Cyclohexanone: Difference between revisions

{{Use American English|date=July 2021}}

{{Distinguish|Cyclexanone}}

|Watchedfields = changed

|verifiedrevid = 443547421

|Reference=<ref>{{Cite web |title=ICSC 0425 – CYCLOHEXANONE |url=https://inchem.org/documents/icsc/icsc/eics0425.htm |access-date=2022-08-24 |website=inchem.org}}</ref><ref>{{Cite web |title=CDC – NIOSH Pocket Guide to Chemical Hazards – Cyclohexanone |url=https://www.cdc.gov/niosh/npg/npgd0166.html |access-date=August 24, 2022|publisher=[[Centers for Disease Control|Centers for Disease Control and Prevention]] (CDC)}}</ref>

|Name = Cyclohexanone

|ImageFileL1_Ref = {{chemboximage|correct|??}}

|ImageFileL1 = Cyclohexanone.svg

|ImageNameL1 = Skeletal formula of cyclohexanone

|ImageSizeL1 = 80px

|ImageFileR1 = Cyclohexanone-from-xtal-top-view-3D-bs-17.png

|ImageNameR1 = Ball-and-stick model of cyclohexanone

|ImageSizeR1 = 125px

|ImageFileL2 = Cyclohexanone-conformation-2D-skeletal.png

|ImageNameL2 = Skeletal formula viewed side-on, showing the non-planar conformation

|ImageSizeL2 = 125px

|ImageFileR2 = Cyclohexanone-from-xtal-side-view-3D-bs-17.png

|ImageNameR2 = Ball-and-stick model of cyclohexanone viewed side-on, showing the non-planar conformation

|ImageSizeR2 = 125px

|PIN = Cyclohexanone

|OtherNames= oxocyclohexane, pimelic ketone, ketohexamethylene, cyclohexyl ketone, ketocyclohexane, hexanon, Hydrol-O, Sextone, K, Anone

|Section1={{Chembox Identifiers

|DrugBank_Ref = {{drugbankcite|correct|drugbank}}

|DrugBank = DB02060

|ChEBI_Ref = {{ebicite|correct|EBI}}

|ChEBI = 17854

|SMILES = C1CCC(=O)CC1

|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

|ChemSpiderID = 7679

|PubChem = 7967

|UNII_Ref = {{fdacite|correct|FDA}}

|UNII = 5QOR3YM052

|KEGG_Ref = {{keggcite|correct|kegg}}

|KEGG = C00414

|InChI = 1/C6H10O/c7-6-4-2-1-3-5-6/h1-5H2

|InChIKey = JHIVVAPYMSGYDF-UHFFFAOYAY

|ChEMBL_Ref = {{ebicite|correct|EBI}}

|ChEMBL = 18850

|StdInChI_Ref = {{stdinchicite|correct|chemspider}}

|StdInChI = 1S/C6H10O/c7-6-4-2-1-3-5-6/h1-5H2

|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}

|StdInChIKey = JHIVVAPYMSGYDF-UHFFFAOYSA-N

|CASNo_Ref = {{cascite|correct|CAS}}

|CASNo = 108-94-1

|EC_number = 203-631-1

}}

|Section2={{Chembox Properties

|Formula = C₆H₁₀O

|MolarMass = 98.15 g/mol

|Appearance = Colorless liquid<ref name="PubChem"/>

|Odor = [[peppermint]] or [[acetone]]-like

|Density = 0.9478 g/mL, liquid

|Solubility = 8.6 g/100 mL (20 °C)

|Solvent = all organic solvents

|SolubleOther = Miscible

|LogP = 0.81

|MeltingPtC = −47

|MeltingPt_ref = <ref name=sigma-aldrich>{{cite web|url=http://www.sigmaaldrich.com/catalog/product/SIAL/398241|publisher=Sigma-Aldrich|title=Cyclohexanone}}</ref>

|BoilingPtC = 155.65

|Viscosity = 2.02 [[Poise (unit)|cP]] at 25 °C<ref name="Wohlfarth2008">{{cite book |author=Ch. Wohlfarth |chapter=Viscosity of cyclohexanone |editor=M.D. Lechner |title=Viscosity of Pure Organic Liquids and Binary Liquid Mixtures · Supplement to IV/18 |doi=10.1007/978-3-540-75486-2_192 |publisher=[[Springer-Verlag]]}}</ref>

