Peracetic acid method

Peroxide Determinations. Bawn and Williamson report two iodometric procedures for determining peracetic acid (Methods I and III below) and one method for determining total peroxide (4) (Method II). Bawn and Jolly report another method for total peroxide (5) (Method IV below). The difference between total peroxide and peracetic acid is assumed to be acetaldehyde monoperacetate (AMP). Each method was tested in our preliminary studies. Method III is preferred for peracetic acid because the results are more reproducible. In Method I a large blank titration was always observed, while in Method III the blank titration was very small. Method IV is preferred for total peroxide because it seems to be more sensitive to total peroxide and less sensitive to water content of the acetic acid solvent. 

Here again the peracetic oxidation method was used to prepare comparison samples of diperoxides. Oxidation of 3-pentanone, for example, gave a 46% yield of 16. This method can also be used to prepare diperoxides such as 15. When equimolar amounts of acetone and 3-pentanone are oxidized by the peracetic acid method, diperoxide 15 is obtained along with 9 and 16. Similarly, oxidation of equimolar amounts of acetone and 2-butanone gave 9, 10, and 11. 

The standard methods of oxidation of pyridines and other heteroaromatic nitrogen compounds malfw use of peroxy (u ids or hydrogen peroxide in carboxylic acid solution. Peracetic acid, peroxymono-phdialic acid and MCraA can all convert simple pyridines to the N-oxides. For example, the pyridine... 

Acid-catalysed peracetic acid oxidation of allobetulone (118) affords (119) and (120) in addition to the expected a-lactone. These results are relevant to the current interest in methods for removal of one or both C-4 methyls from triterpenoids... 

Preparative Methods by the oxidation of thiourea or amino-iminomethanesulfinic acid (formamidinesulfinic acid) with peracetic acid. Many substituted aminoiminomethanesulfonic acids can be prepared in the same way. 2 Others have utilized hydrogen peroxide with sodium molybdate as a catalyst to oxidize the corresponding thioureas to a variety of monosubsUtuted aminoiminomethanesulfonic acids the substituents include phenyl, 2-methylphenyl, 4-fluorophenyl, / -propyl, cyclohexylmethyl, S-a-methylbenzyl, cyclooctyl, and benzhydiyl. ... 

The preparation of 0-enriched dithiolylidene ketones (27 R = Me or Ph) from thiathiophthens, by the sulphuric acid method, has been described, and the same method applied to the coumarin derivative (21 R= Me). Peracetic acid in acetone is reported to be a more effective reagent than mercuric acetate for the conversion of 3-formyl-2,5-diaryl-6a-thiathio-phthens (28) into the corresponding dithiolylidene ketones. ... 

Preparative Methods prepared from 2-bromopyridine by oxidation to the M-oxide using either Perbenzoic Acid or Peracetic Acid, followed by displacement of bromide using either Sodwin Dithionite or Sodium Sulfide and Sodium Hydroxide. An alternative is to treat the N-oxide with Thiourea and then hydrolyze the resulting thiouronium salt. 

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.)... 

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. 

Satisfactory 40% peracetic acid is obtainable from Buffalo Electrochemical Corporation, Food Machinery and Chemical Corporation, Buffalo, New York. The specifications given by the manufacturer for its composition are peracetic acid, 40% hydrogen peroxide, 5% acetic acid, 39% sulfuric acid, 1% water, 15%. Its density is 1.15 g./ml. The peracetic acid concentration should be determined by titration. A method for the analysis of peracid solutions is based on the use of ceric sulfate as a titrant for the hydrogen peroxide present, followed by an iodometric determination of the peracid present.3 The checkers found that peracetic acid of a lower concentration (27.5%) may also be used without a decrease in yield. The product was found to be sufficiently pure, after only one recrystallization from 60 ml. of petroleum ether (b.p. 40-60°) and cooling overnight to —18°, to be used in the next step. 

Intensive technologies are derived from the processes used for the treatment of potable water. Chemical methods include chlorination, peracetic acid, ozonation. Ultra-violet irradiation is becoming a popular photo-biochemical process. Membrane filtration processes, particularly the combination microfiltration/ultrafiltra-tion are rapidly developing (Fig. 3). Membrane bioreactors, a relatively new technology, look very promising as they combine the oxidation of the organic matter with microbial decontamination. Each intensive technique is used alone or in combination with another intensive technique or an extensive one. Extensive... 

Endrin is a stereoisomer of dieldrin produced by the reaction of vinyl chloride and hexachloro-cyclopentadiene to yield a product which is then dehydrochlorinated and condensed with cyclopentadiene to produce isodrin. This intermediate is then epoxidized with peracetic or perbenzoic acid to yield endrin. An alternative production method involves condensation of hexachlorocyclopentadiene with acetylene to yield the intermediate for condensation with cyclopentadiene (EPA 1985e IARC 1974). 

Methylenecyclohexane oxide has been prepared by the oxidation of methylenecyclohexane with benzonitrile-hydrogen peroxide or with peracetic acid by treatment of 1-chlorocyclo-hexylmethanol with aqueous potassium hydroxide and by the reaction of dimethylsulfonium methylide with cyclohexanone. This reaction illustrates a general method for the conversion of ketones and aldehydes into oxiranes using the methylene-transfer reagent dimethyloxosulfonium methylide. The yields of oxiranes are usually high, and the crude products, in most cases, are of sufficient purity to be used in subsequent reactions (e.g., rearrangement to aldehydes) without further purification. 

Another method of making epoxides is the electrophilic reaction of alkenes with a peroxy acid such as peroxyacetic acid (sometimes simply peracetic acid). Thus, cyclohexene may be converted into the epoxide in a single reaction. 

Acetic anhydride may be produced by three different methods. The first procedure involves the in situ production from acetaldehyde of peracetic acid, which in turn reacts with more acetaldehyde to yield the anhydride. In the preferred process, acetic acid (or acetone) is pyrolyzed to ketene, which reacts with acetic acid to form acetic anhydride. A new process to make acetic anhydride involves CO insertion into methyl acetate. This may be the process of the future. 

The RP-HPLC method based on the CL reaction of luminol (124) catalyzed by Co(II) (Section in.B.2.c) can be applied for determination of peroxycarboxylic acids, esters and diacyl peroxides (see examples of LOD in equation 67, Section V.B.2.c) . The biosensor prepared according to equation 70, that is effective in the determination of hydroperoxides (Section V.B.6.b), becomes deactivated after three days of operation when trying to determine t-butyl peracetate. ... 

Particularly for the preparation of aliphatic nitroso compounds, the oxidation of oxaziranes and imines with peracetic acid (Eqs. 6) probably represents the most original and most widely applicable method of preparation. 

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