Article

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

Russian Journal of Physical Chemistry (Impact Factor: 0.49). 08/2007; 81(9):1392-1397. DOI: 10.1134/S0036024407090087

ABSTRACT 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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    Monatshefte fuer Chemie/Chemical Monthly 01/2008; 139(10):1169-1174. · 1.63 Impact Factor
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    ABSTRACT: The mechanism of the Kolbe-Schmitt reaction of sodium 2-naphthoxide is examined by means of the B3LYP/LANL2DZ method. After the initial formation of sodium 2-naphthoxide-CO2 complex, the carbon of the CO2 moiety performs an electrophilic attack on the naphthalene ring. Further transformations lead to the formation of sodium 2-hydroxy-1-naphthoate. Sodium 3-hydroxy-2-naphthoate is formed by a 1,3-rearrangement of the CO2Na group. Our findings are in good agreement with the experimental results on the carboxylation reaction of sodium 2-naphthoxide.
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