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Reactions of Thiiranes with NH Heterocycles: II. C-Bromo/Nitro-1-(thietan-3-yl)pyrazoles as Convenient Synthons for Substituted 1-(Thietan-3-yl)pyrazoles

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Abstract

Reactions of 2-(chloromethyl)thiirane with symmetrically substituted C-bromo/nitropyrazoles in water in the presence of bases were accompanied by thiirane–thietane rearrangement to afford 4-bromo(nitro)- and 3,5-dibromo-4-bromo(nitro)-1-(thietan-3-yl)-1H-pyrazoles as convenient intermediate products for further transformations. Possible modifications of the title compounds via oxidation to 1-(1-oxo-λ4-thietan-3-yl)- and 1-(1,1-dioxo-λ6-thietan-3-yl)pyrazoles, reactions with oxygen and nitrogen nucleophiles with the formation of thietane-containing 5-methoxy- and 5-(morpholin-4-yl)-1H-pyrazoles, and reduction to 4-amino-3-bromo-5-(morpholin-4-yl)-1-(thietan-3-yl)-1H-pyrazole have been demonstrated.

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ACKNOWLEDGMENTS

The NMR spectra were recorded using the facilities of the Chemistry joint center (Ufa Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences) and Agidel regional joint center (Ufa Federal Research Center, Russian Academy of Sciences).

Funding

This study was performed in the framework of state assignment no. AAAA-A20-120012090029-0.

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Authors and Affiliations

  1. Bashkir State Medical University, Ministry of Health of the Russian Federation, 450008, Ufa, Russia

    E. E. Klen, N. N. Makarova, F. A. Khaliullin, S. O. Shepilova & A. R. Ishkinina

  2. Ufa Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences, 450054, Ufa, Russia

    I. P. Baikova

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  1. E. E. Klen
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  2. N. N. Makarova
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  3. F. A. Khaliullin
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  4. S. O. Shepilova
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  5. A. R. Ishkinina
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Correspondence to E. E. Klen or I. P. Baikova.

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Translated from Zhurnal Organicheskoi Khimii, 2022, Vol. 58, No. 9, pp. 926–935 https://doi.org/10.31857/S0514749222090026.

For communication I, see [1].

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Klen, E.E., Makarova, N.N., Khaliullin, F.A. et al. Reactions of Thiiranes with NH Heterocycles: II. C-Bromo/Nitro-1-(thietan-3-yl)pyrazoles as Convenient Synthons for Substituted 1-(Thietan-3-yl)pyrazoles. Russ J Org Chem 58, 1192–1199 (2022). https://doi.org/10.1134/S1070428022090020

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