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An unsymmetrical behavior of reactant units in the Kolbe–Schmitt reaction

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Abstract

Paths of the Kolbe–Schmitt reaction were investigated by the use of RB3LYP/6-311(+)G(d,p) density functional theory calculations. In a monomer model composed of C6H5O−, Na+ and CO2 affording sodium salicylate [C6H4(OH)CO2 −Na+], a proton-shift step (Z Naturforsch 57a:812, 2002) was found to have an unrealistically large activation energy. In consideration of the phenol volatilization in the Kolbe’s experiment and the need of the linearity of the proton-transfer path, a dimer model was constructed. Again, a mutual proton-transfer step has a large activation energy. Alternatively, in a dimer model, a transfer path where the phenoxide ion in one monomer acts as a proton acceptor was found to have a reasonable energy. Addition of one more sodium ion leads to the significant lowering of activation energies. Thus, in the dimer, two monomers behave differently (A + A → A + B); one is as if it were a catalyst.

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Authors and Affiliations

  1. Department of Chemistry, Nara University of Education, Takabatake-cho, Nara, 630-8528, Japan

    Shinichi Yamabe & Shoko Yamazaki

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  1. Shinichi Yamabe
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  2. Shoko Yamazaki
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Correspondence to Shinichi Yamabe.

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Dedicated to Professor Akira Imamura on the occasion of his 77th birthday and published as part of the Imamura Festschrift Issue.

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Yamabe, S., Yamazaki, S. An unsymmetrical behavior of reactant units in the Kolbe–Schmitt reaction. Theor Chem Acc 130, 891–900 (2011). https://doi.org/10.1007/s00214-010-0803-x

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