3235-09-4Relevant articles and documents
Ambident Reactivity of Phenolate Anions Revisited: A Quantitative Approach to Phenolate Reactivities
Mayer, Robert J.,Breugst, Martin,Hampel, Nathalie,Ofial, Armin R.,Mayr, Herbert
, p. 8837 - 8858 (2019/07/08)
Prompted by the observation that the regioselectivities of phenolate reactions (C versus O attack) are opposite to the predictions by the principle of hard and soft acids and bases, we performed a comprehensive experimental and computational investigation of phenolate reactivities. Rate and equilibrium constants for the reactions of various phenolate ions with benzhydrylium ions (Aryl2CH+) and structurally related quinone methides have been determined photometrically in polar aprotic solvents. Quantum chemical calculations at the SMD(MeCN)/M06-2X/6-31+G(d,p) level confirmed that O attack is generally favored under kinetically controlled conditions, whereas C attack is favored under thermodynamically controlled conditions. Exceptions are diffusion-limited reactions with strong electrophiles, which give mixtures of products arising from O and C attack, as well as reactions with metal alkoxides in nonpolar solvents, where oxygen attack is blocked by strong ion pairing. The Lewis basicity (LB) and nucleophilicity (N, sN) parameters of phenolates determined in this work can be used to predict whether their reactions with electrophiles are kinetically or thermodynamically controlled and whether the rates are activation- or diffusion-limited. Comparison of the measured rate constants for the reactions of phenolates with carbocations with the Gibbs energies for single-electron transfer manifests that these reactions proceed via polar mechanisms.
Process for preparing para-hydroxybenzoic acid
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, (2008/06/13)
The improved process for preparing para-hydroxybenzoic acid comprises reacting potassium phenol with carbon dioxide in an inert reaction medium or without using a reaction medium in the presence of at least one compound selected from the group consisting of the compounds represented by the following general formula I or II: STR1 at a reaction temperature of 230°-450° C. and at a carbon dioxide pressure ranging from atmospheric pressure to 6 kg/cm2 (G). The process may comprise two stages and the first-stage reaction described above is followed by the second stage in which the reaction is further continued with the pressure of carbon dioxide in the system being reduced and/or the reaction temperature being elevated within the range specified above. Also, phenol may be used as the starting material instead of potassium phenolate.
