Ethyl peracetate

The only accident that involves a saturated ester is the result of an attempt to extract an organic residue containing hydrogen peroxide with ethyl acetate. The latter was mixed with methanol and refluxed with the residue and hydrogen peroxide in an aqueous solution. A second extraction was carried out with acetate and the liquid was then evaporated. The small quantity of the compound that remained after the evaporation detonated violently. It was thought that this detonation was the result of the violent decomposition of methyl hydroperoxide, peracetic acid and/or ethyl peracetate. 

Ethyl peracetate was the first ester of a peroxy acid, and was characterized by Baeyer and Villiger in 1901. Kinetic studies of perester decomposition were reported by Blomquist and Ferris in 1951, and in 1958 Bartlett and Hiatt proposed that concerted multiple bond scission of peresters could occur when stabilized radicals were formed (equation 46). As noted below (equation 57), polar effects in perester decomposition are also significant. 

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. 

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. 

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). 

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. 

Muconic acid has been obtained in a variety of ways. The procedures that seem most important from a preparative point of view are by treatment of ethyl o ,5-dibromoadipate with alcoholic potassium hydroxide, by condensation of glyoxal (as the sodium bisulfite addition product) with malonic acid, by heating ethyl l-acetoxy-l,4-dihydromuconate (obtained by condensing ethyl oxalate and ethyl crotonate, acetylating, and reducing),and by oxidation of phenol with peracetic acid. ... 

Organic Peroxides — (R-O-O-R) are very hazardous. Most of the compounds are so sensitive to friction, heat, and shock that they cannot be handled without dilution. As a result, organic peroxides present a serious fire and explosion hazard. Commonly encountered organic peroxides include benzoyl peroxide, peracetic acid, and methyl ethyl ketone peroxide. 

Acetylamino-1 -(4-methylmercaptophenyl)-1,3-propanediol Hydrogen chloride Ethyl dichloroacetate Peracetic acid... 

These codes are mentioned for all the substances that are subjected to regulations in Part Three. Amongst the twenty substances chosen previously only four of them have such a code. They are nitromethane and peracetic acid (code 5), acetylene (codes 5 and 6) and ethyl nitrate (code 2). 

Aliphatic amines have much less effect on the later reactions of the gas-phase oxidation of acetaldehyde and ethyl ether than if added at the start of reaction. There is no evidence that they catalyze decomposition of peroxides, but they appear to retard decomposition of peracetic acid. Amines have no marked effect on the rate of decomposition of tert-butyl peroxide and ethyl tert-butyl peroxide. The nature of products formed from the peroxides is not altered by the amine, but product distribution is changed. Rate constants at 153°C. for the reaction between methyl radicals and amines are calculated for a number of primary, secondary, and tertiary amines and are compared with the effectiveness of the amine as an inhibitor of gas-phase oxidation reactions. 

Action of Aliphatic Amines on Oxidation Products of Ethyl Ether. Amines were added during the oxidation of ethyl ether. Both ethylamine (Figure 5) and triethylamine (Figure 6) are more than three times more effective as negative catalysts when added at the start of reaction than during the reaction, and triethylamine has little effect on the subsequent rate of reaction when added at the minimum pressure change [when the maximum concentration of peracetic acid is present (27)]. 

It is prepared by treating ethyl cinnamate with peracetic acid [212] or by condensation of benzaldehyde with ethyl chloroacetate (in the above Darzens reaction, R = H). The glycidate is used as a long-lasting fragrance material for creating harmonic, fruity notes in household and fine fragrances. 

Glutaraldehyde Solution Acetylacetone N-Amyl Mercaptan N-Amyl Alcohol Pentaerythritol 1-Pentene Amyl Acetate N-Amyl Alcohol Ethyl Butanol N-Amyl Chloride N-Amyl Methyl Ketone N - Amyltrochlorosilane Peracetic Acid Urea Peroxide Perchloric Acid Perchloric Acid... 

In the peracid process (Bayer-Degussa technology916) propionic acid is oxidized by hydrogen peroxide in the presence of H2S04 to yield perpropionic acid, which, in turn, is used to oxidize propylene to propylene oxide. The peracetic acid process (Daicel technology ) employs a mixture of acetaldehyde, ethyl acetate, and... 

Low Temperature Reaction. Reaction in the low temperature regime below 320°C. is of a different character. The products include carbon dioxide and significant quantities of peroxy compounds, as well as carbon monoxide, water, formaldehyde, and methanol, but methane and ethylene are formed only in traces. The peroxy compounds comprise hydrogen peroxide from all three ketones, methyl hydroperoxide from acetone (8) and methyl ethyl ketone (I), and ethyl hydroperoxide from diethyl ketone (1). Methyl ethyl ketone also gives large amounts of peracetic acid (1). 

