Concerted aminolysis of diaryl carbonates: Kinetic sensitivity on the basicity of the nucleophile, nonleaving group, and nucleofuge

The kinetics of the reactions of 4‐methylphenyl, phenyl, and 4‐chlorophenyl 2,4,6‐trinitrophenyl carbonates ( 1 , 2 , and 3 , respectively) with a series of anilines and secondary alicyclic (SA) amines has been carried out spectrophotometrically in 44 wt% ethanol–water, at 25.0°C, ionic strength 0.2 M. The Brønsted plots (statistically corrected) for the reactions of carbonates 1 – 3 with anilines and SA amines were linear with slopes ( β N ) in the range of 0.69–0.78 and 0.45–0.48, respectively, attributed to a concerted mechanism. The negative values found for the sensitivity of log k N to the basicity of the nonleaving ( β nlg ) and leaving ( β lg ) groups are discussed. Anilines are more reactive than isobasic SA amines, probably because of the greater steric hindrance offered by the latter. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 604–611, 2012