Peracetic acid alcohol oxidation

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. 

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. 

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. ... 

Oxidation with Stoichiometric Oxidants. Certain peracids reacting with alkanes yield alcohols. Peracetic acid,68 69 perbenzoic acid,70 m-CPBA,71,72 and nitroper-benzoic acids may be used. Alcohols or an equilibrium mixture of the alcohol and the trifluoroacetate77 are formed on the action of pertrifluoroacetic acid. A high degree of regioselectivity (better than 97%), specifically, preferential attack at the tertiary C—H bonds, is usually observed ... 

This work concerns mainly the modification of commercial polymers bearing hydroxy fonctions as alcohol, hydroperoxide or carboxylic acid, by reactive gases or liquid volatil compounds capable to penetrate in the polymer matrix. The modifications of membranes properties as gas permeability or surface tension will also be reported. Few examples will also concern the reaction of double bond with 12 and HBr vapor as well as the oxidation of piperidine group by peracetic acid. 

A remarkably high diastereoselective excess was obtained in the addition of the anion of (S)-(-)-methyl 1-naphthyl sulfoxide to n-alkyl phenyl ketones. The sulfoxide was prepared in optically pure form by oxidation of the complex of methyl 1-naphthyl sulfide and 13-cyclodextrin with peracetic acid followed by crystallization. Desulfurization of the adducts provided enantiomerically pure tertiary alcohols (393]. 

Oxidation of sec-alcohols.1 In the presence of CH3C03H, this chromium(VI) reagent can be used in catalytic amount (2 mole %) for oxidation of sec-alcohols to ketones in high yield. Under these conditions cholesterol is oxidized to A5-3-cholestanone (84% yield). Primary alcohols can be oxidized to aldehydes (—80% yield). f-Butyl hydroperoxide or anhydrous H202 cannot replace the peracetic acid as the reoxidant. 

The oxidation of alcohols to carbonyl compounds with the stable nitroxyl radical TEMPO (86) as catalyst is a well-known preparative method [134, 135]. Hypochlorite or peracetic acid is usually used as the final oxidizing agent and ca. 1 mol% of catalyst 86 is used. In 1996 Rychnovsky et al. reported the synthesis of the chiral, binaphthyl-derived TEMPO analog 87 [136], Results obtained by use of 0.5-1 mol% of catalyst 87 [136] are listed in Table 10.12. In these oxidation reactions 0.6-0.7 equiv. sodium hypochlorite were used as the final oxidizing agent (plus... 

Simpler, aliphatic peracids can also be used for alcohol oxidation under certain conditions. Morimoto and co-workers have reported the smooth oxidation of secondary alcohols and benzylic alcohols to the corresponding carbonyl compounds using peracetic acid (PAA) in the presence of 0.5-1.5 equivalents of sodium bromide in acetic acid solution (Figure 3.36).190... 

Metal species, including chromium,191 iron,192 cobalt,193 cerium194 and ruthenium195 compounds, have also been used to catalyse alcohol oxidation with peracetic acid. 

Aqueous hydrogen peroxide is the oxidant of choice for the preparation of sulfoxides.367 Acetic acid is often used as the solvent due to its specific solvation rather than due to peracetic acid formation.368 Alcohols and ketones have been... 

Oxygenated and highly oxidized compounds (ozone, hydrogen peroxide, phenols, alcohols, persulfate, percarbonate, permanganate, peracetic acid, etc.)... 

Dibromoacetic acid [631 -64-1] (Bi CHCOOH), mol wt 217.8, C2H2Bi 02, 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 oxidizing tdbromoetliene [598-16-3] with peracetic acid... 

With the catalytic system secondaiy alcohols are still oxidized quickly (Scheme 2) and in excellent yield with 2 equiv. of peracetic acid at 0 C. Primary alcohols are also reported to be oxidized to aldehydes in good yields, but details have not been given. 

Forms unstable explosive products in reaction with acetaldehyde + desiccants (forms polyethyUdine peroxide) acetic acid (forms peracetic acid) acetic + 3-thietanol acetic anhydride acetone (forms explosive peroxides) alcohols (products are shock-and heat-sensitive) carboxylic acids (e.g., formic acid, acetic acid, tartaric acid), diethyl ether, ethyl acetate, formic acid -f- metaboric acid, ketene (forms diacetyl peroxide) mercur f(II) oxide + nitric acid (forms mercur f(II) peroxide) thiourea -f- nitric acid polyacetoxyacryUc acid lactone + poly(2-hydroxyacrylic acid) + sodium hydroxide. 

Esters have been prepared in 63-73% yields from several simple cycloalkyl and aryl alkyl ketones by reaction at room temperature with per-benzoic acid. The larger radical of the ketone appears as the alcohol fragment of the ester. Cyclic ketones are oxidized by potassium persulfate and sulfuric acid to esters from which o>-hydroxy aliphatic esters are obtained upon hydrolysis and reesterification. Peracetic acid in acetic anhydride converts salicylaldehyde to o-hydroxyphenyl formate (88%). ... 

A high-valent ruthenium complex is also reported to cleave the sp C-H bond. RuCl3 -3H20 catalyzes the transformation of cyclic alkanes to the corresponding ketones in the presence of peracetic acid, where oxoruthenium species is considered to act as the active species. Alcohol, as a primary product in this oxidation reaction, is obtained as an intermediate in the presence of trifluoroacetic acid (Scheme 14.11) [25]. 

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