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Reductive activation of arenes 22. Reactions of the terephthalonitrile radical anion and dianion with α,ω-dibromoalkanes. New evidence for the charge transfer complex as a key intermediate in the reactions of the dianion

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Abstract

The major products of reactions of the terephthalonitrile radical anion with α,ω-dibromoalkanes Br(CH2)nBr (n = 3–5) were 4-(ω-bromoalkyl)benzonitriles. Analogous reactions of the terephthalonitrile dianion mainly yielded α,ω-bis(4-cyanophenyl)alkanes. Both transformations are convenient one-step routes to otherwise not easily accessible compounds that are valuable as versatile building blocks. The results of alkylation allow one to suggest that reactions of the dianion with intermediate 4-(ω-bromoalkyl)benzonitriles proceed more rapidly than those with the starting α,ω-dibromoalkanes. This was confirmed by competitive reactions of the dianion with 4-(ω-bromoalkyl)benzonitriles and the corresponding alkyl bromides. To explain such a ratio of the reaction rates, a mechanism was proposed for the reaction of the dianion with 4-(ω-bromoalkyl)benzonitriles. According to this mechanism, a charge transfer complex is a key reaction intermediate.

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Authors and Affiliations

  1. N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9 prosp. Akad. Lavrent’eva, 630090, Novosibirsk, Russian Federation

    E. V. Panteleeva, M. Yu. Lukyanova, L. M. Pokrovsky & V. D. Shteingarts

  2. Novosibirsk State University, 2 ul. Pirogova, 630090, Novosibirsk, Russian Federation

    E. V. Panteleeva & V. D. Shteingarts

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  1. E. V. Panteleeva
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  2. M. Yu. Lukyanova
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  3. L. M. Pokrovsky
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  4. V. D. Shteingarts
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Correspondence to V. D. Shteingarts.

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Dedicated to the memory of Academician N. N. Vorozhtsov on the 100th anniversary of his birth.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1069–1077, June, 2007.

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Panteleeva, E.V., Lukyanova, M.Y., Pokrovsky, L.M. et al. Reductive activation of arenes 22. Reactions of the terephthalonitrile radical anion and dianion with α,ω-dibromoalkanes. New evidence for the charge transfer complex as a key intermediate in the reactions of the dianion. Russ Chem Bull 56, 1110–1118 (2007). https://doi.org/10.1007/s11172-007-0168-z

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  • DOI: https://doi.org/10.1007/s11172-007-0168-z

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