Synthesis of 1,2-Diazol-4-sulfonamides, 1,2,4- and 1,2,5-Oxadiazol-3-sulfonamides, 1,2,3-Triazol-4-sulfonamides, and Pyrimidine-5-sulfonamides starting from Cyanomethanesulfonyl Chloride

Summary.

Cyanomethanesulfonyl chloride was reacted with amines yielding cyanomethanesulfonamides which could be transformed into alkoxymethylidene and aminomethylidene derivatives. The reaction of alkoxymethylidene derivatives with phenylhydrazine resulted in the formation of 5-aminopyrazol-4-sulfonamides, whereas from cyanomethanesulfonamides via the N-hydroxyamidine derivatives and their reaction with esters 1,2,4-oxadiazol-3-methanesulfonamides became accessible. Nitrosation of cyanomethanesulfonamides yielded 2-hydroxyimino derivatives which were then transformed into 2-hydroxyimino N-hydroxyamidine derivatives, and finally cyclized into 4-amino-1,2,5-oxadiazol-3-sulfonamides. On the other hand diazotation of cyanomethanesulfonamides gave the 2-arylhydrazono derivatives, which after transformation into N-hydroxyamidine derivatives gave by reaction with POCl₃ 5-amino-1,2,3-triazol-4-sulfonamides. Finally, the reaction between cyanomethanesulfonamides and formamidinium acetate opened an easy access to 4-aminopyrimidine-5-sulfonamides, which could be transformed by trialkyl orthoformiates into substituted pyrimidino[4,5-e][1,2,4]thiadiazine derivatives. All intermediates as well as transformation products of the heterocyclic systems were isolated and well characterized. Mechanisms were discussed, and the stereochemistry, when necessary and possible, was elucidated.