Treatment of 5-(2-hydroxyaryl)thianthreniumyl perchlorates 1 with sodium hydride in tetrahydrofuran at reflux gave the title compounds 5 in excellent yields. For the reactivities of the compounds 5, the selected compounds 5 were subjected under the conditions of electrophilic substitution reactions. Bromination of 5,6-{3-(2-butyl)benzo (}-2,3,8,9)-dibenzo-1,4-dithio-7-oxacyclonona-2,5,8-triene (5f) in acetic acid at (60^{\circ}) afforded two bromo compounds (9(22 %)) and (10(69 %)), which were oxidized by (m)-chloroperbenzoic acid to give tetraoxides (11(95 %)) and (12(97 %)), respectively. Treatment of (5 f) with acetyl chloride in the presence of aluminum chloride in carbon disulfide at (0^{\circ}) gave an acetylated compound (13(58 %)). Nitration of 5 f with nitric acid in acetic acid at (50^{\circ}) gave a nitro compound (17(15 %)) together with 1,4 -dioxide 7 e ( (22 %) ) and a (S)-oxide (18(3 %)) whose regiochemistry has not been established. On the other hand, 5,6-(3-methylbenzo)-2,3,8,9-dibenzo-1,4-dithio-7-oxacyclonona-2,5,8-triene (5a) reacted with acetyl chloride under the same conditions to give two acetylated compounds (15(33 %)) and (16(18 %)). The mechanism for the formation of 5 and the structural elucidation of these compounds are discussed.