The present work describes the preparation of two compounds considered to be likely precursors of an impurity present in samples of the color additives D&C Red No. 27 (Color Index 454101) and D&C Red No. 28 (Color Index 45410, phloxine B) submitted to the U.S. Food and Drug Administration for batch certification. The two compounds, 2-(2',4'-dihydroxy-3'-bromobenzoyl)-3,4,5,6-tetrachlorobenzoic acid (3BrHBBA) and its 5'-brominated positional isomer (5BrHBBA), both not reported previously, were separated from synthetic mixtures by vortex counter-current chromatography (VCCC). 3BrHBBA was prepared by chemoselective ortho-bromination of the dihydroxybenzoyl moiety. Two portions of the obtained synthetic mixture, 200mg and 210mg, respectively, were separated by VCCC using two two-phase solvent systems that consisted of hexane-ethyl acetate-methanol-aqueous 0.2% trifluoroacetic acid (TFA) in the volume ratios of 8255 and 7355, respectively. These separations produced 35mg and 78mg of 3BrHBBA, respectively, each product of over 98% purity by HPLC at 254nm. 5BrHBBA was prepared by monobromination of the dihydroxybenzoyl moiety in the presence of glacial acetic acid. To separate the obtained synthetic mixture, VCCC was performed in the pH-zone-refining mode with a solvent system consisting of hexane-ethyl acetate-methanol-water (6455, v/v) and with TFA used as the retainer acid and aqueous ammonia as the eluent base. Separation of a 1-g mixture under these conditions resulted in 142mg of 5BrHBBA of ∼99% purity by HPLC at 254nm. The isolated compounds were characterized by high-resolution mass spectrometry and proton nuclear magnetic resonance spectroscopy.