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Concerted aminolysis of diaryl carbonates: Kinetic sensitivity on the basicity of the nucleophile, nonleaving group, and nucleofuge
Author(s) -
Castro Enrique A.,
Cubillos María,
Iglesias Rocío,
Santos José G.
Publication year - 2012
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20700
Subject(s) - chemistry , aminolysis , alicyclic compound , steric effects , nucleophile , medicinal chemistry , ionic strength , nucleophilic substitution , kinetics , ionic liquid , organic chemistry , catalysis , physics , quantum mechanics , aqueous solution
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