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Regioselectivity in the amination of azines: Reaction of pyrazine derivatives with O-mesitylenesulfonylhydroxylamine

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Abstract

Treatment of 2-X-substituted pyrazines [X = H, Me, Et, Pr, i-Pr, t-Bu, MeCH(OH), H2N, AcNH] with O-mesitylenesulfonylhydroxylamine gave the corresponding 2-X- and 3-X-(1-amino)pyrazin-1-ium mesitylenesulfonates. 2-Alkylpyrazines (X = Me, Et, Pr, i-Pr) displayed a correlation between the logarithms of the concentration ratio of 2- and 3-substituted cations and substituent steric constants. Wider series of substituted pyrazines [X = H, Me, Et, Pr, i-Pr, MeCH(OH), H2N, AcNH] conformed to a multiparameter correlation between the logarithms of the concentration ratio of 2- and 3-substituted cations, on the one hand, and substituent constants σI, σ oR , and E os , on the other. The obtained data on the regioselectivity of amination of pyrazines were interpreted in terms of DFT/PBE/3Z quantum-chemical calculations.

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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, M. M. Shakirov & 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. M. M. Shakirov
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  4. 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, M.M. Shakirov, V.G. Shubin, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 6, pp. 872–879.

For preliminary communications, see [1, 2].

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Borodkin, G.I., Vorob’ev, A.Y., Shakirov, M.M. et al. Regioselectivity in the amination of azines: Reaction of pyrazine derivatives with O-mesitylenesulfonylhydroxylamine. Russ J Org Chem 47, 889–896 (2011). https://doi.org/10.1134/S1070428011060108

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