The isolation of two unusual pigments from Dalea emoryi, dalrubone 2 and its S-methoxy analog together with coumarin and S-methoxycoumarin was recently reported by Dreyer et al. [l]. The structure of dalrubone and the co-occurrence of coumarin suggest that its biosynthesis in Dalea species may involve Cand Omethylation of tlavylium salt intermediates such as 1, although anthocyanidins or flavylium salts with this unusual oxygenation pattern have not yet been reported from any natural sources. In order to test this hypothesis we have prepared flavylium salt 1 employing a general synthetic method described by Michaelidis and Wizinger [2] and have methylated it under a variety of conditions. Methylation of 1 with Me1 in refluxing methanolic NaOMe (mole ratio 1: 10 :6) gave a complex mixture of Et,O-soluble products most of which were acidic and removed by extraction with aqueous base. Repeated column chromatography of the alkali-insoluble fraction yielded small amounts of two pure pigments. The orange, less polar pigment possessed spectral properties (UV, MS, PMR, IR) and TLC behaviour in a number of solvent systems identical to those reported [l] for dalrubone, and this identity was confirmed by direct comparison with an authentic sample. The yellow, more polar pigment has the molecular formula Cr9H1s04 (MS), and 3 IR absorption bands in the carbonyl region at 1720, 1675 and 1636cm-’ but no OH absorptions. The PMR spectrum in CDCl, was comprised of a pair of AB doublets at 68.35 and 7.71 (J = 10 Hz) indicative of a cis disubstituted olefin, a 4 proton multiplet in the aromatic region at 67.35-7.64, and a 12 proton singlet at 61.39 caused by 4 equivalent Me groups. These data suggest structure 3 for the yellow pigment. This structural assignment was further confirmed by a study of the MS fragmentation pattern which can be rationalized as shown in Scheme 1. Additional support for the scheme was provided by a study of metastable peaks which were observed for all of the transformations shown except m/e 171 + 170. To further support the proposal that biosynthesis of Dalea pigments involves methylation of 2’-hydroxyflavylium intermediates, a sample of D. emoryi was extracted with CH among these were treatment of 1 with (a) Me1 and BaO in DMF (b) Et,O-CH,N*