Synthesis of the title compounds has been achieved starting from 4‐oxo‐3,4‐dihydro‐2H,5H‐thiopyrano[3,2‐c][1]benzothiopyran 6,6‐dioxide (III), which was converted to glyoxylate (IV), β‐ketoester (V), difluoride complex (VII) and β‐diketone (XII) gave with hydrazine, hydroxyl‐amine and glycine ethyl ester several azadithiasteroid analogues.

Some thiadiazasteroid analogues have been synthesized by the reaction of 3‐hydroxymethyl‐enebenzo[h]thiochroman‐4‐one with hydrazine and substituted hydrazines, semicarbazide and thiosemicarbazide. Pmr data supporting the structural assignments have been discussed.

Five [1,4]thiazinocarbazoles have been synthesized from 6‐, 7‐ and 8‐amino‐2H[1,4]benzo‐thiazin‐3(4H)ones by the Jaap‐Klingemann reaction with 2‐hydroxymethylenecyclohexanone followed by Fischer indolisation of the resulting hydrazones. The structures of the hitherto unknown ring systems have been confirmed by pmr spectral data.

Thiochromanondioxid (I) liefert mit β‐Mercaptopropionsäure die Thioether‐säure (II), die zu (IIIa) cyclisiert und weiter zu (IIIb) substituiert werden kann.

Aus dem Amino‐benzothiazinon (Ia) entsteht in hoher Ausbeute das Hydrazon (Ib), das nach Japp‐Klingemann zum Tetracyclus (II) führt.