Fast and reversible migrations of N,S-centered groups around the perimeter of cyclopropene and cycloheptatriene rings |
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Authors: | V. I. Minkin I. E. Mikhailov G. A. Dushenko O. E. Kompan A. Zschunke |
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Affiliation: | (1) Scientific-Research Institute of Physical and Organic Chemistry, Rostov State University, 194/2 prosp. Stachki, 344090 Rostov-on-Don, Russian Federation;(2) Institute of Chemistry, Humboldt University, D-10115 Berlin, Germany |
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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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Keywords: | cyclopropene cycloheptatriene tautomeric rearrangements dynamic NMR organic reaction mechanisms X-ray analysis |
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