α-Cyano-sulphonyl chlorides: their preparation and reactions with amines, alcohols, and enamines

Cyanomethanesulphonyl chloride has been prepared, and some aspects of its chemistry have been investigated. Reactions with primary and secondary amines led to the expected sulphonamides, but sulphonates derived from reactions with alcohols were in most cases too unstable to be isolated. Reactions with enamines gave either substituted thietan 1,1-dioxides or acyclic sulphones, depending upon whether the enamine was derived from an aldehyde or a cyclic ketone. Sulphonamides derived from cyanomethanesulphonyl chloride contain an acidic methylene group, and were found to condense with aldehydes and with isopentyl nitrite in the normal fashion to give, respectively, substituted olefins and an oxime. The course of the coupling reaction with diazonium salts, however, appeared to depend upon whether the sulphonamide was derived from a primary or a secondary amine. Homologues of cyanomethanesulphonyl chloride having an alkyl group attached to the α-carbon atom were markedly less reactive towards nucleophiles than was the parent compound, reactivity decreasing with increase in chain length. A number of sulphonamides were prepared from each homologue.