The stabilities of Meisenheimer complexes. Part 39. Steric effects on rate and equilibrium constants for σ-adduct formation from alkyl 2,4,6-trinitro-phenyl ethers and ethoxide ions in ethanol

Abstract

Rate and equilibrium data are reported for reactions of ethoxide ions in ethanol with four alkyl 2,4,6-trinitrophenyl ethers to give isomeric 1,3 and 1,1 σ-adducts. The results indicate the importance of steric factors in this series. Increasing the size of the alkyl substituent causes decreases in values of k₃, the rate coefficient, and K₃, the equilibrium constant, for reaction at the unsubstituted 3-position, and also causes decreases in values of k₁ for reaction at the substituted position.