N,N-Dialkyl-N′-Chlorosulfonyl Chloroformamidines in Heterocyclic Synthesis. Part XII.* Synthesis and Reactivity of the Pyrazolo[3,4-e][1,2,4]thiadiazine Ring System
Rebecca E. Norman A , Michael V. Perkins A , Andris J. Liepa B and Craig L. Francis B CA 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 68(9) 1455-1466 https://doi.org/10.1071/CH15028
Submitted: 23 January 2015 Accepted: 20 March 2015 Published: 21 May 2015
Abstract
N,N-Dialkyl-N′-chlorosulfonyl chloroformamidines 1 reacted regioselectively with 1-substituted 5-aminopyrazoles 2 via a 1,3-CCN dinucleophilic substitution to afford pyrazolo[3,4-e][1,2,4]thiadiazines 3 as the sole isolated products. Compounds 3, representatives of a very rare ring system, were shown to possess three nucleophilic sites at N2, N4, and N6. Methylation occurred at all three sites. Alkylation with benzylic halides occurred preferentially at N2, but some also occurred at N4, and at C7a. Alkylation with ethyl bromoacetate occurred at both N4 and N6, but the latter derivatives underwent a pyrazole ring expansion to afford pyrimido[4,5-e][1,2,4]thiadiazine derivatives. Compounds 3 were unreactive towards various acylating agents.
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