Organic peracids, functionalization

The organic peracids and peroxides are important oxidants in the atmosphere. These are responsible for the formation of H2SO4 in the aqueous phase and are thought to have toxic effects on plants. They function as reservoirs for the peroxy radicals and reflect the radical levels of the atmosphere. The organic peracids and peroxides should be given serious attention, especially as we begin to control NOx emission levels in an attempt to reduce urban and regional O3 levels. 

Peracids. Peracids are compounds containing the functional group —OOH derived from an organic or inorganic acid functionaHty. Typical stmctures include CH2C(0)OOH derived from acetic acid and H0S(0)200H (peroxymonosulfuric acid) derived from sulfuric acid. Peracids have... 

There are many transition metal ion oxidants used in organic chemistry for the interconversion of functional groups. Those which have been used for the preparation of sulphones from sulphoxides will be discussed below. It is very interesting to note that this type of oxidant often reacts more rapidly with sulphoxides than with sulphides and so sulphoxides may be selectively oxidized with transition metal ion oxidants in the presence of sulphides. This is in direct contrast to the oxidation of sulphides and sulphoxides with peracids and periodate, for example, where the rate of reaction of the sulphide is more than 100 times that for the corresponding sulphoxide. 

The products obtained by the action of peracids upon 3-alkoxy-3,5-dienes are dependent upon the reaction conditions. Aqueous organic solvents and the gradual addition of peracid favour the formation of 6 -hydroxy-4-en-3-one, but when an excess of peracid is added in one portion the product, obtainable in high yield, is the unsaturated aldehyde-ester (393) which has also been obtained (as ethyl ester) by photochemical oxidation of the oxathian (394) followed by a reductive desulphuration. In non-polar solvents a 1 1 adduct (395) is formed between m-chloroperbenzoic acid and 3-acetoxy-3,5-dienes which is sufficiently stable (in the presence of a 17-ketone function) to be isolated and acetylated to the 6 -acetate or oxidised by chromium trioxide in pyridine to the b-ketone. ... 

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