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Dimerization of Intermediate P+–C–O– Dipolar Ions into Carbaphosphatrane Derivatives during Intramolecular Cyclization of 2-R-4,4-Bis(trifluoromethyl)benzo[f][1,3,2]dioxaphosphepin-5-ones

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Abstract

2-R-4,4-Bis(trifluoromethyl)benzo[f][1,3,2]dioxaphosphepin-5-ones containing an endocyclic carbonyl group, when stored or slightly heated, undergo spontaneous intramolecular cyclization into P+–C–O–-bipolar ions containing benzoxaphosphole and oxaphosphethane rings fused along the P–C bond. These ions further dimerize into carbaphosphatrane derivatives with a pentacoordinate phosphorus atom, where the P–C bond is incorporated simultaneously into four-, five-, and six-membered rings. Hydrolysis of the carbaphosphtranes leads to the formation of benzo[d][1,2]oxaphosphole derivatives. The structure of one of the carbaphosphatranes, as well as one of the benzo[d][1,2]oxaphospholes has been proved by X-ray diffraction analysis. Carbon substituents in the carbaphosphatrane occupy apical positions, whereas the more electronegative oxygen atoms are in equatorial positions.

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Funding

The synthetic part of the work was funded through the Priority-2030 Strategic Academic Leadership Program, Kazan (Volga Region) Federal University. Physicochemical measurements were performed at the Collective Spectral Analytical Center for Studying the Structure, Properties and Composition of Substances and Materials, Kazan Scientific Center, Russian Academy of Sciences, under the state budget theme no. AAAA-A18-118040390114-8.

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Authors and Affiliations

  1. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, 420088, Kazan, Russia

    V. F. Mironov, I. A. Litvinov & D. R. Islamov

  2. Kazan (Volga region) Federal University, 420008, Kazan, Russia

    V. F. Mironov, G. A. Ivkova, D. R. Islamov & Kh. R. Khayarov

Authors
  1. V. F. Mironov
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  2. G. A. Ivkova
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  3. I. A. Litvinov
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  4. D. R. Islamov
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  5. Kh. R. Khayarov
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Correspondence to V. F. Mironov.

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Translated from Zhurnal Organicheskoi Khimii, 2022, Vol. 58, No. 8, pp. 813–822 https://doi.org/10.31857/S0514749222080055.

In memory of Academician A.I. Konovalov

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Mironov, V.F., Ivkova, G.A., Litvinov, I.A. et al. Dimerization of Intermediate P+–C–O– Dipolar Ions into Carbaphosphatrane Derivatives during Intramolecular Cyclization of 2-R-4,4-Bis(trifluoromethyl)benzo[f][1,3,2]dioxaphosphepin-5-ones. Russ J Org Chem 58, 1099–1107 (2022). https://doi.org/10.1134/S107042802208005X

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