Electrochemical contributions: Adolph Wilhelm Hermann Kolbe (1818–1884)

Hermann Kolbe (Figure 1) was a German scientist who greatly contributed to the development of organic chemistry, transforming it to the state as we know it now. Kolbe pioneered organic synthesis from inorganic sources and introduced the term “synthesis” in the meaning how we use it in chemistry now. His name is associated with several synthetic reactions in organic chemistry, e.g., the Kolbe-Schmitt reaction in the preparation of aspirin, the Kolbe nitrile synthesis, etc. His work is particularly remembered in connection to electrolysis of carboxylic acids resulting in the synthesis of various organic compounds, known as the Kolbe reaction.

The Kolbe reaction (Figure 2), proceeding as the electrolysis, results in the oxidative decarboxylation of carboxylic acids yielding free radicals, which dimerize producing symmetrical products. For example, the Kolbe electrolysis process can proceed in an aqueous solution of sodium acetate (Figure 2). The acetate ions get decomposed and form methyl radicals. These combine with other free methyl radicals, which leads to the generation of ethane. In general, Kolbe's electrolysis method uses sodium salts of fatty acids to form the corresponding alkanes as products (D. Klüh, W. Waldmüller, M. Gaderer, Clean. Technol. 2021, 3, 1–18). A similar electrochemical synthesis can be used to produce more sophisticated products (Figure 2B). If the initial mixture includes two different acids, the reaction results in three different products from the cross-reaction of two different free radicals. The Kolbe electrolytic decarboxylation of 1,2-dicarboxylic acids results in the formation of double or triple chemical bonds (Figure 3). When carboxylic groups are located at a longer distance in a molecule, the electrolytic decarboxylation may result in the intramolecular radical cyclization of the reaction product.

It should be noted that the Kolbe electrolysis reaction may result in the formation of numerous byproducts (Figure 4). The formation of side products depends on the ease of the follow-up oxidation, which leads to carbenium ions, and their subsequent rearrangements. The exact mechanism and kinetics study of the electrochemical Kolbe process have been investigated confirming the complexity of the electrochemical reaction (A.K. Vijh, B.E. Conway, Chem. Rev. 1967, 67, 6, 623-664).

The author declares no conflict of interest.