Synthese von Benzo[b]thioxanthenen

Synthesis of Benzo[b]thioxanthenes Benzo[b]thioxanthenes, heterocyclic compounds related to tetracenes and tetracyclines can be obtained by the reaction of 2H-benzo[b]thiete ( 1 ) and 1,4-naphthoquinones ( 3a–g ). The primary cycloadducts 4a–g undergo an autoxidation process leading to the quinones 6a–g . The dihydroxy compound 4e shows an additional isomerization by a tetrafold H transfer ( 4e → 5e ′). Another preparative route to benzo[b]thioxanthenes makes use of the cycloadditon reaction of 1 and 1,4-epoxynaphthalenes ( 7a–d ). The primary adducts can be transformed to the title compounds by catalytic dehydration processes ( 8a–d → 9a-d ). An alternate regioselective opening of the oxygen bridge can be performed by the action of trimethyliodosilane ( 8a → 10a ). Methylation of 9a furnishes the sulfonium salt 14a which rearranges in a strongly alkaline medium to 16a ; in the presence of oxygen ketone 17a is generated.