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Reversible pH-dependent cyclization of hydroxy-substituted gem-chloronitroso compounds to isoxazoline N-oxides and 5,6-dihydro-4H-1,2-oxazine N-oxides

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Abstract

Cyclization of hydroxy-substituted gem-chloronitroso compounds under the action of bases affords cyclic nitronates, namely, isoxazoline N-oxides and 5,6-dihydro-4H-1,2-oxazine N-oxides. The process is reversible, viz., the chloronitroso compounds are regenerated upon the action of hydrogen chloride on the cyclization products. A method for the synthesis of cyclic nitronates from aldols using the title reaction was developed. The cyclization mechanism was studied and the kinetic parameters of the process were determined using UV—Vis and IR monitoring and the results of quantum chemical calculations.

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Funding

This work was financially supported by the Russian Science Foundation (Project No. 22-13-00230); u]https://rscf.ru/project/22-13-00230/.

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Authors and Affiliations

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

    R. S. Malykhin & A. Yu. Sukhorukov

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  1. R. S. Malykhin
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  2. A. Yu. Sukhorukov
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Correspondence to A. Yu. Sukhorukov.

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The authors declare no competing interests.

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On the occasion of the 90th anniversary of the N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, Vol. 73, No. 5, pp. 1303–1311, May, 2024.

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Malykhin, R.S., Sukhorukov, A.Y. Reversible pH-dependent cyclization of hydroxy-substituted gem-chloronitroso compounds to isoxazoline N-oxides and 5,6-dihydro-4H-1,2-oxazine N-oxides. Russ Chem Bull 73, 1303–1311 (2024). https://doi.org/10.1007/s11172-024-4247-1

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  • DOI: https://doi.org/10.1007/s11172-024-4247-1

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