N, N-Dialkyl-N '-Chlorosulfonyl Chloroformamidines in Heterocyclic Synthesis. Part XIII.* Cleavage and Rearrangement Reactions of Pyrazolo[1,5-b][1,2,4,6] thiatriazine 1,1-Dioxides

摘要

Treatment of pyrazolo[1,5-b][1,2,4,6] thiatriazines 1 with the Vilsmeier-Haack reagent afforded pyrazolo[1,5-a][1,3,5] triazines 5. Reaction of compounds 1 with trifluoroacetic anhydride, dimethyl sulfoxide, and triethylamine afforded 5-dimethylsulfanylidene derivatives 8. The guanidino-pyrazole-sulfonic acid 9 was produced from treatment of compounds 1 with trifluoroacetic acid under anhydrous conditions. Similar treatment in the presence of water afforded the desulfonated pyrazolo-guanidine 6. Reactions of 6 with one-carbon electrophiles provided various 4-substituted pyrazolo[1,5-a][1,3,5] triazines 5. Attempted catalytic hydrogenolysis of N7-benzyl pyrazolo[1,5-b][1,2,4,6] thiatriazines 2 in alcohols led to sulfamates 12 from thiatriazine ring cleavage. Ethyl acetate or tert-butanol as solvent allowed successful debenzylation to provide compounds 1. Aminolysis of compounds 2 gave sulfamides 13. Thermal rearrangement of compounds 2 afforded 6-benzyl-pyrazolo[3,4-e][1,2,4] thiadiazines 14.