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Oximes of fluoroalkyl-containing 1,3-diketones: specific features of synthesis, analysis, and thermal stability

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Abstract

Nitrosation of lithium 1,3-diketonates bearing fluoroalkyl and aryl (or hetaryl) substituents in positions 1 and 3 results in 3-polyfluoroalkyl-1,2,3-propanetrione 2-oximes (from this point on, oximes). Under similar conditions, lithium (Z)-1,1,1-trifluoro-4-oxo-4-(thien-2-yl)-2-buten-2-olate forms a hydration product of the corresponding oxime. Nitrosation of fluoroalkyl-containing lithium 1,3-diketonates is accompanied by retro-decomposition of the initial lithium 1,3-diketonates and the target oximes (or their hydration products) followed by oxidation and hydrolysis of the reaction products. Under the GC-MS conditions, the oximes undergo partial thermal decomposition to 2-aryl(hetaryl)-2-oxoethanenitriles. An analysis of solutions of the oximes in DMSO-d6 by 1H and 19F NMR spectroscopies revealed isomerization and hydration of these compounds. The temperature ranges of stability of the oximes were determined by thermogravimetric analysis and differential thermal analysis. The molecular and crystal structures of 4,4-difluoro-1-(4-methoxyphenyl)-1,2,3-butanetrione 2-oxime and 4,4,4-trifluoro-1-(thien-2-yl)-1,2,3-butanetrione 2-oxime were determined by X-ray diffraction.

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Funding

This work was carried out within the framework of the State Assignment (Contract No. 0398-2019-0005 AAAA-A19-119012290117-6) using facilities at the Russian Federal Nuclear Center — Zababakhin All-Russia Scientific Research Institute of Technical Physics and at the Center for Collective Use “Spectroscopy and Analysis of Organic Compounds” (CCU SAOC).

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Authors and Affiliations

  1. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences, 22/20 ul. S. Kovalevskoy, 620108, Ekaterinburg, Russia

    N. S. Boltacheva, P. A. Slepukhin, M. G. Pervova, V. I. Filyakova & V. N. Charushin

  2. Russian Federal Nuclear Center — Zababakhin All-Russia Scientific Research Institute of Technical Physics, 13 ul. Vasilyeva, 456770, Snezhinsk, Chelyabinsk Region, Russia

    A. Kh. Rudina, I. V. Chemagina, N. P. Taibinov & B. G. Loboiko

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  1. N. S. Boltacheva
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  2. P. A. Slepukhin
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  3. M. G. Pervova
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  4. A. Kh. Rudina
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  5. I. V. Chemagina
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  6. N. P. Taibinov
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  7. V. I. Filyakova
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  8. B. G. Loboiko
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  9. V. N. Charushin
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Corresponding author

Correspondence to V. I. Filyakova.

Additional information

Dedicated to Academician of the Russian Academy of Sciences V. I. Ovcharenko on the occasion of his 70th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1464–1473, July, 2022.

No human or animal subjects were used in this research.

The authors declare no competing interests.

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Boltacheva, N.S., Slepukhin, P.A., Pervova, M.G. et al. Oximes of fluoroalkyl-containing 1,3-diketones: specific features of synthesis, analysis, and thermal stability. Russ Chem Bull 71, 1464–1473 (2022). https://doi.org/10.1007/s11172-022-3552-9

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  • DOI: https://doi.org/10.1007/s11172-022-3552-9

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