Cyclohexanone is the

organic compound Some chemical authorities define an organic compound as a chemical compound that contains a carbon–hydrogen or carbon–carbon bond; others consider an organic compound to be any chemical compound that contains carbon. For example, carbon-co ...

with the

formula In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwe ...

(CH₂)₅CO. The molecule consists of six-carbon

cyclic molecule A cyclic compound (or ring compound) is a term for a compound in the field of chemistry in which one or more series of atoms in the compound is connected to form a ring. Rings may vary in size from three to many atoms, and include examples where ...

with a

ketone In organic chemistry, a ketone is an organic compound with the structure , where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group (a carbon-oxygen double bond C=O). The simplest ketone is acetone ( ...

functional group. This colorless oily liquid has a sweet odor reminiscent of

benzaldehyde Benzaldehyde (C6H5CHO) is an organic compound consisting of a benzene ring with a formyl substituent. It is among the simplest aromatic aldehydes and one of the most industrially useful. It is a colorless liquid with a characteristic almond-li ...

. Over time, samples of cyclohexanone assume a pale yellow color. Cyclohexanone is slightly soluble in water and miscible with common organic solvents. Millions of tonnes are produced annually, mainly as a precursor to

nylon Nylon is a family of synthetic polymers characterised by amide linkages, typically connecting aliphatic or Polyamide#Classification, semi-aromatic groups. Nylons are generally brownish in color and can possess a soft texture, with some varieti ...

History and synthesis

The compound was discovered by in 1888 among the products of AC electrolysis of slightly acidified water solutions of phenol. He named it hydrophenoketone and correctly suggested that phenol was first hydrogenated by electrolytic hydrogen to cyclohexanol, which he wasn't able to isolate, and then oxidized by electrolytic oxygen.

Laboratory synthesis

Cyclohexanone can be prepared from cyclohexanol by oxidation with

chromium trioxide Chromium trioxide (also known as chromium(VI) oxide or chromic anhydride) is an inorganic compound with the formula . It is the acidic anhydride of chromic acid, and is sometimes marketed under the same name. This compound is a dark-purple solid ...

( Jones oxidation). An alternative method utilizes the safer and more readily available oxidant

sodium hypochlorite Sodium hypochlorite is an alkaline inorganic chemical compound with the formula (also written as NaClO). It is commonly known in a dilute aqueous solution as bleach or chlorine bleach. It is the sodium salt of hypochlorous acid, consisting of ...

Industrial production

Cyclohexanone is produced by the oxidation of

cyclohexane Cyclohexane is a cycloalkane with the molecular formula . Cyclohexane is non-polar. Cyclohexane is a colourless, flammable liquid with a distinctive detergent-like odor, reminiscent of cleaning products (in which it is sometimes used). Cyclohexan ...

in air, typically using cobalt catalysts: :C₆H₁₂ + O₂ → (CH₂)₅CO + H₂O This process forms cyclohexanol as a

by-product A by-product or byproduct is a secondary product derived from a production process, manufacturing process or chemical reaction; it is not the primary product or service being produced. A by-product can be useful and marketable or it can be cons ...

, and this mixture, called "KA Oil" for ketone-alcohol oil, is the main feedstock for the production of

adipic acid Adipic acid or hexanedioic acid is the organic compound with the formula C6H10O4. It a white crystalline powder at standard temperature and pressure. From an industrial perspective, it is the most important dicarboxylic acid at about 2.5 billion ...

. The oxidation involves radicals and the

hydroperoxide Hydroperoxides or peroxols are Chemical compound, compounds of the form ROOH, where R stands for any group, typically Organic compound, organic, which contain the hydroperoxy functional group (). Hydroperoxide also refers to the hydroperoxide anio ...

C₆H₁₁O₂H as an intermediate. In some cases, purified cyclohexanol, obtained by hydration of

cyclohexene Cyclohexene is a hydrocarbon with the formula . It is a cycloalkene. At room temperature, cyclohexene is a colorless liquid with a sharp odor. Among its uses, it is an chemical intermediate, intermediate in the commercial synthesis of nylon. Prod ...

, is the precursor. Alternatively, cyclohexanone can be produced by the partial

hydrogenation Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to redox, reduce or Saturated ...

phenol Phenol (also known as carbolic acid, phenolic acid, or benzenol) is an aromatic organic compound with the molecular formula . It is a white crystalline solid that is volatile and can catch fire. The molecule consists of a phenyl group () ...

: :C₆H₅OH + 2 H₂ → (CH₂)₅CO This process can also be adjusted to favor the formation of cyclohexanol.

ExxonMobil Exxon Mobil Corporation ( ) is an American multinational List of oil exploration and production companies, oil and gas corporation headquartered in Spring, Texas, a suburb of Houston. Founded as the Successors of Standard Oil, largest direct s ...

developed a process in which benzene is hydroalkylated to cyclohexylbenzene. This latter product is

oxidized Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...

to a

and then cleaved into phenol and cyclohexanone. Therefore, this newer process without producing the acetone by-product appears attractive and is similar to the

cumene process The cumene process (cumene-phenol process, Hock process) is an industrial process for synthesizing phenol and acetone from benzene and propylene. The term stems from cumene (isopropyl benzene), the intermediate material during the process. It ...

as a hydroperoxide is formed and then decomposed to yield two key products.

Uses

The great majority of cyclohexanone is consumed in the production of precursors to Nylon 6,6 and Nylon 6. About half of the world's supply is converted to

, one of two precursors for nylon 6,6. For this application, the KA oil (see above) is oxidized with

nitric acid Nitric acid is an inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into nitrogen oxide, oxides of nitrogen. Most com ...

. The other half of the cyclohexanone supply is converted to cyclohexanone oxime. In the presence of

sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid (English in the Commonwealth of Nations, Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, ...

catalyst Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...

, the oxime rearranges to caprolactam, a precursor to nylon 6: ::

Other reactions

In addition to the large scale reactions conducted in service of the polymer industry, many reactions have been developed for cyclohexanone. In the presence of light, it undergoes alpha-chlorination to give 2-chlorocyclohexanone. It forms a trimethylsilylenol ether upon treatment with trimethylsilylchloride in the presence of base. It forms an enamine with pyrrolidine. Treatment with nitrosyl chloride and ethanol in

sulfur dioxide Sulfur dioxide (IUPAC-recommended spelling) or sulphur dioxide (traditional Commonwealth English) is the chemical compound with the formula . It is a colorless gas with a pungent smell that is responsible for the odor of burnt matches. It is r ...

gives the oximinecarboxylic ester: :

Illicit use

Cyclohexanone has been used in the illicit production of

phencyclidine Phencyclidine or phenylcyclohexyl piperidine (PCP), also known in its use as a street drug as angel dust among other names, is a dissociative anesthetic mainly used recreationally for its significant mind-altering effects. PCP may cause hall ...

and its analogs and is often subject to purchase restrictions, such as being listed on the Special Surveillance List in the US.

Safety

Like cyclohexanol, cyclohexanone is not carcinogenic and is moderately toxic, with a TLV of 25 ppm for the vapor. It is an irritant.

References

{{Authority control 6 IARC Group 3 carcinogens