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Asymmetric nitrogen. 73. Geminal systems. 47. Configuration stability and mechanism for inversion of N-chloroxaziridines

  • Organic Chemistry
  • Published:
Bulletin of the Academy of Sciences of the USSR, Division of chemical science Aims and scope

Abstract

We have studied the kinetics of racemization and thermolysis of (+)-2-chloro-3,3-pentamethyleneoxaziridine (I). The activation energy determined for inversion of the nitrogen atom in (I) in n-heptane is 28.9 kcal/mole lower than the value calculated (ab initio, 3–21G) for 2-chloroxaziridine (II). Based on this and also on the increase in the inversion rate of (I) with an increase in the polarity of the solvent and the entropy of activation (−43.5 cal/mole·K, n-heptane), we conclude that the mechanism for inversion of N-chloroxaziridines is “nonclassical,” by means of reversible ionization of the N-Cl bond through a solvate-unseparated ion pair.

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Authors and Affiliations

  1. N. N. Semenov Institute of Chemical Physics, Academy of Sciences of the USSR, Moscow

    G. V. Shustov, S. V. Varlamov, A. Yu. Shibaev, Yu. V. Puzanov & R. G. Kostyanovskii

Authors
  1. G. V. Shustov
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  2. S. V. Varlamov
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  3. A. Yu. Shibaev
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  4. Yu. V. Puzanov
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  5. R. G. Kostyanovskii
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Additional information

For the previous communication, see [1].

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1816–1819, August, 1989.

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Shustov, G.V., Varlamov, S.V., Shibaev, A.Y. et al. Asymmetric nitrogen. 73. Geminal systems. 47. Configuration stability and mechanism for inversion of N-chloroxaziridines. Russ Chem Bull 38, 1663–1665 (1989). https://doi.org/10.1007/BF00956952

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  • DOI: https://doi.org/10.1007/BF00956952

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