CHLOROSULFONATION OF 9-ARYL 3,3,6,6-TETRAMETHYLOCTAHYDROXANTHEN-1,8-DIONES

The 9-aryl-3,3,6,6-tetramethyloctahydroxanthendiones (4-20) react with chlorosulfonic acid to give the sulfonyl chlorides (25, 34, 43, 53, 55, 59, 63 and 65). The xanthendione (7) from m-anisaldehyde afforded the bis-sulfonyl chloride (30). The products were converted into 35 sulfonamides, 4-hydrazides (48, 56, 57, 69a) and 2 hydrazones (49, 69b) required for screening as potential pesticides. Dimedone (1) (2 moles) and cinnamaldehyde (1 mole) in ethanol-piperidine (catalyst) afforded an abnormal product probably (76), however an equimolar reaction with cinnamaldehyde or the alpha-methyl derivative in pyridine gave the 2-phenylpyrans (78, 79). Dimedone with salicylaldehyde or o-vanillin afforded the pyran derivatives (72, 73); the former reacted with chlorosulfonic acid to give the sulfonyl chloride (74), characterized as the morpholidate (75). The xanthendione (15) with chlorosulfonic acid afforded the chloride (70), characterized as the morpholidate (71). Attempted chlorosulfonation of the substrates (16, 77, 78 and 79) all gave impure products and 13 failed to react. The NMR spectral data of the compounds are briefly discussed.