The Kolbe–Schmitt reaction or Kolbe process (named after Hermann Kolbe and Rudolf Schmitt) is a

carboxyl In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an R-group. The general formula of a carboxylic acid is or , with R referring to the alkyl, alkenyl, aryl, or other group. Carboxylic ...

ation

chemical reaction A chemical reaction is a process that leads to the IUPAC nomenclature for organic transformations, chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the pos ...

that proceeds by heating sodium phenoxide (the

sodium Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable ...

salt of

phenol Phenol (also called carbolic acid) is an aromatic organic compound with the molecular formula . It is a white crystalline solid that is volatile. The molecule consists of a phenyl group () bonded to a hydroxy group (). Mildly acidic, it ...

) with

carbon dioxide Carbon dioxide ( chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is trans ...

under pressure (100 atm, 125 °C), then treating the product with sulfuric acid. The final product is an

aromatic In chemistry, aromaticity is a chemical property of cyclic ( ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to satur ...

hydroxy acid which is also known as salicylic acid (the precursor to

aspirin Aspirin, also known as acetylsalicylic acid (ASA), is a nonsteroidal anti-inflammatory drug (NSAID) used to reduce pain, fever, and/or inflammation, and as an antithrombotic. Specific inflammatory conditions which aspirin is used to treat inc ...

). 500px, center, The Kolbe–Schmitt reaction By using

potassium hydroxide Potassium hydroxide is an inorganic compound with the formula K OH, and is commonly called caustic potash. Along with sodium hydroxide (NaOH), KOH is a prototypical strong base. It has many industrial and niche applications, most of which exp ...

4-hydroxybenzoic acid 4-Hydroxybenzoic acid, also known as ''p''-hydroxybenzoic acid (PHBA), is a monohydroxybenzoic acid, a phenolic derivative of benzoic acid. It is a white crystalline solid that is slightly soluble in water and chloroform but more soluble in polar ...

is accessible, an important precursor for the versatile paraben class of biocides used e.g. in personal care products. The methodology is also used in the industrial synthesis of 3-hydroxy-2-naphthoic acid; the regiochemistry of the carboxylation in this case is sensitive to temperature..

Reaction mechanism

The Kolbe–Schmitt reaction proceeds via the nucleophilic addition of a

phenoxide Phenolates (also called phenoxides) are anions, salts, and esters of phenols. They may be formed by reaction of phenols with strong base. Properties Alkali metal phenolates, such as sodium phenolate hydrolyze in aqueous solution to form basic s ...

, classically sodium phenoxide (NaOC₆H₅), to

to give the salicylate. The final step is the reaction (

protonation In chemistry, protonation (or hydronation) is the adding of a proton (or hydron, or hydrogen cation), (H+) to an atom, molecule, or ion, forming a conjugate acid. (The complementary process, when a proton is removed from a Brønsted–Lowry acid ...

) of the salicylate

anion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conve ...

with an acid to form the desired salicylic acids (ortho- and para- isomers). Kolbe-Schmitt-reaction-mechanism

References

External links

English Translation of Kolbe's seminal 1860 German article in Annalen der Chemie und Pharmacie that describes the discovery of this reaction. English title: 'On the syntheses of salicylic acid'; German title "Ueber Synthese der Salicylsäure".

An animation of the reaction mechanism. {{DEFAULTSORT:Kolbe-Schmitt reaction Addition reactions Carbon-carbon bond forming reactions Industrial processes Name reactions