|RefractIndex = 1.447

|VaporPressure = 5 mmHg (20°C)<ref name=PGCH/>

|MagSus = -62.04·10⁻⁶ cm³/mol

}}

|Section3={{Chembox Thermochemistry

|DeltaHf = −270.7 kJ mol⁻¹

|DeltaHc = −3519.3 kJmol⁻¹

|Entropy = +229.03 J.K⁻¹.mol⁻¹

}}

|Section4={{Chembox Hazards

|FlashPtC = 44

|AutoignitionPtC = 420

|ExploLimits = 1.1–9.4%

|NFPA-H = 1

|NFPA-F = 2

|NFPA-R = 0

|GHSPictograms = {{GHS02}}{{GHS06}}{{GHS07}}

|GHSSignalWord = Danger<ref name="sigma">{{Sigma-Aldrich|Sial|id=398241|name=Cyclohexanone|access-date=2022-03-17}}</ref>

|HPhrases = {{H-phrases|226|302|305|312|332|315|318}}<ref name="sigma"/>

|PPhrases = {{P-phrases|280|305+351+338}}<ref name="sigma"/>

|PEL = TWA 50 ppm (200 mg/m³)<ref name=PGCH>{{PGCH|0166}}</ref>

|IDLH = 700 ppm<ref name=PGCH/>

|REL = TWA 25 ppm (100 mg/m³) [skin]<ref name=PGCH/>

|LD50 = 1200 mg/kg (cat, orally); 2362 mg/kg (rat, orally)<ref>Cyclohexanone: toxicity for animals and humans</ref>

|LC50 = 8000 ppm (rat, 4 hr)<ref name=IDLH>{{IDLH|108941|Cyclohexanone}}</ref>

|LCLo = 4706 ppm (mouse, 1.5 hr)<ref name=IDLH/>

}}

|Section5={{Chembox Related

|OtherFunction_label = [[ketone]]s

|OtherFunction = [[Cyclopentanone]], [[cycloheptanone]]

|OtherCompounds = [[Cyclohexanol]]

}}

'''Cyclohexanone''' is the [[organic compound]] with the [[chemical formula|formula]] (CH₂)₅CO. The molecule consists of six-carbon [[alicyclic compound|cyclic molecule]] with a [[ketone]] functional [[Functional group|group]]. This colorless oily liquid<ref name="PubChem">{{cite web|title=Cyclohexanone (CID 7967)|url=https://pubchem.ncbi.nlm.nih.gov/compound/7967#:~:text=is%20a%20colorless,%20liquid|website=[[PubChem]]}}</ref> has a sweet odor reminiscent of [[benzaldehyde]]. Over time, samples of cyclohexanone assume a pale yellow color.<ref>{{cite web|publisher=[[PubChem]]|title=Cyclohexanone (CID 7967)|url=https://pubchem.ncbi.nlm.nih.gov/compound/7967#:~:text=pale,liquid}}</ref> Cyclohexanone is slightly soluble in water and miscible with common organic solvents. Millions of tonnes are produced annually, mainly as a precursor to [[nylon]].<ref name=Ullmann>{{cite book|last=Musser|first=Michael T.|chapter=Cyclohexanol and Cyclohexanone|date=October 15, 2011|chapter-url=https://onlinelibrary.wiley.com/doi/10.1002/14356007.a08_217.pub2|title=Ullmann's Encyclopedia of Industrial Chemistry|pages=|publisher=Wiley-VCH Verlag GmbH & Co. KgaA|location=Weinheim, Germany|doi=10.1002/14356007.a08_217.pub2 |oclc=46878292|isbn=978-3-527-30673-2|access-date=January 27, 2009}}</ref>

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

[[ExxonMobil]] developed a process in which benzene is [[alkylation|hydroalkylated]] to [[cyclohexylbenzene]]. This latter product is [[oxidized]] to a [[hydroperoxide]] and then cleaved into phenol and cyclohexanone.<ref name="acs phenol">{{cite web |url=https://www.acs.org/content/acs/en/pressroom/cutting-edge-chemistry/what-s-new-in-phenol-production-.html |title=What's New in Phenol Production? |last=Plotkin |first=Jeffrey S. |publisher=American Chemical Society |date=2016-03-21 |access-date=2019-10-27 |archive-url=https://web.archive.org/web/20191027122212/https://www.acs.org/content/acs/en/pressroom/cutting-edge-chemistry/what-s-new-in-phenol-production-.html |archive-date=2019-10-27 }}</ref> 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.<ref name="essential chemical">{{cite web |url=http://www.essentialchemicalindustry.org/chemicals/phenol.html |title=Phenol – The essential chemical industry online |date=2017-01-11 |access-date=2019-10-27}}</ref>

