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Revision as of 16:11, 8 August 2011 editHRoestBot (talk | contribs)53,714 editsm r2.6.5) (robot Adding: de:Cyclopropanon← Previous edit		Latest revision as of 18:47, 25 September 2024 edit undoMarbletan (talk | contribs)Extended confirmed users5,256 editsNo edit summary
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			{{short description|Chemical compound}}
	{{chembox		{{chembox
			| Watchedfields = changed
	| verifiedrevid = 399737901		| verifiedrevid = 443700313
	|ImageFile=Cyclopropanone.png		| ImageFile =Cyclopropanone.png
	|ImageSize=150px		| ImageSize =150px
	|IUPACName=cyclopropanone
			| PIN =Cyclopropanone
	|OtherNames=
	|Section1= {{Chembox Identifiers		|Section1={{Chembox Identifiers
	| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}		| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
	| ChemSpiderID = 122027		| ChemSpiderID = 122027
	| InChI = 1/C3H4O/c4-3-1-2-3/h1-2H2		| InChI = 1/C3H4O/c4-3-1-2-3/h1-2H2
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	| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}		| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
	| StdInChIKey = VBBRYJMZLIYUJQ-UHFFFAOYSA-N		| StdInChIKey = VBBRYJMZLIYUJQ-UHFFFAOYSA-N
			| CASNo_Ref = {{cascite|correct|??}}
	| CASNo=5009-27-8		| CASNo =5009-27-8
	| PubChem=138404		| PubChem =138404
	| SMILES=C1CC1=O		| SMILES =C1CC1=O
	}}		}}
	|Section2= {{Chembox Properties		|Section2={{Chembox Properties
	| Formula=C<sub>3</sub>H<sub>4</sub>O
			| C=3 | H=4 | O=1
	| MolarMass=56.06326
	| Appearance=		| Appearance = Colorless
	| Density=0.867 g/mL at 25 °C		| Density =0.867 g/mL at 25&nbsp;°C
			| MeltingPtC = −90
	| MeltingPt=−90 °C
			| BoilingPtC = 50 to 53
	| BoilingPt=50-53 °C at 22 mmHg
			| BoilingPt_notes = at 22 mmHg
	| Solubility=
			| Solubility =
	}}		}}
	|Section3= {{Chembox Hazards
	| MainHazards=
	| FlashPt=
	| Autoignition=
	}}
	}}		}}
	'''Cyclopropanone''' is an ] with ] C<sub>3</sub>H<sub>4</sub>O consisting of a ] carbon framework with a ] ]. The parent compound is labile with ] −90 °C and has been prepared by reaction of ] with ] at −145 °C.<ref>''Preparation and characterization of cyclopropanone, methylcyclopropanone, 2,2-dimethylcyclopropanone and tetramethylcyclopropanone'' N. J. Turro and W. B. Hammond, '']'', Volume 24, Issue 18, '''1968''', Pages 6017-6028 {{doi|10.1016/S0040-4020(01)90985-8}}</ref><ref>''Cryochemical synthesis and molecular energetics of cyclopropanone and some related compounds'' E. F. Rothgery, R. J. Holt, H. A. McGee, , Jr. '']''; '''1975'''; 97(17); 4971-4973. {{DOI|10.1021/ja00850a034}}</ref> Derivatives of cyclopropanone are of some interest to ].<ref>''Cyclopropanones'' Nicholas J. Turro, '']''; '''1969'''; 2(1); 25-32. {{DOI|10.1021/ar50013a004}}</ref>		'''Cyclopropanone''' is an ] with ] (CH<sub>2</sub>)<sub>2</sub>CO consisting of a ] carbon framework with a ] ]. The parent compound is labile, being highly sensitive toward even weak nucleophiles. Surrogates of cyclopropanone include the ]s.<ref name=Patai/>
			==Preparation==
	In ] the use of cyclopropanone itself is substituted by that of ]s like ]s ''cyclopropanone ethyl hemiacetal''<ref> ], Coll. Vol. 7, p.131 (1990); Vol. 63, p.147 ('''1985'''). </ref> or ''cyclopropanone ethyl trimethylsilyl acetal''.<ref>Datasheet commercial supplier </ref>
