Comparison of the intrinsic reactivities of carbon and oxygen nucleophiles at the 1,3,5-trinitro-substituted aromatic ring

Abstract

Kinetic and equilibrium data are reported for nucleophilic attack by nitroalkane anions at unsubstituted ring positions of 1,3,5-trinitrobenzene and of 2,4,6-trinitrotoluene. The results allow the calculation for this reaction type of values for intrinsic rate coefficients, k₀, of 0.18 for CH₂NO₂^– and 0.22 for MeCHNO₂^–. The corresponding value for the malononitrile anion, CH(CN)₂^–, is 2.5 × 10⁴, and for the methoxide ion the value is 10³. The results are discussed in terms of the electronic-structural and solvational reorganisation occurring during reaction.