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Domino reaction of (2-haloethyl)polyfluorophenyl sulfides, sulfoxides, and sulfones with ammonia or amines: one-pot synthesis of 3,4-dihydro-2H-1,4-benzothiazines polyfluorinated at the benzene ring and the corresponding 1-oxides and 1,1-dioxides

Chemistry of Heterocyclic Compounds volume 53, pages 1350–1361 (2017)Cite this article

5,7,8-Trifluoro-3,4-dihydro-2H-1,4-benzothiazine, corresponding 1-oxide and 1,1-dioxide, as well as some of their 4- and 6-substituted derivatives were prepared in 39–88% yields via the reaction of ammonia or primary aliphatic amines with (2-haloethyl)-2,3,5,6-tetrafluorophenyl sulfides, sulfoxides, or sulfones. Formation of the heterocyclic moiety was shown to proceed as a two-stage process starting from halogen replacement at the side chain followed by intramolecular aminodefluorination. The ratio of the reaction rates of the two processes depends on the nature of the reagent used. Chemical structures of the cyclization products were proved by precise analysis of the NMR spectra and by comparing the experimental NMR parameters with those calculated by an empirical additivity scheme and quantum chemistry methods (DFT).

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Figure 1.

Notes

  1. To provide correct comparison of calculated and experimental data, we measured fluorine chemical shifts for 5% solutions in 95% aq EtOH, so the fluorine chemical shifts in Table 1 and in the Experimental are not the same (the chemical shifts given in the Experimental were measured for solutions in CDCl3 or CDCl3–DMSO-d6).

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The research described was supported in part by the Russian Foundation for Basic Research (grant No. 14-03-00108 А). The authors thank the Chemical Service Center, SB RAS, Novosibirsk, for recording spectra of the compounds described and the Information Technology Centre of the Novosibirsk State University for providing access to the cluster computational resources to carry out quantumchemical calculations.

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Authors and Affiliations

  1. N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9 Akademika Lavrentieva Ave, Novosibirsk, 630090, Russia

    Andrey S. Kondratyev, Vitalij D. Shteingarts, Evgeny V. Tretyakov & Alexey V. Tkachev

  2. Institute of Chemical Biology and Fundamental Medicine, Siberian Branch of the Russian Academy of Sciences, 8 Akademika Lavrentieva Ave, Novosibirsk, 630090, Russia

    Vladimir V. Litvak

  3. Novosibirsk State University, 2 Pirogova St, Novosibirsk, 630090, Russia

    Evgeny V. Tretyakov & Alexey V. Tkachev

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  1. Andrey S. Kondratyev
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  2. Vitalij D. Shteingarts
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Correspondence to Andrey S. Kondratyev.

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Vitalij D. Shteingarts and Vladimir V. Litvak are deceased

Published in Khimiya Geterotsiklicheskikh Soedinenii, 2017, 53(12), 1350–1361

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Kondratyev, A.S., Shteingarts, V.D., Litvak, V.V. et al. Domino reaction of (2-haloethyl)polyfluorophenyl sulfides, sulfoxides, and sulfones with ammonia or amines: one-pot synthesis of 3,4-dihydro-2H-1,4-benzothiazines polyfluorinated at the benzene ring and the corresponding 1-oxides and 1,1-dioxides. Chem Heterocycl Comp 53, 1350–1361 (2017). https://doi.org/10.1007/s10593-018-2217-y

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