Peracetic acid

Diphenic acid. Phenanthrene upon oxidation in acetic acid solution at 85° with 30 per cent, hydrogen peroxide gives diphenic acid (diphenyl-2 2 -di-carboxyHc acid) no phenanthraquinone is formed under these experimental conditions. The reaction is essentially an oxidation of phenanthrene with peracetic acid. (For another method of preparation, see Section I V,74.)... 

The epoxides may be converted into 1 2-glycols by hydrolysis. In some cases the 1 2-glycol may be produced directly by carrying out the epoxidation in the presence of water. If the 1 2-glycol is desired, it is usually better to employ performic acid or peracetic acid, the latter best in the presence of a trace of sulphuric acid. An epoxide is first formed, followed by the hydroxy-formate or hydroxy-acetate, and ultimately the 1 2-glycol ... 

The antibacterial [(5-nitrofuryl)vinyl]thiazole-N-oxides (193) were prepared by oxidizing the corresponding thiazoles with hydrogen peroxide or peracetic acid (Scheme 89) (475). 

Little work has been carried out on thiazole N-oxides. These products are unstable and breakdown by autoxidation to give thiazolium-A -oxide sulfates and other decomposition products (264). They are prepared by direct oxidation with hydrogen peroxide, or by tungstic acid (264, 265) or peracetic acid (265-267). 

Ozonolysis of 2-styryl-4-methylthiazole followed by oxidation of the intermediate carbonyl compound with peracetic acid yields 4-methyl-2-thiazolecarboxylic acid (30). 

Acetaldehyde, first used extensively during World War I as a starting material for making acetone [67-64-1] from acetic acid [64-19-7] is currendy an important intermediate in the production of acetic acid, acetic anhydride [108-24-7] ethyl acetate [141-78-6] peracetic acid [79-21 -0] pentaerythritol [115-77-5] chloral [302-17-0], glyoxal [107-22-2], aLkylamines, and pyridines. Commercial processes for acetaldehyde production include the oxidation or dehydrogenation of ethanol, the addition of water to acetylene, the partial oxidation of hydrocarbons, and the direct oxidation of ethylene [74-85-1]. In 1989, it was estimated that 28 companies having more than 98% of the wodd s 2.5 megaton per year plant capacity used the Wacker-Hoechst processes for the direct oxidation of ethylene. 

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). 

Figure 3 shows the production of acetaldehyde in the years 1969 through 1987 as well as an estimate of 1989—1995 production. The year 1969 was a peak year for acetaldehyde with a reported production of 748,000 t. Acetaldehyde production is linked with the demand for acetic acid, acetic anhydride, cellulose acetate, vinyl acetate resins, acetate esters, pentaerythritol, synthetic pyridine derivatives, terephthaHc acid, and peracetic acid. In 1976 acetic acid production represented 60% of the acetaldehyde demand. That demand has diminished as a result of the rising cost of ethylene as feedstock and methanol carbonylation as the preferred route to acetic acid (qv). 

The nameplate capacities for acetaldehyde production for the United States in 1989 are shown in Table 5 (120). Synthetic pyridine derivatives, peracetic acid, acetate esters by the Tischenko route, and pentaerythritol account for 40% of acetaldehyde demand. This sector may show strong growth in some products but all of these materials maybe prepared from alternative processes. 

The price of acetaldehyde duriag the period 1950 to 1973 ranged from 0.20 to 0.22/kg. Increased prices for hydrocarbon cracking feedstocks beginning in late 1973 resulted in higher costs for ethylene and concurrent higher costs for acetaldehyde. The posted prices for acetaldehyde were 0.26/kg in 1974, 0.78/kg in 1985, and 0.92/kg in 1988. The future of acetaldehyde growth appears to depend on the development of a lower cost production process based on synthesis gas and an increase in demand for processes based on acetaldehyde activation techniques and peracetic acid. 

About half of the wodd production comes from methanol carbonylation and about one-third from acetaldehyde oxidation. Another tenth of the wodd capacity can be attributed to butane—naphtha Hquid-phase oxidation. Appreciable quantities of acetic acid are recovered from reactions involving peracetic acid. Precise statistics on acetic acid production are compHcated by recycling of acid from cellulose acetate and poly(vinyl alcohol) production. Acetic acid that is by-product from peracetic acid [79-21-0] is normally designated as virgin acid, yet acid from hydrolysis of cellulose acetate or poly(vinyl acetate) is designated recycle acid. Indeterrninate quantities of acetic acid are coproduced with acetic anhydride from coal-based carbon monoxide and unknown amounts are bartered or exchanged between corporations as a device to lessen transport costs. 

By-product acetic acid is obtained chiefly from partial hydrolysis of cellulose acetate [9004-35-7]. Lesser amounts are obtained through the reaction of acetic anhydride and cellulose. Acetylation of saHcyHc acid [69-72-7] produces one mole of acetic acid per mole of product and the oxidation of allyl alcohol using peracetic acid to yield glycerol furnishes by-product acid, but the net yield is low. 

Dibromoacetic acid [631-64-1] (Br2CHCOOH), mol wt 217.8, C2H2Br202, mp 48°C, bp 232—234°C (decomposition), is soluble in water and ethyl alcohol. It is prepared by adding bromine to boiling acetic acid, or by oxidi2ing tribromoethene [598-16-3] with peracetic acid. 

