Russian Chemical Bulletin

, Volume 42, Issue 11, pp 1806–1810 | Cite as

Quantum chemical study on the mechanisms of nucleophilic substitution of a nitro group in 2,4,6-trinitrotoluene and 1,3,5-trinitrobenzene

  • V. N. Solkan
  • S. A. Shevelev
Physical Chemistry
  • 36 Downloads

Abstract

The semiempirical MNDO-PM3 method is employed for calculations of the enthalpies of formation of Meisenheimerortho- andipso-σ-complexes of 1,3,5-trinitrobenzene (TNB) and 2,4,6-trinitrotoluene (TNT) with the methoxide ion in the gas phase and in water (using the pseudocontinual point-dipole solvation model). The calculated reaction enthalpies for the replacement of a TNB and TNT nitro group with a methoxy group reveal in principle the possibility for TNB to react with the methoxide ion in water by theSNAr mechanism through an intermediateipso-σ-complex. In the gas phase this reaction can not follow theSNAr mechanism due to its strong endothermicity (20 kcal/mol). The analogous nucleophilic substitution of a TNT nitro group by a methoxy group may be suppressed by the faster formation of the stable trinitrobenzene anion.

Key words

Meisenheimer complexes 1,3,5-trinitrobenzene 2,4,6-trinitrotoluene quantum chemical calculations MNDO-PM3 method reaction mechanism 

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Copyright information

© Plenum Publishing Corporation 1994

Authors and Affiliations

  • V. N. Solkan
    • 1
  • S. A. Shevelev
    • 1
  1. 1.N.D.Zelinsky Institute of Organic ChemistryRussian Academy of SciencesMoscowRussian Federation

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