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Latest revision as of 02:00, 23 October 2024 edit undoCitation bot (talk | contribs)Bots5,429,154 edits Added bibcode. | Use this bot. Report bugs. | Suggested by Dominic3203 | Category:Reagents for organic chemistry | #UCB_Category 69/228 |
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{{chembox |
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{{chembox |
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| verifiedrevid = 443549682 |
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| verifiedrevid = 444852630 |
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|Reference=<ref> at ]</ref> |
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|ImageFile=Cyclohexenone.png |
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| ImageFileL1 = Cyclohexenone.png |
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| ImageSizeL1 = 80px |
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|ImageSize=100px |
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| ImageAltL1 = Skeletal formula of cyclohexenone |
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|IUPACName=1-Cyclohex-2-enone |
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| ImageFileR1 = Cyclohexenone 3D ball.png |
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|OtherNames= |
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| ImageSizeR1 = 130 |
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|Section1= {{Chembox Identifiers |
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| ImageAltR1 = Ball-and-stick model of the cyclohexenone molecule |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| PIN = Cyclohex-2-en-1-one |
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| OtherNames = 1-Cyclohex-2-enone |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 13005 |
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| ChemSpiderID = 13005 |
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| KEGG_Ref = {{keggcite|correct|kegg}} |
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| KEGG_Ref = {{keggcite|correct|kegg}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo=930-68-7 |
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| CASNo=930-68-7 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| PubChem=13594 |
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| UNII = 445160R1U6 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| PubChem=13594 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 15977 |
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| ChEBI = 15977 |
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| EC_number = 213-223-5 |
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| Gmelin = 2792 |
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| Beilstein = 1280477 |
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| 3DMet = B00440 |
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| SMILES=C1CC=CC(=O)C1 |
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| SMILES=C1CC=CC(=O)C1 |
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|Section2= {{Chembox Properties |
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|Section2={{Chembox Properties |
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| C=6 | H=8 | O=1 |
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| Formula=C<sub>6</sub>H<sub>8</sub>O |
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| Appearance=Clear colorless liquid |
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| MolarMass=96.12712 |
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| Density=0.993 g/mL <ref name=sig> at ]</ref> |
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| Appearance=Clear colorless liquid |
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| Density=0.993 g/mL |
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| Solubility = 41.3 g/L (25 °C) |
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| MeltingPt=−53 °C |
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| MeltingPtC=−53 |
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| MeltingPt_ref = <ref name=sig /> |
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| BoilingPt=171-173 °C |
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| BoilingPtC=171 to 173 |
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| Solubility= |
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| BoilingPt_ref = <ref name=sig /> |
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|Section3= {{Chembox Hazards |
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|Section3={{Chembox Hazards |
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| MainHazards= |
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| FlashPt= |
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| NFPA-H = 1 |
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| Autoignition= |
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| NFPA-F = 3 |
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}} |
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| NFPA-R = 0 |
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| GHSPictograms = {{GHS02}}{{GHS06}}{{GHS07}} |
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| GHSSignalWord = Danger |
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| HPhrases = {{H-phrases|226|301|310|319|330|331}} |
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| PPhrases = {{P-phrases|210|233|240|241|242|243|260|261|262|264|270|271|280|284|301+310|302+350|303+361+353|304+340|305+351+338|310|311|320|321|322|330|337+313|361|363|370+378|403+233|403+235|405|501}} |
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| LD50 = 220 mg kg<sup>−1</sup> (rat, oral) |
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| FlashPt = |
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| AutoignitionPt = |
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| ExploLimits = |
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'''Cyclohexenone''' is an ] which is a versatile intermediate used in the ] of a variety of chemical products such as pharmaceuticals and fragrances.<ref>Podraze, K.F. ''Org. Prep. Proced. Int.'', 1991, 23, p. 217.</ref> It is a clear colorless liquid with a boiling point of 171-173 °C. |
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'''Cyclohexenone''' is an ] which is a versatile intermediate used in the ] of a variety of chemical products such as pharmaceuticals and fragrances.<ref>Podraze, K.F. ''Org. Prep. Proced. Int.'', 1991, 23, p. 217.</ref> It is colorless liquid, but commercial samples are often yellow. |
