A number of 4- (2-hydroxyalkyl) -1, 3-benzenediols (4) were synthesized by thermolysis of 1, 3-cyclohexadiones (3), which were obtained by the reaction of α-phenylsulfiny1-γ-butyrolactones (I) with α, β-unsaturated ketones (2), providing a new aromatic annelation. One of the compounds thus obtained, 4- (3, 4-dihydro-4-hydroxy-7-methoxy-2H-1-benzopyran-3-yl) -1, 3-benzenediol (4n), was converted to isomedicarpin (5b) and homopterocarpin (5c).