Abstract
Functionalized pyrroleьvьЄ enols, 2-(1-hydroxy-2.2-dicyanoethenyl)-1-methylpyrroles, at heating (75–135°C) unexpectedly readily rearranged in high yield into 3-isomers. Evidently the migration of the enol fragment involves a mesomeric zwitterion formed as a result of an intra- and intermolecular autoprotonation of the pyrrole ring by the acidic enol hydroxy group. Under similar conditions no migration of the ethenyl moiety occurred in 2-(1-hydroxy-2-carbamoyl-2-cyanoethenyl)-1-methylpyrroles. The quantum-chemical calculations (MP2/6-311G**) show a clear-cut distinction in the relative stability of 2- and 3-isomers of 1H- and 1-methylhydroxyethenylpyrroles: in the former case the 2-isomer is more stable, whereas in the 1-methyl-substituted compound, the 3-isomer.
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Dedicated to the Full Member of the Russian Academy of Sciences G.A. Tolstikov on occasion of his 75th anniversary
Original Russian Text © L.N. Sobenina, V.N. Drichkov, O.V. Petrova, I.A. Ushakov, T.V. Kashik, L.B. Krivdin, Yu.Yu. Rusakov, E.V. Zykova, A.I. Mikhaleva, B.A. Trofimov, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 2, pp. 246–255.
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Sobenina, L.N., Drichkov, V.N., Petrova, O.V. et al. Incomparably easy migration of functionalized enol substituent in pyrrole ring. Russ J Org Chem 44, 237–246 (2008). https://doi.org/10.1134/S1070428008020097
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DOI: https://doi.org/10.1134/S1070428008020097