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Industrially, cyclohexenone is prepared from ] by ].<ref>''Organic Building Blocks of the Chemical Industry'', Harry H. Szmant, ISBN 978-0471855453 </ref> |
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Industrially, cyclohexenone is prepared from ] by ].<ref>''Organic Building Blocks of the Chemical Industry'', Harry H. Szmant, {{ISBN|978-0-471-85545-3}}</ref> |
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Common reactions involving cyclohexenone include ] with ], ]s and ]s.<ref>{{cite journal|doi=10.1021/ed073p1193|author=Michael G. Organ and Paul Anderson|title=Carbonyl and Conjugate Additions to Cyclohexenone: Experiments Illustrating Reagent Selectivity|journal=Journal of Chemical Education|year=1996|volume=73|issue=12|pages=1193}}</ref><ref>''Tet. Lett.'' 34, 3881, (1993)</ref> |
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Cyclohexenone is a ], or more precisely an ]. Common reactions include ] with ], ]s and ]s.<ref>{{cite journal|doi=10.1021/ed073p1193|author=Michael G. Organ and Paul Anderson|title=Carbonyl and Conjugate Additions to Cyclohexenone: Experiments Illustrating Reagent Selectivity|journal=Journal of Chemical Education|year=1996|volume=73|issue=12|pages=1193|bibcode=1996JChEd..73.1193O }}</ref><ref>''Tetrahedron Lett.'' 34, 3881, (1993)</ref> |
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==Synthesis== |
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Several routes exist for the production of cyclohexenone. For the laboratory scale, it can be produced from ] via 1,3-cyclohexanedione.<ref>{{cite journal |doi=10.15227/orgsyn.027.0021|title=Dihydroresorcinol|author=R. B. Thompson|journal=Organic Syntheses|year=1947|volume=27|page=21}}</ref> |
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:] |
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Cyclohexenone is obtained by ] of ] followed by acid hydrolysis. |
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:] |
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It can be obtained from cyclohexanone by α-bromination followed by treatment with base. Hydrolysis of 3-chloro cyclohexene followed by oxidation of the cyclohexenol is yet another route. |
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Cyclohexenone is produced industrially by catalytic oxidation of cyclohexene, for example with ] and ] catalysts. Several patents describe diverse oxidizing agents and catalysts. |
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==Reactions== |
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Cyclohexenone is a widely used building block in organic synthesis chemistry, as it offers many different ways to extend molecular frameworks. |
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As an ], cyclohexenone is easily adapted to ] with nucleophiles (such as ]s or silyl enol ethers) or, it could be employed by a ] with electron-rich ]s. Furthermore, this compound reacts with ]s from 1,4-addition (Michael addition), or with Grignard reagents 1,2-addition, i.e., with attack of the nucleophile at the carbonyl carbon atom. Cyclohexenone is also used in multi-step synthesis in the construction of polycyclic natural products. It is prochiral. |
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With strong bases, the positions 4 and 6 (the two CH<sub>2</sub>-groups of the carbonyl group and the C-C double bond adjacent) are deprotonated. |
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Cyclohexenone is an ''in-vitro'' catalyst for a relatively mild ] of ].<ref name="hashimoto">Researchers in Japan were attempting to use ] as a catalyst for decarboxylation using a solvent choice of ]. Curiously they found that when they used lower-purity (e.g. technical grade, 98%) cyclohexanol, the reaction proceeded as much as 4 times faster compared to when they used relatively pure cyclohexanol (>99.3%). They found that cyclohexanol contained cyclohexenone as a natural impurity, which was three times more abundant in the technical grade cyclohexenone compared to the more purified cyclohexanol (~0.3% versus ~0.1%). Further research showed that 1% cyclohexenone in cyclohexanol will decarboxylate most alpha-amino acids, including non-standard ones, with a yield of 80-95% in a matter of several hours. The exceptions are certain amino acids like ], which was reported to take over 26 hours, and poly-amino acids, which fail to decarboxylate using 2-cyclohexenone and another route must be found instead.{{cite journal|last1=Hashimoto|first1=M|last2=Eda|first2=Y|last3=Yasutomo|first3=O|last4=Toshiaki|first4=I|last5=Aoki|first5=S|title=A novel decarboxylation of .ALPHA.-amino acids. A facile method of decarboxylation by the use of 2-cyclohexen-1-one as a catalyst.|journal=Chemistry Letters|date=1986|volume=15|issue=6|pages=893–896|url=https://www.jstage.jst.go.jp/article/cl1972/15/6/15_6_893/_article|accessdate=4 January 2016|doi=10.1246/cl.1986.893}}</ref> <ref name="laval">{{cite journal|last1=Laval|first1=G|last2=Golding|first2=B|title=One-pot Sequence for the Decarboxylation of α-Amino Acids|journal=Synlett|date=2003|issue=4|pages=542–546|doi=10.1055/s-2003-37512|url=https://www.thieme-connect.com/products/ejournals/abstract/10.1055/s-2003-37512|accessdate=4 January 2016}}</ref> |
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==Related compounds== |
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*] |
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*cyclobutenone<ref>{{cite journal |doi=10.15227/orgsyn.089.0491 |title=Preparation of Cyclobutenone |journal=Organic Syntheses |date=2012 |volume=89 |page=491|author=A. G. Ross, X. Li, S. J. Danishefsky |
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|doi-access=free }}</ref> |
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*] |
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*cycloheptenone<ref>{{cite journal |doi=10.15227/orgsyn.059.0113 |title=One-Carbon Ring Expansion of Cycloalkanones to Conjugated Cycloalkenones: 2-Cyclohepten-1-One |journal=Organic Syntheses |date=1979 |volume=59 |page=113|author=Y. Ito, S. Fujii, M. Nakatuska, F. Kawamoto,T. Saegusa }}</ref> |
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==References== |
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==References== |
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{{Reflist}} |
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<references/> |
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