Cyclohexanone oxime is an

organic compound In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. The ...

containing the functional group

oxime In organic chemistry, an oxime is a organic compound belonging to the imines, with the general formula , where R is an organic side-chain and R’ may be hydrogen, forming an aldoxime, or another organic group, forming a ketoxime. O-substituted ...

. This colorless solid is an important intermediate in the production of

nylon 6 Nylon 6 or polycaprolactam is a polymer, in particular semicrystalline polyamide. Unlike most other nylons, nylon 6 is not a condensation polymer, but instead is formed by ring-opening polymerization; this makes it a special case in the comparis ...

, a widely used

polymer A polymer (; Greek '' poly-'', "many" + ''-mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...

Preparation

Cyclohexanone oxime can be prepared from the

condensation reaction In organic chemistry, a condensation reaction is a type of chemical reaction in which two molecules are combined to form a single molecule, usually with the loss of a small molecule such as water. If water is lost, the reaction is also known as a ...

between

cyclohexanone Cyclohexanone is the organic compound with the formula (CH2)5CO. The molecule consists of six-carbon cyclic molecule with a ketone functional group. This colorless oily liquid has an odor reminiscent of acetone. Over time, samples of cyclohexan ...

and

hydroxylamine Hydroxylamine is an inorganic compound with the formula . The material is a white crystalline, hygroscopic compound.Greenwood and Earnshaw. ''Chemistry of the Elements.'' 2nd Edition. Reed Educational and Professional Publishing Ltd. pp. 431–43 ...

:J. C. Eck and C. S. Marvel "ε-Benzoylaminocaproic Acid" Org. Synth. 1939, volume 19, pp. 20. :C₅H₁₀CO + H₂NOH → C₅H₁₀C=NOH + H₂O Alternatively, another industrial route involves the reaction of

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

with

nitrosyl chloride Nitrosyl chloride is the chemical compound with the formula NOCl. It is a yellow gas that is commonly encountered as a component of aqua regia, a mixture of 3 parts concentrated hydrochloric acid and 1 part of concentrated nitric acid. It is a st ...

, which is a

free radical reaction A free-radical reaction is any chemical reaction involving free radicals. This reaction type is abundant in organic reactions. Two pioneering studies into free radical reactions have been the discovery of the triphenylmethyl radical by Moses Gomber ...

. This method is advantageous as cyclohexane is much cheaper than cyclohexanone.

Reactions

The most famous and commercially important reaction of cyclohexanone oxime is

Beckmann rearrangement The Beckmann rearrangement, named after the German chemist Ernst Otto Beckmann (1853–1923), is a rearrangement of an oxime functional group to substituted amides. The rearrangement has also been successfully performed on haloimines and nitrones ...

yielding ε-caprolactam: Beckmann rearrangement of cyclohexanone oxime

This reaction is catalyzed by

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

, but industrial scale reactions use

solid acid Solid is one of the four fundamental states of matter (the others being liquid, gas, and plasma). The molecules in a solid are closely packed together and contain the least amount of kinetic energy. A solid is characterized by structural ri ...

s. Typical of oximes, the compound can be reduced by

sodium amalgam Sodium amalgam, commonly denoted Na(Hg), is an alloy of mercury and sodium. The term amalgam is used for alloys, intermetallic compounds, and solutions (both solid solutions and liquid solutions) involving mercury as a major component. Sodium amal ...

to produce

cyclohexylamine Cyclohexylamine is an organic compound, belonging to the aliphatic amine class. It is a colorless liquid, although, like many amines, samples are often colored due to contaminants. It has a fishy odor and is miscible with water. Like other amines, ...

.W. H. Lycan, S. V. Puntambeker, and

C. S. Marvel Carl Shipp "Speed" Marvel (September 11, 1894 – January 4, 1988) was an American chemist who specialized in polymer chemistry. He made important contributions to U.S. synthetic rubber program during World War II, and later worked at developing ...

"n-Heptylamine" Org. Synth. 1931, volume 11, pp. 58. It can also be hydrolyzed with

acetic acid Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main component ...

to give back cyclohexanone.

References

{{Authority control Cyclohexanes Ketoximes