic acid which then reacts with more acetaldehyde to yield acetaldehyde monoperoxyacetate [7416-48-0], the Loesch ester (26). Subsequently, parallel reactions lead to formation of acetic acid and anhydride plus water. 

A fixed-bed reactor for this hydrolysis that uses feed-forward control has been described (11) the reaction, which is first order ia both reactants, has also been studied kiaeticaHy (12—14). Hydrogen peroxide interacts with acetyl chloride to yield both peroxyacetic acid [79-21-0] and acetyl peroxide... 

Electrolytic oxidation gives acetylene dicarboxyhc acid [142-45-0] (2-butynedioic acid) in good yields (49) chromic acid oxidation gives poor yields (50). Oxidation with peroxyacetic acid gives malonic acid [141-82-2] (qv) (51). 

Esters. The monoisobutyrate ester of 2,2,4-trimethyl-1,3-pentanediol is prepared from isobutyraldehyde ia a Tishchenko reaction (58,59). Diesters, such as trimethylpentane dipelargonate (2,2,4-trimethylpentane 1,3-dinonanoate), are prepared by the reaction of 2 mol of the monocarboxyhc acid with 1 mol of the glycol at 150—200°C (60,61). The lower aUphatic carboxyHc acid diesters of trimethylpentanediol undergo pyrolysis to the corresponding ester of 2,2,4-trimethyl-3-penten-l-ol (62). These unsaturated esters reportedly can be epoxidized by peroxyacetic acid (63). 

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). 

The aromatic ring of a phenoxy anion is the site of electrophilic addition, eg, in methylolation with formaldehyde (qv). The phenoxy anion is highly reactive to many oxidants such as oxygen, hydrogen peroxide, ozone, and peroxyacetic acid. Many of the chemical modification reactions of lignin utilizing its aromatic and phenoHc nature have been reviewed elsewhere (53). 

Three peroxyacids are produced commercially for the merchant market peroxyacetic acid as a 40 wt % solution in acetic acid, y -chloroperoxybenzoic acid, and magnesium monoperoxyphthalate hexahydrate. Other peroxyacids are produced for captive use, eg, peroxyformic acid generated in situ as an epoxidizing agent. 

Peracetic Acid. Peracetic acid (peroxyacetic acid) [79-21-0] the peroxide of acetic acid, is a disinfectant having the desirable properties... 

Entries 1 and 2 in Scheme 2.9 are typical of concerted syn addition to alkene double bonds. On treatment with peroxyacetic acid, the Z-alkene affords the cis-oxirane, whereas the -alkene affords only the iraws-oxirane. Similarly, addition of dibromocarbene to Z-2-butene yields exclusively l,l-dibromo-cw-2,3-dimethylcyclopropane, whereas only 1,1-dibromo-/ra 5-2,3-dimethylcyclopropane is formed from -2-butene. There are also numerous stereospecific anti additions. Entiy 3 shows the anti stereochemistry typical of bromination of simple alkenes. 

Peroxyacetic acid, >43% and with >6% hydrogen peroxide PETN (dry)... 

PERACETIC ACID see PEROXYACETIC ACID PERCHLORATES, INORGANIC, n.o.s. 

Chemical Designations - Synonyms Acetyl hydroperoxide Peroxyacetic acid Chemical Formula CH3COOOH-CH3COOH. 

Mt iliyliiiiLiiic-, Anhydrous 74-89-5 1000 Peracetic Acid (concentration greater than 60% Acetic Acid also called Peroxyacetic Acid) 79-2I- 1 i i t... 

It has recently been suggested that a free radical mechanism i.e., homo-lytic cleavage of the oxygen-oxygen bond rather than the heterolytic cleavage pictured) may be involved in the reaction of some substituted benzophenones and peroxyacetic acid. 

Oxidation of perjliwro- 1,4-benzoquinone hy peroxyacetic acid gives comparatively good yields of 2,3-difluoromaleic acid [74] (equation 65). 

Destruction of the aromatic ring is the mam reaction in the oxidation of tetrafluoro-o phenyleiiediamine with lead tetraacetate by products are tetrafluorobenzotnazole and tetrafluorochinoxalme denvatives [92] (equation 85) Polyfluonnated benzylideneanilines are oxidized by peroxyacids to different products dependmg on reaction contitions at room temperature the benzylidene carbon is oxidized with the formation of peroxy bonds [93 94] (equation 86), whereas in refluxing agent, the azomethme bond is cleaved [93] (equation 86) Pentafluorobenzylidencanilme is oxidized by peroxyacetic acid in dichlo-romethane at room temperature to perfluorobenzoic acid in a 77% yield [93]... 

Pentafluorobenzyl bromide [II] and a partially fluonnated alkyl iodide [12] react with potassium carboxylates An interesting replacement of iodine in a fluonnated alkyl iodide by an acetate group takes place with peroxyacetic acid [13] (equations 10-12)... 

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