Secondary oxidants peracetic acid

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. 

This reaction has been proposed to occur in the vapor phase by McDowell and Sifniedes (20). The peracetoxy radical in the first mechanism proposed will be produced by Reaction 13, which in this case is a secondary reaction. Reoxidation of the metal ion in the 2+ oxidation state could also lead to by-products at low metal ion-peracetic acid ratios (4,19). 

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... 

With the catalytic system secondary 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. ... 

Oxidative Methods. - Corey et al. have reported on the use of the cyclic chromate ester (1) as a catalyst for the peracetic acid oxidation of secondary alcohols. The reagent oxidises primary alcohols very slowly, and is compatible with tetrahydropyranyl protection of alcohols furthermore, it has the great advantage of avoiding the toxicological and disposal problems associated with stoichiometric chromium reagents. The selective oxidation of benzylic alcohols in the presence of... 

Various aliphatic and aromatic secondary alcohols can be oxidized with peracetic acid in the presence of RUCI3 catalyst to give the corresponding ketones highly efficiently [75]. 

Tertiary alkyl primary amines can be oxidized to nitro compounds in excellent yields with KMn04.39S This type of nitro compound is not easily prepared in other ways. All classes of primary amine (including primary, secondary, and tertiary alkyl as well as aryl) are oxidized to nitro compounds in high yields with dimethyldioxirane.399 Other reagents that oxidize various types of primary amines to nitro compounds are dry ozone,4,111 various peracids,401 including peracetic and peroxytrifluoroacetic acids, f-butyl hydroperoxide in the presence of certain molybdenum and vanadium compounds,402 F7-H20-MeCN,41123 and sodium perborate.403... 

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