Durch Bromirung ausgeloeste Umlagerung tertiaerer Allylalkohole: Der Einfluss eines Fluor-Substituent auf Reactionsgeschwindigkeit und reactionsverlauf

Article abstract of DOI:10.1002/hlca.19800630517

The allyl alcohol bearing a methyl and a t-butyl group at the hydroxylated position was found to undergo a rearrangement when treated with bromine (or N-bromosuccinimide) in an aqueous medium and to afford a product mixture containing two regioisomeric ketones and one oxirane.Introduction of an additional methyl group or a fluorine atom at the non-terminal olefinic center led to a more selective discrimination between potential migratory groups.As the result of an exclusive t-butyl shift only one product, a ketone, was formed in both cases.Whereas the reaction rate only was slightly affected by the additional methyl group, it was substantually decreased by the fluorine atom.