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.