Peroxyacetic acid, synthesis

In the synthesis of Travoprost, an antiglaucoma agent, a bicyclo[2.2.1]heptan-2-one is converted to a lactone.240 The commercial process uses peroxyacetic acid as the oxidant and gives a 40% yield. The regioselectivity in this case is only 3 1 but the unwanted isomer can be removed by selective hydrolysis. 

The synthesis of 1,3,5,7-tetranitroadamantane (104) from 1,3,5,7-tetraaminoadamantane (103) has been improved upon by the use of dimethyldioxirane (91 %), and also, by using a mixture of sodium percarbonate and A,A,iV, iV -tetraacetylethylenediamine in a biphasic solvent system, followed by treating the crude product with ozone (91 %) the latter involving the in situ generation of peroxyacetic acid. 

IIIA). The latter compounds were used for the synthesis of 6-acetyl- and 6-nitro-substituted ll-phenoxynaphthacene-5,12-quinone by acetylation with acetic anhydride in the presence of catalytic content of sulfuric acid and by oxidation with peroxyacetic acid, respectively. 

Just as carbon-based alkyl groups can be oxidized, a silicon-based silane unit can be oxidized under certain conditions. Alkylsilanes can be converted to a hydroxy unit, but either an aryl group (R—SiR 2Ar) or another silyl group (RSi—SiR 3) must be attached to silicon. In an early version of this reaction, Fleming used a two-step process to transform the silane unit to an alcohol unit, treatment with mercuric acetate and peroxyacetic acid, followed by reduction with lithium aluminum hydride (see sec. 4.2.A for reductions with LiAlHq). Comins et al. used this procedure to convert dimethylphenylsilane (397) to alcohol 398 in 93% yield for the two steps, which was part of a synthesis of A-acetyl-A-methylphlegmarine. ... 

The Baeyer-Villiger reaction is a very useful synthesis reaction. An example is the reaction of acetone with peroxyacetic acid to give an ester and a carboxylic acid. This reaction can be generalized as ... 

Isoprene (90) has also been considered as a starting material for the building block 73. Selective oxidation of isoprene (90) with 82% peroxyacetic acid gave an 80% yield of 3,4-epoxy-3-methylbut-l-ene (91), which was transformed into the chloroaldehyde 88 by treatment with cupric chloride in the presence of lithium chloride [32]. A short synthesis of 73 from isoprene (90) has been worked out [33]. 3-Methyl-4-nitrobut-2-en-l-yl acetate (92), obtained in excellent yield by nitroacetyloxylation of isoprene (90), was reduced with iron in acetic acid to give a mixture of oxime 93 and acetoxyaldehyde 73. Steam distillation at pH 2.5 in the presence of formaldehyde furnished distilled 73 in a 40% overall yield based on 90. 

The most common laboratory method for the synthesis of epoxides from alkenes is oxidation with a peroxycarboxylic acid (a peracid), RCO3H. One peracid used for this purpose is peroxyacetic acid ... 

Reviews discuss the advantages of heterogeneous and homogeneous catalytic oxidations for organic synthesis, and catalytic oxygen atom transfer reactions. The new Cr(VI) reagent (51) catalyses the oxidation of secondary alcohols to ketones with peroxyacetic acid. The tetra(diperoxotungsto)-phosphate(3-) anion has been structurally characterised it catalyses stereospecific olefin epoxidations. ... 

The Baeyer-Villiger oxidation of aromatic ketones by peroxyacids is a widely applicable method for the synthesis of phenols . This oxidation can be carried out by organic peroxyacids such as peroxyacetic , trifluoroperoxyacetic , 4-nitro-and 3,5-dinitroperoxybenzoic acids . However, m-chloroperoxybenzoic acid is most frequently used. Hydrogen peroxide is sometimes used, but it works only in the presence of strong acids . 

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