The Duff reaction forms aryl aldehydes from substituted phenols which are important compounds when making the principal components of vanilla and cinnamon, and biochemicals like testosterone, progesterone, and cortisone. The Duff reaction’s major drawback is that it can take up to five days to run under reflux and the product yields can be lower. By using a microwave for the heat source, the reaction times can be dramatically reduced and yields generally increased. This project looks at the regiochemistry and yields of products formed from a Duff Reaction with the three regioisomers of bromophenol. The products are identified with 1H NMR, GC/MS, and comparison to pure forms of the predicted products (where available). From the reactions run with para, meta, and ortho-bromophenol, p-bromophenol forms one product with high yields around 64 percent. The meta and ortho chemicals produce two to three possible products with yields as high as 98 percent. The o-bromophenol is specifically interesting because it produces a mono-aldehyde and aldehyde product in the same reaction. Previous mechanistic work on the Duff reactions stated that the aldehyde is added ortho to the phenol group, but this work shows formylation can also occur para to the phenol group. Mechanistic details will be discussed.

Microwave assisted Duff formylation reactions

2019 Spring National Meeting

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