Figure 6 shows the variation of peroxide concentration in methyl ethyl ketone slow combustion, and similar results, but with no peracid formed, have been found for acetone and diethyl ketone. The concentrations of the organic peroxy compounds run parallel to the rate of reaction, but the hydrogen peroxide concentration increases to a steady value. There thus seems little doubt that the degenerate branching intermediates at low temperatures are the alkyl hydroperoxides, and with methyl ethyl ketone, peracetic acid also. The tvfo types of cool flames given by methyl ethyl ketone may arise from the twin branching intermediates (1) observed in its combustion. 

Purification of the Organoselenium Compounds. After the oxidation of 2-butene with selenium dioxide was completed, the acetic acid solvent and the volatile reaction products were distilled at reduced pressure (10 mm. HgA). The residue, a yellow oil, was purified by adsorption chromatography in a column packed with silica gel. n-Hexane and ethyl ether were used as eluents. The same procedure was applied to the fractionation and purification of the organoselenium compounds obtained from the oxidation of bis(l-methyl-2-acetoxypropyl) selenide with peracetic acid. 

Illustrative of the preparation of epoxyacetylenes are the reaction of perbenznio acid with 1 -ethyl-3-buten-1 -yne16 and of peracetic acid with 3>0-ditnethyl-2,4 Octadien-4-yne,10 as shown in Kqs. (8) and (9). 

Nitroso-tert-octane may also be prepared by oxidation of tert-octylamine with peracetic acid in ethyl acetate, obtained by the submitters from the Union Carbide Corporation. To a 1-L, three-necked flask equipped with a mechanical stirrer and an addition funnel are added 51.7 g of tert-octylamine (0.4 mol), 50 nL of water, and 50 nL of ethyl acetate. The flask is placed in an ice bath and the contents are stirred until the temperature reaches 0-5°C. A solution of peracetic acid in ethyl acetate (3.15 M... 

Peracetic acid solution (107.7 g of 9.0 wt % peracetic acid) at ambient temperature was added to a reaction flask equipped with mechanical stirrer and thermocouple, nitrogen inlet adapter and addition funnel. A 20 wt % stock solution of the dienolsilyl ether of codeinone (41.7 g) was added through the addition funnel over a period of about 5 min and the temperature of the contents maintained at 28°C. The batch was stirred at 22°C for at least 3 hours. In order to test reaction completeness, a small sample was withdrawn from the batch and quenched with saturated sodium bicarbonate solution, and extracted with ethyl acetate. The EtOAc layer was spotted onto a TLC plate and subsequently checked for the disappearance of starting dienolsilyl ether of codeinone. The TLC mobile phase was a mixture of 95 5 of dichloromethane and methanol plus 3-5 drops of concentrated ammonium hydroxide. If the reaction was adjudged incomplete, the mixture was stirred at the same temperature for an additional 2 hours then analyzed by TLC again. Alternatively completion of the reaction was pushed by the addition of 10 g of peracetic acid (9.0 wt %) and stirring for an additional 1 h (analysis was then once more performed using TLC). 

Hydrogen chloride Ethyl dichloroacetate Peracetic acid... 

Acetic acid Acetic anhydride, chloroacetic acid, ethyl acetate, peracetic acid, vinyl acetate, cellulose acetate, terephthalic acid Food additives, solvent, monomers, resin Cheryan etal., 1997 Ravinder etal., 2000 Patel etal., 2006... 

Typical procedure for the oxidation of hydrocarbons. To a stirred mixture of hydrocarbon (2 mmol) and 3 (100 mg) in 1,2-dichloroethane/ethy acetate (7 1) was added a 30% solution of peracetic acid in ethyl acetate (6 mmol in 4 ml) dropwise at reflux over the period of 2 h. After 2 h at reflux the mixture was cooled, the supported ruthenium complex filtered off and the product analysed. 

We have found it useful to prepare authentic samples of the various diperoxides encountered by using a variation of the Baeyer-Villiger oxidation conditions. Oxidation of ketones at low temperatures using peracetic acid has been reported (23) to give diperoxides instead of the esters produced under Baeyer-Villiger conditions. Authentic samples of 10 and 11, can be prepared, respectively, by the peracetic oxidation of acetone and methyl ethyl ketone jointly or methyl ethyl ketone alone. We are studying the mechanism of this interesting oxidation reaction. 

Similar stereochemical possibilities are present when 11 is obtained from trans-l,3-dimethyl-3-hexene, 13, as a cross diperoxide from the ozon-olysis of 12 or from the peracetic acid oxidation of methyl ethyl ketone. 

No information is available as to the individual steps of the reaction, and none is likely to issue from kinetic studies with higher alkyl peroxides (C > 2) or peracids. The reasons are implicit in the data of Table VIII (1, 69,101a, 162, 164), which show that the observed rate constants for Compound I formation (k, app) with peracetic acid, hydroxymethyl hydroperoxide, and ethyl hydrogen peroxide are of the same order of magnitude (2.5 dt 0.5 X 10 M sec" ) in spite of differences in the following ... 

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