Hydroperoxides peroxycarboxylic acid

The oxidation of saturated hydrocarbons in the presence of iron- or manganese-containing catalysts can be achieved by using a variety of oxidants including alkyl hydroperoxides, peroxycarboxylic acids, iodosyl-benzene, dihydrogen peroxide, and dioxygen (9-11). It has been shown that chiral iron- and manganese-porphyrin complexes catalyze the asymmetric epoxidation of unfunctionalized alkenes (75). Except for a number of experiments in which up to 96 % enantiomeric excess (ee) has been reported (16,17), in most epoxidation reactions with chiral porphyrins only a low to moderate enantiomeric excess of the product is obtained (18,19). In association with these catalysts, alkyl hydroperoxides and iodosylbenzene are often used as primary oxidants (18,19). 

The selenides prepared by any of these methods can be converted to selenoxides by such oxidants as hydrogen peroxide, sodium metaperiodate, peroxycarboxylic acids, 1-butyl hydroperoxide, or ozone. 

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. ... 

Upid hydroperoxide determination, 676 Methylenecyclohexene, final ozonide, 718 Methylenecyclopentene, final ozonide, 718 Methylene increment, peroxycarboxylic acids, 158... 

The oxidation of sulfides to sulfoxides or sulfones depend on the reaction conditions used. Hydrogen peroxide and ferf-butyl hydroperoxide have both been used as also has a variety of peroxycarboxylic acids. Since all of the peroxycarboxylic acids are stronger oxidants than hydrogen peroxide, reagents such as MCPBA have been used to oxidise sulfides to sulfoxides under very mild conditions. In the example shown in Eq. (38) the diastereomeric sulfoxides were obtained in good yield [46]. 

Peroxycarboxylic acid esters are utilized as initiators for radical polymerization and are interesting intermediates for the decarboxylation of carboxylic acids. They are generally prepared by the acylation of hydro peroxides with acid chlorides, acid anhydrides, or imidazolides in the presence of a base. Condensation of carboxylic acids (20) with /-butyl-hydroperoxide (21) has been smoothly achieved by the use of diethyl phophorocyanidate and NEt3 under mild conditions giving f-butyl peroxycarboxylates (22) in good yield.9... 

The influence of leaving group ability on the rate constant for oxygen transfer to (EDTA)Fe(III) from peroxycarboxylic acids and hydroperoxides, Proc. Natl. AcadSci. USA 84 1734(1987). 

Peroxycarboxylic acid esters from hydroperoxides CO Cl COOgR... 

Alcohols can be converted to o-nitrophenylselenides by reaction with o nitrophenyl selenocyanate and tri(rt-butylphosphine). Several oxidants have been employed to convert selenides to selenoxides and bring about elimination. Hydrogen peroxide, sodium metaperiodate, peroxycarboxylic acids, tert bnty hydroperoxide, and ozone have been used most frequently. 

The first such process is a variant of the oxacyclo-propanation reaction discussed in Section 12-10, as applied specifically to 2-propenyl (allylic) alcohols. However, instead of a peroxycarboxylic acid, the reagent is ferf-butyl hydroperoxide in the presence of titanium (TV) isopropoxide ( Sharpless epoxidation ), the function of the chiral auxiliary being assumed by tartaric acid diethyl ester (Real Life 5-3). The naturally occurring (-l-)-[2/ ,3/ ]-diethyl tartrate and its nonnatural (—)-(25,35) mirror image are both commercial products. One delivers oxygen to one face of the double bond, the other to the opposite face, as shown below, giving either enantiomer of the oxacyclopropane product with high enantiomer excess (Section 5-2). 

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