2-Methyl-5, 8-dihydroxy-6, 7-benzochromone (IV) was obtained by means of either hydroxylation of 2-methyl-8-hydroxy-6, 7-benzochromone (I) or reduction of 2-methyl-4H-naphtho [2, 3-b] pyrane-4, 5, 10 (5H, 10H)-trione (III), and synthesis of 2-methyl-5, 8-dimethoxy-6, 7-benzochromone (V), in which the furan ring of khellin (VI) was replaced by a benzenoid ring, was accomplished by means of methylation of IV. It was found that V underwent irreversible ring isomerization to form 2-methyl-5, 6-dihydroxy-7, 8-benzochromone (VIII) during demethylation of V with hydriodic acid.