The action of sodium methanethiolate (in boiling DMF) towards haloazines (i.e.chloro-or bromo-pyridines and quinolines) (1) (with halogen substituent in non-aza-activated position) causes sequentially halogen ipso-substitution to methylthioazines (2) and then S-demethylation to azinethiolates (3A),which were:i) subjected to S-methylation,ii) oxidized to diazinyl disulfides (4) and iii) oxidatively chlorinated to azinesulfonyl chlorides (5).alpha-and gamma-pyridine-and quinolinesulfonyl chlorides (5a,5c,5d and 5f) were prepared by oxidative chlorination of respective disulfides (4) performed in conc,hydrochloric acid and characterized by ~1H and ~(13)C NMR spectra.All azinesulfonyl chlorides (5) were effectively converted to corresponding azinesulfonamides (6).
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