The Baeyer-Villiger (B-V) oxidation of ketones is an important reaction for synthesis of esters that may be difficult to obtain by other synthetic routes, but it is not covered in many laboratory textbooks and may even receive less attention in the lecture course. While B-V oxidation of aldehydes typically yields carboxylic acids, benzaldehydes substituted with certain highly electron-donating groups (EDGs) give formate esters, often undergoing hydrolysis under the reaction conditions to substituted phenols. We have used the B-V oxidation of benzaldehyde and acetophenone in the undergraduate organic chemistry laboratory to explore the known relative migratory aptitude of groups, and also to explore the well-documented anomalous migration of p-methoxyphenyl groups. We explore this effect in our undergraduate laboratories as an application of the effect of EDGs on aromatic systems, and present our students with an extended ranking for B-V migratory aptitude. Traditional relative migratory aptitude: hydrogen &gt; 3o alkyl &gt; phenyl ~ 2o alkyl &gt; 1o alkyl &gt; methyl Extended relative migratory aptitude: p-methoxyphenyl &gt; hydrogen &gt; 3o alkyl &gt; phenyl ~ 2o alkyl &gt; 1o alkyl &gt; methyl As part of enrichment efforts for our undergraduate laboratory curriculum, we are investigating the outcome of B-V reactions on p-anisaldehyde, p-tolualdehyde, benzaldehyde, acetophenone, and p-nitroacetophenone using Oxone(R) and mCPBA as oxidants. We continue to explore the effect of other EDGs and other oxidants.

Investigation of the relative migratory aptitude of phenyl and substituted phenyl groups in the Baeyer-Villiger reaction

251st National Meeting (2016)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.