The conversion of dihydroquercetin to catechin and procyanidin was studied in maturing wild type barley (Hordeum vulgare L., cv. Nordal) seeds and proanthocyanidin free mutants blocked in four different genes, ant 13, ant 17. ant 18 and ant 19. In the wild type barley grown under controlled conditions, maximal rate of synthesis of catechin, procyanidin B3 and procyanidin C2 occurred 8-16 days after flowering. Dihydroquercetin was radioactively labelled by feeding ( 1 -'4C)-acetate and (2-'4C)-acetate to flowerbuds of a petunia mutant accumulating this flavonoid. When fed to pericarp-testa tissue of wild type barley labelled catechin, procyanidin B3 and procyanidin C2 were synthesized establishing dihydroquercetin as a precursor of these compounds. In addition labelled 2,3-trans-3,4-cis-leucocyanidin was synthesized indicating that this compound is an intermediate. The leucocyanidin was identified by co-chromatography with an authentic standard prepared chemically by reduction ofdihydroquercetin with NaBH,. The major product of this reduction, however, was the 2,3-trans-3,4-trans-leucocyanidin. Only mutant ant 18-102 accumulated dihydroquercetin in the seeds. Feeding ('4C)-dihydroquercetin to pericarp-testa tissue from the mutants revealed that ant 17-139 was capable of synthesizing significant amounts of labelled catechin and procyanidin, whereas ant 13-101, ant 13-152, ant 18-102 and ant 19-109 synthesized none or only very small amounts of these compounds. It is concluded that (i) ant 18 controls the reduction of dihydroquercetin to 2,3-trans-3,4-cis-leucocyanidin, (ii) ant 19 controls the reduction of the leucocyanidin to catechin, and (iii) ant 13 and ant 17 control unidentified steps prior to dihydroquercetin.Abbreviations: BAW = n-butanol-acetic acid-water; BW = n-butanol-water; CAW = chloroform-acetic acid-water; 'H N M R = proton nuclear magnetic resonance; HOAc = acetic acid; HPLC = high pressure liquid chromatography; MS = massspectroscopy; sBAWC =s-butanol-acetic acid-water-chloroform; 3,4-cis-diol = (2R,3S,4S)-3, 4,5,7,3',4'-hexahydroxyflavan; 3,4-trans-diol = (2R,3S,4R)-3,4,5,7,Y,4'-hexahydroxyflavan; TLC = thin layer chromatography; UV = ultra violet; WsB = water saturated s-butanol.