Cyclohexanone

Last updated

Cyclohexanone [1] [2]
Skeletal formula of cyclohexanone Cyclohexanone.svg
Skeletal formula of cyclohexanone
Ball-and-stick model of cyclohexanone Cyclohexanone-from-xtal-top-view-3D-bs-17.png
Ball-and-stick model of cyclohexanone
Skeletal formula viewed side-on, showing the non-planar conformation Cyclohexanone-conformation-2D-skeletal.png
Skeletal formula viewed side-on, showing the non-planar conformation
Ball-and-stick model of cyclohexanone viewed side-on, showing the non-planar conformation Cyclohexanone-from-xtal-side-view-3D-bs-17.png
Ball-and-stick model of cyclohexanone viewed side-on, showing the non-planar conformation
Names
Preferred IUPAC name
Cyclohexanone
Other names
oxocyclohexane, pimelic ketone, ketohexamethylene, cyclohexyl ketone, ketocyclohexane, hexanon, Hydrol-O, Sextone, K, Anone
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.003.302 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 203-631-1
KEGG
PubChem CID
UNII
  • InChI=1S/C6H10O/c7-6-4-2-1-3-5-6/h1-5H2 Yes check.svgY
    Key: JHIVVAPYMSGYDF-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C6H10O/c7-6-4-2-1-3-5-6/h1-5H2
    Key: JHIVVAPYMSGYDF-UHFFFAOYAY
  • C1CCC(=O)CC1
Properties
C6H10O
Molar mass 98.15 g/mol
AppearanceColorless liquid [3]
Odor Peppermint or acetone-like
Density 0.9478 g/mL, liquid
Melting point −47 °C (−53 °F; 226 K) [4]
Boiling point 155.65 °C (312.17 °F; 428.80 K)
8.6 g/100 mL (20 °C)
Solubility in all organic solventsMiscible
log P 0.81
Vapor pressure 5 mmHg (20 °C) [5]
−62.04·10−6 cm3/mol
1.447
Viscosity 2.02  cP at 25 °C [6]
Thermochemistry
Std molar
entropy (S⦵298)
+229.03 J·K−1·mol−1
−270.7 kJ·mol−1
−3519.3 kJ·mol−1
Hazards
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-skull.svg GHS-pictogram-exclam.svg
Danger [7]
H226, H302, H305, H312, H315, H318, H332 [7]
P280, P305+P351+P338 [7]
NFPA 704 (fire diamond)
NFPA 704.svgHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 2: Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. Flash point between 38 and 93 °C (100 and 200 °F). E.g. diesel fuelInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
1
2
0
Flash point 44 °C (111 °F; 317 K)
420 °C (788 °F; 693 K)
Explosive limits 1.1–9.4%
Lethal dose or concentration (LD, LC):
1200 mg/kg (cat, orally); 2362 mg/kg (rat, orally) [8]
8000 ppm (rat, 4 hr) [9]
4706 ppm (mouse, 1.5 hr) [9]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 50 ppm (200 mg/m3) [5]
REL (Recommended)
TWA 25 ppm (100 mg/m3) [skin] [5]
IDLH (Immediate danger)
700 ppm [5]
Related compounds
Related ketones
Cyclopentanone, cycloheptanone
Related compounds
 Cyclohexanol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

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 [3] has a sweet odor reminiscent of benzaldehyde. Over time, samples of cyclohexanone assume a pale yellow color. [10]

Contents

Cyclohexanone is slightly soluble in water and miscible with common organic solvents. Millions of tonnes are produced annually, mainly as a precursor to nylon. [11]

History and synthesis

The compound was discovered by Edmund Drechsel  [ de ] 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. [12] [13]

Laboratory synthesis

Cyclohexanone can be prepared from cyclohexanol by oxidation with chromium trioxide (Jones oxidation). An alternative method utilizes the safer and more readily available oxidant sodium hypochlorite. [14] [15]

Industrial production

Cyclohexanone is produced by the oxidation of cyclohexane in air, typically using cobalt catalysts: [11]

C6H12 + O2 → (CH2)5CO + H2O

This process forms cyclohexanol as a by-product, and this mixture, called "KA Oil" for ketone-alcohol oil, is the main feedstock for the production of adipic acid. The oxidation involves radicals and the hydroperoxide C6H11O2H as an intermediate. In some cases, purified cyclohexanol, obtained by hydration of cyclohexene, is the precursor. Alternatively, cyclohexanone can be produced by the partial hydrogenation of phenol:

