Concerted aminolysis of diaryl carbonates: Kinetic sensitivity on the basicity of the nucleophile, nonleaving group, and nucleofuge
✍ Scribed by Enrique A. Castro; María Cubillos; Rocío Iglesias; José G. Santos
- Book ID
- 102450091
- Publisher
- John Wiley and Sons
- Year
- 2012
- Tongue
- English
- Weight
- 262 KB
- Volume
- 44
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
Abstract
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