Acetaldehyde Baeyer-Villiger

Addition of acetaldehyde to the peracetic acid and Baeyer-Villiger rearrangement to produce two moles of acetic acid ... 

A combination of known reactions has been used for the a -alkoxycarbonylmethyl-ation of a/3-unsaturated ketones, (146), by photochemical [2 + 2] addition of ketene dimethyl acetal and subsequent Baeyer-Villiger oxidation to give a mixture of the expected lactone and the derived unsaturated acid, arising from hydrolysis of the lactone and dehydration. A final alkylation step serves to convert both compounds into the desired ester (147). The enol acetate of acetaldehyde can be used in place of the ketene, although here of course, an extra oxidation step is required. ... 

Scheme 9.132. A representation of the Mn -catalyzed oxygen (O2) oxidation of ethanal (acetaldehyde, CHaCHO) to perethanoic acid (peracetic acid.CHaCOaH) and the snbseqnent transformation of the peracid and additional ethanal (acetaldehyde, CH3CHO) to ethanoic acid (acetic acid, CHaC02H), via a Baeyer-Villiger transformation, or to ethanoic anhydride [acetic anhydride, (CHaCO)20].

Supercritical CO2 is a non-polar, aprotic solvent and promotes radical mechanisms in oxidation reactions, similar to liquid-phase oxidation. Thus, wall effects might occur as known, e.g. from olefin epoxidation with 02 or H202 which may decrease epoxide selectivities. The literature covers the synthesis of fine chemicals by oxidation either without catalysts (alkene epoxidation, cycloalkane oxidation, " Baeyer-Villiger oxidation of aldehydes and ketones to esters ), or with homogeneous metal complex catalysts (epoxidation with porphyrins, salenes or carbonyls ). Also, the homogeneously catalysed oxidation of typical bulk chemicals like cyclohexane (with acetaldehyde as the sacrificial agent ), toluene (with O2, Co +/NaBr ) or the Wacker oxidation of 1-octene or styrene has been demonstrated. 

A computational study of the Baeyer-Villiger oxidation of benzaldehyde and acetaldehyde has been reported. Computational studies with peroxyacetic acid suggest that the first step is rate limiting and the addition of the peroxyacetic acid oxidation catalyst to the ketone carbonyl to produce the Criegee or tetrahedral intermediate (Scheme 163) "... 

A compound which closely resembled the tarry substance was prepd in 1900 by Baeyer and Villiger by adding 0-lg of acetaldehyde to a mixture of lg H2O2(10 sol) and 2g SOa, cooled to 0°. The oil which separated on standing gave,on cooling in ice, a volatile solid which exploded violently on impact or heating. They called the compound Diacetaldehydperoxyd, but did not determine its composition... 

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