C6H5OH + 2 H2 → (CH2)5CO

This process can also be adjusted to favor the formation of cyclohexanol. [11]

ExxonMobil developed a process in which benzene is hydroalkylated to cyclohexylbenzene. This latter product is oxidized to a hydroperoxide and then cleaved into phenol and cyclohexanone. [16] Therefore, this newer process without producing the acetone by-product appears attractive and is similar to the cumene process as a hydroperoxide is formed and then decomposed to yield two key products. [17]

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 adipic acid, one of two precursors for nylon 6,6. For this application, the KA oil (see above) is oxidized with nitric acid. The other half of the cyclohexanone supply is converted to cyclohexanone oxime. In the presence of sulfuric acid catalyst, the oxime rearranges to caprolactam, a precursor to nylon 6: [11]

Caprolactam Synth.png

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. [18] It forms a trimethylsilylenol ether upon treatment with trimethylsilylchloride in the presence of base. [19]

It forms an enamine with pyrrolidine. [20]

Treatment with nitrosyl chloride and ethanol in sulfur dioxide gives the oximinecarboxylic ester: [21]

(CH2)5CO + C2H5OH + NOCl → HON=CH(CH2)4CO2C2H5 + HCl

Illicit use

Cyclohexanone has been used in the illicit production of phencyclidine and its analogs [22] and is often subject to purchase restrictions, such as being listed on the Special Surveillance List in the US. [23]

Safety

Like cyclohexanol, cyclohexanone is not carcinogenic and is moderately toxic, with a TLV of 25 ppm for the vapor. It is an irritant. [11]

Related Research Articles

<span class="mw-page-title-main">Ketone</span> Organic compounds of the form >C=O

In organic chemistry, a ketone is an organic compound with the structure R−C(=O)−R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group −C(=O)−. The simplest ketone is acetone, with the formula (CH3)2CO. Many ketones are of great importance in biology and industry. Examples include many sugars (ketoses), many steroids, and the solvent acetone.

<span class="mw-page-title-main">Phenol</span> Organic compound (C6H5OH)

Phenol is an aromatic organic compound with the molecular formula C6H5OH. It is a white crystalline solid that is volatile. The molecule consists of a phenyl group bonded to a hydroxy group. Mildly acidic, it requires careful handling because it can cause chemical burns.

Cyclohexane is a cycloalkane with the molecular formula C6H12. Cyclohexane is non-polar. Cyclohexane is a colourless, flammable liquid with a distinctive detergent-like odor, reminiscent of cleaning products. Cyclohexane is mainly used for the industrial production of adipic acid and caprolactam, which are precursors to nylon.

Cyclohexene is a hydrocarbon with the formula (CH2)4C2H2. It is an example of a cycloalkene. At room temperature, cyclohexene is a colorless liquid with a sharp odor. Among its uses, it is an intermediate in the commercial synthesis of nylon.

<span class="mw-page-title-main">Cyclohexanol</span> Chemical compound

Cyclohexanol is the organic compound with the formula HOCH(CH2)5. The molecule is related to cyclohexane by replacement of one hydrogen atom by a hydroxyl group. This compound exists as a deliquescent colorless solid with a camphor-like odor, which, when very pure, melts near room temperature. Millions of tonnes are produced annually, mainly as a precursor to nylon.

<span class="mw-page-title-main">Adipic acid</span> Chemical compound

Adipic acid or hexanedioic acid is the organic compound with the formula (CH2)4(COOH)2. From an industrial perspective, it is the most important dicarboxylic acid: about 2.5 billion kilograms of this white crystalline powder are produced annually, mainly as a precursor for the production of nylon. Adipic acid otherwise rarely occurs in nature, but it is known as manufactured E number food additive E355. Salts and esters of adipic acid are known as adipates.

<span class="mw-page-title-main">Caprolactam</span> Chemical compound

Caprolactam (CPL) is an organic compound with the formula (CH2)5C(O)NH. This colourless solid is a lactam (a cyclic amide) of caproic acid. Global demand for this compound is approximately five million tons per year, and the vast majority is used to make Nylon 6 filament, fiber, and plastics.

<span class="mw-page-title-main">Pimelic acid</span> Chemical compound

Pimelic acid is the organic compound with the formula HO2C(CH2)5CO2H. Pimelic acid is one CH
2 unit longer than a related dicarboxylic acid, adipic acid, a precursor to many polyesters and polyamides. However compared to adipic acid, pimelic acid is relatively small in importance industrially. Derivatives of pimelic acid are involved in the biosynthesis of the amino acid lysine and the vitamin biotin.

