Unveiling the chemistry behind bromination of quercetin: the 'violet chromogen'

Bromination of quercetin with N-bromosuccinimide in neutral aqueous methanol occurs surprisingly in the electron-deficient A-ring only. Deprotonation of the acidic 7-OH is a major driver of this regioselective reaction. The increase of electron density makes in fact the quercetin anion suitable for an electrophilic attack by bromine at positions 8 and 6. Several pieces of evidence (NMR spectra and H/D exchange) are presented to substantiate the mechanism advanced. Bromoquinones/quinomethides produced in excess of N-bromosuccinimide are responsible for the formation of a stable 'violet chromogen'.