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Fast and reversible migrations of N,S-centered groups around the perimeter of cyclopropene and cycloheptatriene rings

  • Organic Chemistry
  • Published:
Russian Chemical Bulletin Aims and scope

Abstract

The kinetics and mechanism of circumambulatory rearrangements of N-centered (NCS) and S-centered (SPh, SC3Ph3, SC(OEt)=S) groups in corresponding derivatives of 1,2,3-triphenylcyclopropene and cycloheptatriene were studied by dynamic1H and13C NMR spectroscopy. Migrations of the isothiocyanate group occur by the dissociation-recombination mechanism with intermediate formation of a tight ionic pair. Migrations of the phenylthio group around the perimeter of cyclopropene and cycloheptatriene rings occur by the 1,2-shift mechanism. It was found that rearrangements of theO-ethyl dithiocarbonate group inS-(1,2,3-triphenylcyclopropen-3-yl)-O-ethyl dithiocarbonate occur by the 3,3-sigmatropic shift mechanism. The molecular and crystal structure ofO-ethylS-(1,2,3-triphenylcyclopropen-3-yl) dithiocarbonate was studied by X-ray analysis.

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Authors and Affiliations

  1. Scientific-Research Institute of Physical and Organic Chemistry, Rostov State University, 194/2 prosp. Stachki, 344090, Rostov-on-Don, Russian Federation

    V. I. Minkin, I. E. Mikhailov, G. A. Dushenko & O. E. Kompan

  2. Institute of Chemistry, Humboldt University, D-10115, Berlin, Germany

    A. Zschunke

Authors
  1. V. I. Minkin
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  2. I. E. Mikhailov
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  3. G. A. Dushenko
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  4. O. E. Kompan
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  5. A. Zschunke
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Additional information

Institut für Chemie, Humboldt Universität, D-10115 Berlin, Deutschland.

Translated fromIzvestiya Akademii Nauk Seriya Khimicheskaya, No. 5, pp. 913–923, May, 1998.

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Minkin, V.I., Mikhailov, I.E., Dushenko, G.A. et al. Fast and reversible migrations of N,S-centered groups around the perimeter of cyclopropene and cycloheptatriene rings. Russ Chem Bull 47, 884–894 (1998). https://doi.org/10.1007/BF02498157

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  • DOI: https://doi.org/10.1007/BF02498157

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