<span class="mw-page-title-main">Allyl alcohol</span> Organic compound (CH2=CHCH2OH)

Allyl alcohol is an organic compound with the structural formula CH2=CHCH2OH. Like many alcohols, it is a water-soluble, colourless liquid. It is more toxic than typical small alcohols. Allyl alcohol is used as a precursor to many specialized compounds such as flame-resistant materials, drying oils, and plasticizers. Allyl alcohol is the smallest representative of the allylic alcohols.

<span class="mw-page-title-main">1,4-Benzoquinone</span> Chemical compound

1,4-Benzoquinone, commonly known as para-quinone, is a chemical compound with the formula C6H4O2. In a pure state, it forms bright-yellow crystals with a characteristic irritating odor, resembling that of chlorine, bleach, and hot plastic or formaldehyde. This six-membered ring compound is the oxidized derivative of 1,4-hydroquinone. The molecule is multifunctional: it exhibits properties of a ketone, being able to form oximes; an oxidant, forming the dihydroxy derivative; and an alkene, undergoing addition reactions, especially those typical for α,β-unsaturated ketones. 1,4-Benzoquinone is sensitive toward both strong mineral acids and alkali, which cause condensation and decomposition of the compound.

<span class="mw-page-title-main">Hydroperoxide</span> Class of chemical compounds

Hydroperoxides or peroxols are compounds of the form ROOH, where R stands for any group, typically organic, which contain the hydroperoxy functional group. Hydroperoxide also refers to the hydroperoxide anion and its salts, and the neutral hydroperoxyl radical (•OOH) consist of an unbond hydroperoxy group. When R is organic, the compounds are called organic hydroperoxides. Such compounds are a subset of organic peroxides, which have the formula ROOR. Organic hydroperoxides can either intentionally or unintentionally initiate explosive polymerisation in materials with unsaturated chemical bonds.

<span class="mw-page-title-main">Dakin oxidation</span> Organic redox reaction that converts hydroxyphenyl aldehydes or ketones into benzenediols

The Dakin oxidation (or Dakin reaction) is an organic redox reaction in which an ortho- or para-hydroxylated phenyl aldehyde (2-hydroxybenzaldehyde or 4-hydroxybenzaldehyde) or ketone reacts with hydrogen peroxide (H2O2) in base to form a benzenediol and a carboxylate. Overall, the carbonyl group is oxidised, whereas the H2O2 is reduced.

<span class="mw-page-title-main">Ethylamine</span> Chemical compound

Ethylamine, also known as ethanamine, is an organic compound with the formula CH3CH2NH2. This colourless gas has a strong ammonia-like odor. It condenses just below room temperature to a liquid miscible with virtually all solvents. It is a nucleophilic base, as is typical for amines. Ethylamine is widely used in chemical industry and organic synthesis. It is a DEA list I chemical by 21 CFR § 1310.02.

<span class="mw-page-title-main">Nitrosyl chloride</span> Chemical compound

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 strong electrophile and oxidizing agent. It is sometimes called Tilden's reagent, after William A. Tilden, who was the first to produce it as a pure compound.

<span class="mw-page-title-main">Isophorone</span> Alpha-beta unsaturated cyclic ketone

Isophorone is an α,β-unsaturated cyclic ketone. It is a colorless liquid with a characteristic peppermint-like odor, although commercial samples can appear yellowish. Used as a solvent and as a precursor to polymers, it is produced on a large scale industrially.

<span class="mw-page-title-main">Cyclohexenone</span> Chemical compound

Cyclohexenone is an organic compound which is a versatile intermediate used in the synthesis of a variety of chemical products such as pharmaceuticals and fragrances. It is colorless liquid, but commercial samples are often yellow.

In nitrile reduction a nitrile is reduced to either an amine or an aldehyde with a suitable chemical reagent.

<span class="mw-page-title-main">Cyclohexanone oxime</span> Chemical compound

Cyclohexanone oxime is an organic compound containing the functional group oxime. This colorless solid is an important intermediate in the production of nylon 6, a widely used polymer.

<span class="mw-page-title-main">Cyclohexylbenzene</span> Chemical compound

Cyclohexylbenzene is the organic compound with the structural formula C6H5−C6H11. It is a derivative of benzene with a cyclohexyl substituent (C6H11). It is a colorless liquid.

