Issue 5, 2003

Carboxylations of alkali metal phenoxides with carbon dioxide

Abstract

The reaction mechanism of the Kolbe–Schmitt reaction of phenol and 2-naphthol has been investigated. An alkali metal phenoxide–CO2 complex is not an intermediate that can be easily transformed into a carboxylic acid, such as salicylic acid (SA) and p-hydroxybenzoic acid (pHBA). A direct carboxylation of phenoxide with CO2 takes place even at room temperature, and is competitive with the formation of the CO2 complex. The resulting complex decomposes thermally (above ca. 100 °C) to phenoxide, which then undergoes further competitive reactions. Experiments using a carbon-13 labeled complex support a mechanism of direct carboxylation, and not the mechanism via a CO2 complex. The reactivity, C-13 NMR and MOPAC/PM3 calculations suggest a new carbonate-like structure for the CO2 complex.

Graphical abstract: Carboxylations of alkali metal phenoxides with carbon dioxide

Additions and corrections

Article information

Article type
Paper
Submitted
01 Nov 2002
Accepted
06 Jan 2003
First published
05 Feb 2003

Org. Biomol. Chem., 2003,1, 817-821

Carboxylations of alkali metal phenoxides with carbon dioxide

Y. Kosugi, Y. Imaoka, F. Gotoh, M. A. Rahim, Y. Matsui and K. Sakanishi, Org. Biomol. Chem., 2003, 1, 817 DOI: 10.1039/B210793G

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