N,N-Dialkyl-N′-Chlorosulfonyl Chloroformamidines in Heterocyclic Synthesis. Part XV.* Some Unexpected Reactions with Anilines
Dylan Innes A , Michael V. Perkins A , Andris J. Liepa B and Craig L. Francis B CA College of Science and Engineering, Flinders University, Bedford Park, SA 5042, Australia.
B Biomedical Synthetic Chemistry Group, CSIRO, Clayton, Vic. 3168, Australia.
C Corresponding author. Email: craig.francis@csiro.au
Australian Journal of Chemistry 71(8) 610-623 https://doi.org/10.1071/CH18252
Submitted: 28 May 2018 Accepted: 8 August 2018 Published: 12 September 2018
Abstract
N,N-Dimethyl-N′-chlorosulfonyl chloroformamidine 1a underwent reactions with various anilines. In addition to the benzo[e][1,2,4]thiadiazine dioxides 8, from 1,3-NCC bis-nucleophilic substitution and bis-anilino adducts 9, some unexpected products were formed, particularly when sterically hindered or electron-poor anilines were used. In these cases, products such as the [1,3,2,4,6]dithiatriazine 1,1,3,3-tetraoxides 17 and, on occasion, N,N,5-trimethyl-4-(arylimino)-4,5-dihydro-[1,3,5]triazin-2-amines 14 were produced in significant yields. Reaction of dichloride 1a with 3-bromoaniline afforded the unusual eight-membered-ring product 2,6-bis(3-bromophenyl)-3,7-bis(dimethylamino)-2H,6H-[1,5,2,4,6,8]dithiatetrazocine 1,1,5,5-tetraoxide 28, in addition to the dithiatriazine tetraoxide 17k. These uncommon heterocyclic structures are of interest for bioactive molecule discovery screening programs.
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