Cyclohexanone

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Cyclohexanone[1][2]
Skeletal formula of cyclohexanone
Ball-and-stick model of cyclohexanone
Skeletal formula 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
KEGG
UNII
Properties
C6H10O
Molar mass 98.15 g/mol
Appearance Colorless liquid
Odor peppermint or acetone-like
Density 0.9478 g/mL, liquid
Melting point −47 °C (−53 °F; 226 K)[5]
Boiling point 155.65 °C (312.17 °F; 428.80 K)
8.6 g/100 mL (20 °C)
Solubility in all organic solvents Miscible
Vapor pressure 5 mmHg (20°C)[3]
-62.04·10−6 cm3/mol
1.447
Viscosity 2.02 cP at 25 °C[4]
Thermochemistry
+229.03 J.K−1.mol−1
−270.7 kJ mol−1
−3519.3 kJmol−1
Hazards
GHS pictograms GHS-pictogram-flamme.svgGHS-pictogram-exclam.svgGHS-pictogram-acid.svg
GHS signal word Danger[6]
H226, H302, H312, H332, H315, H318[6]
P280, P305+351+338[6]
NFPA 704
Flammability code 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 fuelHealth code 1: Exposure would cause irritation but only minor residual injury. E.g., turpentineReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g., liquid nitrogenSpecial hazards (white): no codeNFPA 704 four-colored diamond
2
1
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):
8000 ppm (rat, 4 hr)[7]
4706 ppm (mouse, 1.5 hr)[7]
US health exposure limits (NIOSH):
PEL (Permissible)
TWA 50 ppm (200 mg/m3)[3]
REL (Recommended)
TWA 25 ppm (100 mg/m3) [skin][3]
IDLH (Immediate danger)
700 ppm[3]
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).
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Infobox references

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 oil has an odor reminiscent of that of acetone. Over time, samples of cyclohexanone assume a yellow color. Cyclohexanone is slightly soluble in water and miscible with common organic solvents. Billions of kilograms are produced annually, mainly as a precursor to nylon.[8]

Production[edit]

Cyclohexanone is produced by the oxidation of cyclohexane in air, typically using cobalt catalysts:[8]

C6H12 + O2 → (CH2)5CO + H2O

This process co-forms cyclohexanol, 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 intermediacy of the hydroperoxide C6H11O2H. 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.[8]

Laboratory methods[edit]

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.[9]

Uses[edit]

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:[8]

Caprolactam Synth.png

Laboratory reactions[edit]

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.[10] It forms a trimethylsilylenol ether upon treatment with trimethylsilylchloride in the presence of base.[11] It also forms an enamine with pyrolidine.[12]

Illicit use[edit]

Cyclohexanone has been used in the illicit production of phencyclidine and its analogues[13] and as such is often subject to additional checks before purchase.

Safety[edit]

Like cyclohexanol, cyclohexanone is not carcinogenic and is moderately toxic, with a TLV of 25 ppm for the vapor. It is an irritant.[8]

References[edit]

  1. ^ International Chemical Safety Card 0425
  2. ^ NIOSH Pocket Guide to Chemical Hazards
  3. ^ a b c d "NIOSH Pocket Guide to Chemical Hazards #0166". National Institute for Occupational Safety and Health (NIOSH). 
  4. ^ Data extract from Landolt-Börnstein IV/25: Viscosity of Pure Organic Liquids and Binary Liquid Mixtures
  5. ^ Sigma-Aldrich - Cyclohexanone
  6. ^ a b c Sigma-Aldrich Co., Cyclohexanone. Retrieved on 2017-11-20.
  7. ^ a b "Cyclohexanone". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH). 
  8. ^ a b c d e Michael T. Musser "Cyclohexanol and Cyclohexanone" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005.doi:10.1002/14356007.a08_217
  9. ^ "Archived copy". Archived from the original on 2012-04-26. Retrieved 2012-07-09. 
  10. ^ M. S. Newman, M. D. Farbman, H. Hipsher (1945). "2-chlorocyclohexanone". Org. Synth. 25: 22. doi:10.15227/orgsyn.025.0022. 
  11. ^ 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. 
  12. ^ R. B. Woodward, I. J. Pachter, M. L. Scheinbaum (1974). "2,2-(Trimethylenedithio)cyclohexanone". Org. Synth. 54: 39. doi:10.15227/orgsyn.054.0039. 
  13. ^ 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.