29368-59-0Relevant articles and documents
Reinterpretation of curved hammett plots in reaction of nucleophiles with aryl benzoates: Change in rate-determining step or mechanism versus ground-state stabilization
Um, Ik-Hwan,Han, Hyun-Joo,Ahn, Jung-Ae,Kang, Swan,Buncel, Erwin
, p. 8475 - 8480 (2002)
A kinetic study is reported for the reaction of the anionic nucleophiles OH-, CN-, and N3- with aryl benzoates containing substituents on the benzoyl as well as the aryloxy moiety, in 80 mol % H2O-20 mol % dimethyl sulfoxide at 25.0 °C. Hammett log k vs σ plots for these systems are consistently nonlinear. However, a possible traditional explanation in terms of a mechanism involving a tetrahedral intermediate with curvature resulting from a change in rate-determining step is considered but rejected. The proposed explanation involves ground-state stabilization through resonance interaction between the benzoyl substituent and the electrophilic carbonyl center in the two-stage mechanism. Accordingly, the data are nicely accommodated on the basis of the Yukawa-Tsuno equation, which gives linear plots for all three nuceophiles. Literature reports of the mechanism of acyl transfer processes are reconsidered in this light.
The role of the leaving group in the dissociation of radical anions of 9-(aryloxymethyl)anthracenes [4]
Kimura
, p. 3824 - 3825 (2007/10/03)
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Electrochemistry of electron-transfer probes. The role of the leaving group in the cleavage of radical anions of α-aryloxyacetophenones
Andersen, Mogens L.,Mathivanan,Wayner, Danial D. M.
, p. 4871 - 4879 (2007/10/03)
The formal reduction potential (E°) of α-phenoxyacetophenone has been determined from the voltammetric peak potential obtained by linear sweep voltammetry in combination with the rate constant for fragmentation of the radical anion which had been determin