Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

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

Rebecca E. Norman A , Michael V. Perkins A , Andris J. Liepa B and Craig L. Francis B C
+ Author Affiliations
- Author Affiliations

A School of Chemical and Physical Sciences, Flinders University, Bedford Park, SA 5042, Australia.

B CSIRO Manufacturing Flagship, Clayton, Vic. 3168, Australia.

C Corresponding author. Email: craig.francis@csiro.au

Australian Journal of Chemistry 69(1) 61-75 https://doi.org/10.1071/CH15445
Submitted: 24 July 2015  Accepted: 26 August 2015   Published: 15 October 2015

Abstract

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.


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