Mechanism of the Kolbe-Schmitt reaction with lithium and sodium phenoxides

Russian Journal of Physical Chemistry (Impact Factor: 0.56). 08/2007; 81(9):1392-1397. DOI: 10.1134/S0036024407090087


The mechanisms of the carboxylation reactions of lithium and sodium phenoxides are investigated by means of the DFT method
with a CEP-31 + G(d) basis set. The introduction of diffusion functions does not affect the outcome of the calculations. As a consequence, the
results of this investigation are in good agreement with the findings obtained by means of the LANL2DZ basis set. Lithium
phenoxide yields only salicylic acid in the Kolbe-Schmitt reaction. The reaction of sodium phenoxide can proceed in the ortho and para positions, but the para-substituted product can be expected at a very low concentration in the reaction mixture. The deviation of lithium and sodium
phenoxides from the mechanisms of carboxylations of other alkali metals is a consequence of the small ionic radii of lithium
and sodium.

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Available from: Zoran Marković, May 17, 2014
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