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Kinetics and mechanism of the nitrosobenzene deoxygenation by trivalent phosphorous compounds

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Abstract

The reaction of aryl nitroso compounds with organic phosphines and phosphites in aerated media is a convenient non-photolytic procedure to generate aromatic nitroso oxides. The reaction rate constants and activation parameters of the key (for the proposed method of nitroso oxide generation) reaction of nitrosobenzene with tripenyl phosphite or para-substituted phosphines (4-RC6H4)3P (R = MeO, Me, H, F), as well as that of para-methoxynitrosobenzene with triphenylphosphine in acetonitrile were determined by kinetic spectrophotometry and chemiluminescence. A significant transfer of the electron density to the nitroso compound occurs in the transition state of the reaction as was revealed using the Hammett correlation analysis and DFT calculations in the M06L/6-311+G(d,p) approximation. The introduction of the electron-donor substituent MeO into the para-position of PhNO decreases the reactivity of the nitroso compound by two orders of magnitude. The reactivity of triphenyl phosphite in the oxygen atom transfer reaction is lower by two orders of magnitude compared to that of triphenylphosphine. In the case of the reactions of PhNO with phosphines, the apparent rate constant depends on the oxygen content in the reaction medium.

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Authors and Affiliations

  1. Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054, Ufa, Bashkortostan, Russian Federation

    V. S. Khursan, V. A. Shamukaev, E. M. Chainikova, S. L. Khursan & R. L. Safiullin

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  1. V. S. Khursan
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  2. V. A. Shamukaev
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  3. E. M. Chainikova
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  4. S. L. Khursan
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  5. R. L. Safiullin
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Correspondence to R. L. Safiullin.

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Dedicated to Academician of the Russian Academy of Sciences M. P. Egorov on the occasion of his 60th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2477–2486, Novemer, 2013.

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Khursan, V.S., Shamukaev, V.A., Chainikova, E.M. et al. Kinetics and mechanism of the nitrosobenzene deoxygenation by trivalent phosphorous compounds. Russ Chem Bull 62, 2477–2486 (2013). https://doi.org/10.1007/s11172-013-0359-8

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  • DOI: https://doi.org/10.1007/s11172-013-0359-8

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