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]].<ref>{{cite web |url=http://www2.volstate.edu/CHEM/2010/Labs/Cyclohexanone.html |title=Oxidation of Cyclohexanol to Cyclohexanone |access-date=2012-07-09 |archive-url=https://web.archive.org/web/20120426194932/http://www2.volstate.edu/CHEM/2010/Labs/Cyclohexanone.html |archive-date=2012-04-26}}</ref><ref>{{cite journal |last1=Mohrig |first1=Jerry R. |last2=Nienhuis |first2=David M. |last3=Linck |first3=Catherine F. |last4=Van Zoeren |first4=Carol |last5=Fox |first5=Brian G. |last6=Mahaffy |first6=Peter G. |title=The design of laboratory experiments in the 1980's: A case study on the oxidation of alcohols with household bleach |journal=Journal of Chemical Education |date=June 1985 |volume=62 |issue=6 |pages=519 |doi=10.1021/ed062p519}}</ref>

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 [[Beckmann rearrangement|rearranges]] to [[caprolactam]], a precursor to [[nylon 6]]:<ref name=Ullmann/>

::[[Image:Caprolactam Synth.png|340px]]

===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.<ref>{{cite journal|title=2-chlorocyclohexanone |author=M. S. Newman |author2=M. D. Farbman |author3=H. Hipsher|journal=Org. Synth.|year=1945|volume=25|page=22|doi=10.15227/orgsyn.025.0022}}</ref> It forms a trimethylsilylenol ether upon treatment with [[trimethylsilylchloride]] in the presence of base.<ref>{{cite journal|title=Alkylations Using Hexacarbonyl(Propargylium)dicobalt Salts: 2-(1-methyl-2-propynyl)cyclohexanone |author=Valsamma Varghese |author2=Manasi Saha |author3=Kenneth M. Nicholas|journal=Org. Synth.|year=1989|volume=67|page=141|doi=10.15227/orgsyn.067.0141}}</ref>

It forms an enamine with [[pyrrolidine]].<ref>{{cite journal|title=2,2-(Trimethylenedithio)cyclohexanone |author=[[R. B. Woodward]] |author2=I. J. Pachter |author3=M. L. Scheinbaum|journal=Org. Synth.|year=1974|volume=54|page=39|doi=10.15227/orgsyn.054.0039}}</ref>

Treatment with [[nitrosyl chloride]] and ethanol in [[sulfur dioxide]] gives the oximinecarboxylic ester:<ref>{{March6th|page=1736}}</ref>

:{{chem2|(CH2)5CO + C2H5OH + NOCl -> HON\dCH(CH2)4CO2C2H5 + HCl}}

===Illicit use===

Cyclohexanone has been used in the illicit production of [[phencyclidine]] and its analogs<ref>{{cite journal|last1=Shulgin|first1=A. T.|last2=MacLean|first2=D. E.|title=Illicit Synthesis of Phencyclidine (PCP) and Several of Its Analogs|journal=Clinical Toxicology|date=25 September 2008|volume=9|issue=4|pages=553–560|doi=10.3109/15563657608988157|pmid=975751 }}</ref> and is often subject to purchase restrictions, such as being listed on the [[Special Surveillance List]] in the US.<ref name="DEA">{{cite web|url=http://www.deadiversion.usdoj.gov/chem_prog/advisories/surveillance.htm |title=Special Surveillance List of Chemicals, Products, Materials and Equipment Used in the Clandestine Production of Controlled Substances or Listed Chemicals |archive-url=https://web.archive.org/web/20110420054619/http://www.deadiversion.usdoj.gov/chem_prog/advisories/surveillance.htm |archive-date=April 20, 2011 }}</ref>

==Safety==

Like [[cyclohexanol]], cyclohexanone is not carcinogenic and is moderately toxic, with a [[Threshold Limit Value|TLV]] of 25 ppm for the vapor. It is an irritant.<ref name=Ullmann/>

{{Authority control}}

[[Category:Cycloalkanones|6]]