Boron tribromide → Robustaflavone

Participants

Reaction Steps

To a solution of 10 (75.0 mg, 0.12 mmol) in 10 mL dry CHC3 was added BBr3 (1.0 M in CH2Cl2, 1.45 mL, 1.45 mmol), and the resulting yellow slurry was stirred at reflux overnight. The reaction mixture was cooled to room temperature, quenched by the careful addition of MeOH, and evaporated in vacuo. The resulting orange solid was triturated with MeOH, the solvent again evaporated in vacuo, and the solid was partitioned between EtOAc and 1 M NaOH. The organic layer was discarded, and the aqueous layer was extracted with EtOAc. After cooling to 0° C., the aqueous layer was carefully acidified to pH 3.0 by the dropwise addition of 3 M HCl. The resulting yellow precipitate was collected by vacuum filtration, rinsed with water and air dried (38.7 mg). The crude material was chromatographed through silica gel, eluting with a mixture of toluene/pyridine/formic acid (20:10:1). Appropriate fractions were combined and evaporated to afford 19.4 mg (30.0%) robustaflavone. An analytical sample was obtained via recrystallization from pyridine/H2O (1:1); mp 370-372° C., dec. (lit.1 mp 350-352° C.). Spectral data of synthetic robustaflavone was identical to that recently reported1 for the natural product isolated from Rhus succedanea. Anal. calcd for C30H18O10.1.25 H2O: C, 64.23; H, 3.68. Found: C, 64.17; H, 3.68.

Provenance & Evidence