Hydroxymethylation is a chemical reaction that installs the CH2OH group. The transformation can be implemented in many ways and applies to both industrial and biochemical processes.

References

  1. ↑ "ICSC 0425 – CYCLOHEXANONE". inchem.org. Retrieved 2022-08-24.
  2. ↑ "CDC – NIOSH Pocket Guide to Chemical Hazards – Cyclohexanone". Centers for Disease Control and Prevention (CDC). Retrieved August 24, 2022.
  3. 1 2 "Cyclohexanone (CID 7967)". PubChem .
  4. ↑ "Cyclohexanone". Sigma-Aldrich.
  5. 1 2 3 4 NIOSH Pocket Guide to Chemical Hazards. "#0166". National Institute for Occupational Safety and Health (NIOSH).
  6. ↑ Ch. Wohlfarth. "Viscosity of cyclohexanone". In M.D. Lechner (ed.). Viscosity of Pure Organic Liquids and Binary Liquid Mixtures · Supplement to IV/18. Springer-Verlag. doi:10.1007/978-3-540-75486-2_192.
  7. 1 2 3 Sigma-Aldrich Co., Cyclohexanone.
  8. ↑ Cyclohexanone: toxicity for animals and humans
  9. 1 2 "Cyclohexanone". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  10. ↑ "Cyclohexanone (CID 7967)". PubChem.
  11. 1 2 3 4 5 Musser, Michael T. (October 15, 2011). "Cyclohexanol and Cyclohexanone". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KgaA. doi:10.1002/14356007.a08_217.pub2. ISBN   978-3-527-30673-2. OCLC   46878292 . Retrieved January 27, 2009.
  12. ↑ E. Drechsel (1888). "Ueber Elektrolyse des Phenols mit Wechselströmen". Journal für praktische Chemie (in German). 38 (1): 65–74. doi:10.1002/PRAC.18880380105. ISSN   0021-8383. Wikidata   Q56441554.
  13. ↑ Perkin, William Henry; Plant, Sydney Glenn Preston (1921). "Derivatives of tetrahydrocarbazole". Journal of the Chemical Society, Transactions. 119 (0): 1825–1839. doi:10.1039/CT9211901825. ISSN   0368-1645.
  14. ↑ "Oxidation of Cyclohexanol to Cyclohexanone". Archived from the original on 2012-04-26. Retrieved 2012-07-09.
  15. ↑ Mohrig, Jerry R.; Nienhuis, David M.; Linck, Catherine F.; Van Zoeren, Carol; Fox, Brian G.; Mahaffy, Peter G. (June 1985). "The design of laboratory experiments in the 1980's: A case study on the oxidation of alcohols with household bleach". Journal of Chemical Education. 62 (6): 519. doi:10.1021/ed062p519.
  16. ↑ Plotkin, Jeffrey S. (2016-03-21). "What's New in Phenol Production?". American Chemical Society. Archived from the original on 2019-10-27. Retrieved 2019-10-27.
  17. ↑ "Phenol – The essential chemical industry online". 2017-01-11. Retrieved 2019-10-27.
  18. ↑ M. S. Newman; M. D. Farbman; H. Hipsher (1945). "2-chlorocyclohexanone". Org. Synth. 25: 22. doi:10.15227/orgsyn.025.0022.
  19. ↑ Valsamma Varghese; Manasi Saha; Kenneth M. Nicholas (1989). "Alkylations Using Hexacarbonyl(Propargylium)dicobalt Salts: 2-(1-methyl-2-propynyl)cyclohexanone". Org. Synth. 67: 141. doi:10.15227/orgsyn.067.0141.
  20. ↑ R. B. Woodward; I. J. Pachter; M. L. Scheinbaum (1974). "2,2-(Trimethylenedithio)cyclohexanone". Org. Synth. 54: 39. doi:10.15227/orgsyn.054.0039.
  21. ↑ Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, p. 1736, ISBN   978-0-471-72091-1
  22. ↑ Shulgin, A. T.; MacLean, D. E. (25 September 2008). "Illicit Synthesis of Phencyclidine (PCP) and Several of Its Analogs". Clinical Toxicology. 9 (4): 553–560. doi:10.3109/15563657608988157. PMID   975751.
  23. ↑ "Special Surveillance List of Chemicals, Products, Materials and Equipment Used in the Clandestine Production of Controlled Substances or Listed Chemicals". Archived from the original on April 20, 2011.
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