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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Notes
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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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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DOI: https://doi.org/10.1007/s10593-015-1781-7