Propylene oxide-based glycerol can be produced by rearrangement of propylene oxide [75-56-9] (qv) to allyl alcohol over triUthium phosphate catalyst at 200—250°C (yield 80—85%) (4), followed by any of the appropriate steps shown in Figure 1. The specific route commercially employed is peracetic acid epoxidation of allyl alcohol to glycidol followed by hydrolysis to glycerol (5). The newest international synthesis plants employ this basic scheme. 

Medroxyprogesterone acetate (74) is stmcturaHy related to and has been prepared from hydroxyprogesterone (39) (Fig. 10). Formation of the bis-ketal accomplishes the protection of the ketones and the required migration of the double bond. Epoxidation with peracetic acid produces a mixture of epoxides (75), with a predominating. Treatment of the a-epoxide with methyl magnesium bromide results in diaxial opening of the epoxide. Deprotection of the ketones provides (76), which is dehydrated to (77) by treatment with dilute sodium hydroxide in pyridine. Upon treatment with gaseous hydrochloric... 

Earlier reports have indicated that esters can form before significant amounts of acids accumulate (16). The Bayer-ViUiger oxidations of ketones with intermediate hydroperoxides and/or peracids have been suggested as ester forming mechanisms (34,56). However, the reactions of simple aUphatic ketones with peracetic acid are probably too slow to support this mechanism (57,58). Very early proposals for ester formation, although imaginative, appear improbable (59). 

A thkd method utilizes cooxidation of an organic promoter with manganese or cobalt-ion catalysis. A process using methyl ethyl ketone (248,252,265—270) was commercialized by Mobil but discontinued in 1973 (263,264). Other promoters include acetaldehyde (248,271—273), paraldehyde (248,274), various hydrocarbons such as butane (270,275), and others. Other types of reported activators include peracetic acid (276) and ozone (277), and very high concentrations of cobalt catalyst (2,248,278). 

Another method of preparing mercuric acetate is the oxidation of mercury metal using peracetic acid dissolved in acetic acid. Careful control of the temperature is extremely important because the reaction is quite exothermic. A preferred procedure is the addition of approximately half to two-thirds of the required total of peracetic acid solution to a dispersion of mercury metal in acetic acid to obtain the mercurous salt, followed by addition of the remainder of the peracetic acid to form the mercuric salt. The exothermic reaction is carried to completion by heating slowly and cautiously to reflux. This also serves to decompose excess peracid. It is possible and perhaps more economical to use 50% hydrogen peroxide instead of peracetic acid, but the reaction does not go quite as smoothly. 

Ozone accelerates the autoxidation of acetaldehyde to peracetic acid at below 15°G. Acetaldehyde hemiacetal peracetate, an intermediate product, is... 

Peracetic acid then reacts with propylene at 320—350 K and 1.00—1.34 MPa (10—13.2 atm), forming propylene oxide and acetic acid. 

Although this process has not been commercialized, Daicel operated a 12,000-t/yr propylene oxide plant based on a peracetic acid [79-21-0] process during the 1970s. The Daicel process involved metal ion-catalyzed air oxidation of acetaldehyde in ethyl acetate solvent resulting in a 30% peracetic acid solution in ethyl acetate. Epoxidation of propylene followed by purification gives propylene oxide and acetic acid as products (197). As of this writing (ca 1995), this process is not in operation. 

Fig. 2. Synthesis of uma2enil (18). The isonitrosoacetanihde is synthesized from 4-f1iioroani1ine. Cyclization using sulfuric acid is followed by oxidization using peracetic acid to the isatoic anhydride. Reaction of sarcosine in DMF and acetic acid leads to the benzodiazepine-2,5-dione. Deprotonation, phosphorylation, and subsequent reaction with diethyl malonate leads to the diester. After selective hydrolysis and decarboxylation the resulting monoester is nitrosated and catalyticaHy hydrogenated to the aminoester. Introduction of the final carbon atom is accompHshed by reaction of triethyl orthoformate to...

Ca.ta.lysts, A small amount of quinoline promotes the formation of rigid foams (qv) from diols and unsaturated dicarboxyhc acids (100). Acrolein and methacrolein 1,4-addition polymerisation is catalysed by lithium complexes of quinoline (101). Organic bases, including quinoline, promote the dehydrogenation of unbranched alkanes to unbranched alkenes using platinum on sodium mordenite (102). The peracetic acid epoxidation of a wide range of alkenes is catalysed by 8-hydroxyquinoline (103). Hydroformylation catalysts have been improved using 2-quinolone [59-31-4] (104) (see Catalysis). 

Peracids are also available as aqueous solutions that contain the peracid in equihbrium with hydrogen peroxide and the parent acid. Peracetic acid [79-21-0] is commercially available as a 40% solution in dilute acetic acid. The water and dilution of the peracid make these solutions easier to handle than their sohd counterparts, but they still require careful handling and protection from heat. 

Synthetic Fibers. Most synthetic fibers are sufficientiy white and do not requite bleaching. For white fabrics, unbleached synthetic fibers with duorescent whitening agents are usually used. When needed, synthetic fibers and many of theit blends are bleached with sodium chlorite solutions at pH 2.5—4.5 for 30—90 min at concentrations and temperatures that depend on the type of fiber. Solutions of 0.1% peracetic acid are also used at pH 6—7 for 1 h at 80—85°C to bleach nylon. 

Apphcations of phase-transfer catalysis with these additional oxidants are known peracetic acid, air—KOH, K2[Pe(CN)g], KO2, K CrO, ... 

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

Organism Peracetic acid Active chlorine Benzalkonium chloride... 

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