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Structure-kinetics relations holding in the amination of six-membered nitrogen-containing heterocyclic compounds

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Abstract

Relative rates of the amination of 3-X- and 4-X-substituted pyridines (X = H, 3-Me, 4-Me, 3-F3C, 3-CN, 4-CN, 3-Cl, 3-Br, 4-MeO, 4-Me2N), pyrazine, quinoline, isoquinoline, 2,2′- and 4,4′-bipyridines, and 1,10-phenanthroline with O-mesitylenesulfonylhydroxylamine were estimated by NMR spectroscopy. Correlations were found between logarithms of the relative amination rate constants and substituent constants σ or σI and σR for X-substituted pyridines. A wide series of nitrogen-containing heterocyclic compounds turned out to fit correlations between logarithms of the relative amination rate constants, on the one hand, and relative stabilities of N-aminoazinium cations, energies of activation of the amination process, and gas-phase proton affinities, calculated by the DFT/PBE/3z and DFT/B3LYP/L2 methods, on the other.

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Authors and Affiliations

  1. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences, pr. Akademika Lavrent’eva 9, Novosibirsk, 630090, Russia

    G. I. Borodkin, A. Yu. Vorob’ev & V. G. Shubin

  2. Novosibirsk State University, Novosibirsk, Russia

    G. I. Borodkin & A. Yu. Vorob’ev

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  1. G. I. Borodkin
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  2. A. Yu. Vorob’ev
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  3. V. G. Shubin
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Correspondence to G. I. Borodkin.

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Original Russian Text © G.I. Borodkin, A.Yu. Vorob’ev, V.G. Shubin, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 6, pp. 880–886.

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Borodkin, G.I., Vorob’ev, A.Y. & Shubin, V.G. Structure-kinetics relations holding in the amination of six-membered nitrogen-containing heterocyclic compounds. Russ J Org Chem 47, 897–903 (2011). https://doi.org/10.1134/S107042801106011X

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