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Effect of the nature of the substituents in 2,4,6-trisubstituted phenols on their reactions with nitric acid

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Summary

  1. 1.

    The electrophilic reaction of 2,4,6-trisubstituted phenols with nitric acid was studied.

  2. 2.

    As a result of the considerable electromeric effect given by the hydroxy group, the nitronium ion reacts with a phenol that is already substituted in the para or ortho position, and m-nitrophenols are not formed.

  3. 3.

    The course of the reaction depends on the competition of the electromeric effect of the hydroxy group mainly with the negative inductive effect of the substituent.

  4. 4.

    Reaction leads initially to the formation of nitro p- or o-quinonoid compounds, which, depending on the nature of the substituent, are either stable, or are converted rapidly into o- or p-nitrophenols (displacement nitration).

  5. 5.

    The nature of the solvent does not affect the course of the reaction.

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Additional information

This paper is published in accordance with a resolution of the Conference of Chief Editors of Journals of the Academy of Sciences of the USSR, July 12, 1962, as a dissertation paper by G. A. Zlobina.

The authors thank N M. Émanuél for his constant interest in this work.

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1666–1675, September, 1964

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Zlobina, G.A., Ershov, V.V. Effect of the nature of the substituents in 2,4,6-trisubstituted phenols on their reactions with nitric acid. Russ Chem Bull 13, 1570–1577 (1964). https://doi.org/10.1007/BF00846293

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Keywords

  • Phenol
  • Nitric Acid
  • Nitration
  • Hydroxy Group
  • Inductive Effect