A new direct synthesis of benzo(k,1)thioxanthene-3,4-dicarboxylic anhydride from 4-nitro-naphthalene-1,8-dicarboxylic anhydride and 2-aminobenzenethiol is reported; 4-(2-aminophenylthio) naphthalene-1,8-dicarboxylic anhydride and 4-phenylthionaphthalene-1,8-dicarboxylic anhydride are also formed. Similar reaction in presence of amyl nitrite or sodium nitrite results in formation of larger amounts of 4-phenylthionaphthalene-1,8-dicarboxylic anhydride, together with other products arising from the oxidation of 2-aminobenzenethiol; one such product is the new heterocycle 9,10-dithiaphenanthrene. 4-(2-Aminophenylthio)-naphthalene-1,8-dicarboxylic anhydride is rapidly converted by amyl nitrite or sodium nitrite in dimethylformamide into benzo(k,1)thioxanthene-3,4-dicarboxylic anhydride, constituting a novel one-stage intramolecular cyclisation reaction of greater convenience than the conventional two stage Pschorr cyclisation.