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N-Alkylation and N-amination of isomeric nitro derivatives of 3-methyl-4-(1H-pyrazol-3(5)-yl)furazan

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Chemistry of Heterocyclic Compounds Aims and scope

The reaction of bromoacetone and hydroxylamine-О-sulfonic acid with isomeric mono- and dinitropyrazoles containing a furazanyl moiety at position 3(5) gave pairs of regioisomeric products from pyrazole ring N-acetonylation and N-amination, respectively, that were characterized in detail by multinuclear NMR spectroscopy. X-ray structural study of the four synthesized N-amino derivatives indicated a non-planar structure, while the conformational analysis pointed to conformational lability of such molecules, and the role of intermolecular interactions in determining the crystal structure.

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Scheme 1
Scheme 2
Scheme 3
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Figure 2
Figure 3

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Notes

  1. Here and further the isomer а corresponds to the product with N-substituent most distant from the main substituent, namely, the furazan moiety, while the isomer b corresponds to the isomer where these substituents are closer together.

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The work was performed with financial support from the Russian Scientific Fund (project RNF 14-13-01153).

The authors would like to thank Dr. Yu. A. Strelenko (Institute of Organic Chemistry, Russian Academy of Sciences) for the assistance in registration and interpretation of 2D NMR spectra.

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Authors and Affiliations

  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Ave., Moscow, 119991, Russia

    Igor L. Dalinger, Alexandr V. Kormanov, Irina A. Vatsadze, Tatyana K. Shkineva, Andrei M. Kozeev & Aleksei B. Sheremetev

  2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova St., Moscow, 119991, Russia

    Boris B. Averkiev

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  1. Igor L. Dalinger
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  2. Alexandr V. Kormanov
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  3. Irina A. Vatsadze
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  4. Tatyana K. Shkineva
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  6. Boris B. Averkiev
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  7. Aleksei B. Sheremetev
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Correspondence to Aleksei B. Sheremetev.

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Translated from Khimiya Geterotsiklicheskikh Soedinenii, 2015, 51(9), 819–828

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Dalinger, I.L., Kormanov, A.V., Vatsadze, I.A. et al. N-Alkylation and N-amination of isomeric nitro derivatives of 3-methyl-4-(1H-pyrazol-3(5)-yl)furazan. Chem Heterocycl Comp 51, 819–828 (2015). https://doi.org/10.1007/s10593-015-1781-7

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