			Cyclopropanone has been prepared by reaction of ] with ]<ref name=Patai>{{cite book |doi=10.1002/0470023449.ch23|chapter=The Chemistry of Cyclopropanones|title=PATAI'S Chemistry of Functional Groups: Cyclopropyl Group|year=1987|last1=Wasserman|first1=Harry H.|last2=Berdahl|first2=Donald R.|last3=Lu|first3=Ta-Jung|pages=1455–1532|isbn=9780470023440}}</ref><ref>{{Cite journal | doi = 10.1021/ar50013a004| title = Cyclopropanones| journal = Accounts of Chemical Research| volume = 2| pages = 25–32| year = 1969| last1 = Turro| first1 = Nicholas J.}}</ref> in an unreactive solvent such as ].<ref name=EROS>{{cite encyclopedia|doi=10.1002/047084289X.rc302|entry=Cyclopropanone|first=Norbert|last=De&nbsp;Kimpe|encyclopedia=]}}</ref> These solutions are stable at −78&nbsp;°C. In the presence of protic reagents such as carboxylic acids, primary and secondary amines, and alcohols, cyclopropanone converts to adducts, which are often isolatable at room temperature:<ref>{{cite journal|first1=J. |last1=Salaün|first2=J.|last2=Marguerite|title=Cyclopropanone Ethyl Hemiacetal from Ethyl 3-Chloropropanoate|journal=Organic Syntheses|year=1985|volume=63|pages=147|doi=10.15227/orgsyn.063.0147}}</ref><ref>{{cite journal |doi=10.1021/cr00058a002|title=Cyclopropanone Hemiacetals|year=1983|last1=Salaun|first1=Jacques|journal=Chemical Reviews|volume=83|issue=6|pages=619–632}}</ref>
			:(CH<sub>2</sub>)<sub>2</sub>CO + X-H → (CH<sub>2</sub>)<sub>2</sub>C(X)(OH)&nbsp;&nbsp;&nbsp;&nbsp;(X-H = R<sub>2</sub>N-H, HO-H, RO-H)
			==Structure==
			The C<sub>3</sub>O atoms are coplanar. As deduced from the ], the H<sub>2</sub>C-CH<sub>2</sub> bond length of 157.5 ] is unusually long. By contrast, the C-C bond lengths in ] are 151 pm. The C=O bond length of 119 pm is short compared to the 123 pm bond length in ].<ref name=Patai/>
			The value of ν<sub>C=O</sub> in the ] is near 1815&nbsp;cm<sup>−1</sup>, ca. 70&nbsp;cm<sup>−1</sup> higher than values for a typical ketone.
	==Derivatives==		==Derivatives==
	Cyclopropanones are intermediates in the ] with cyclic ketones where ] formation is accompanied by ring-contraction.		Cyclopropanones are intermediates in the ] with cyclic ketones where ] formation is accompanied by ring-contraction.
	An interesting feature of cyclopropanones is that they react as ]s in ]s for instance with cyclic dienes such as ].<ref>''Cyclopropanones. XII. Cycloaddition reactions of cyclopropanones'' Nicholas J. Turro, Simon S. Edelson, John R. Williams, Thomas R. Darling, Willis B. Hammond, '']''; '''1969'''; 91(9); 2283-2292. {{DOI|10.1021/ja01037a018}}</ref><ref>''Cyclopropanones. XVII. Kinetics of the cycloaddition reaction of cyclopropanones with 1,3-dienes'' Simon S. Edelson, Nicholas J. Turro ]; '''1970'''; 92(9); 2770-2773. {{DOI|10.1021/ja00712a030}}</ref> An oxyallyl intermediate or ] (formed by cleavage of the C2-C3 bond) is suggested as the active intermediate or even a ] structure (compare to the related ]).		Cyclopropanones react as ]s in ]s for instance with cyclic dienes such as ].<ref name=Patai/> An oxyallyl intermediate or ] (formed by cleavage of the C2-C3 bond) is suggested as the active intermediate or even a ] structure (compare to the related ]).
	]		:]
	Experimental evidence is not conclusive. Other reactions of cyclopropanones take place through this intermediate. For instance ] (+)-''trans''-2,3-di-tert-butylcyclopropanone ] when heated to 80 °C.<ref>''Thermal reactions of a cyclopropanone. Racemization and decarbonylation of trans-2,3-di-tert-butylcyclopropanone'' Frederick D. Greene, David B. Sclove, Jose F. Pazos, Ronald L. Camp ]; '''1970'''; 92(25); 7488-7488. {{DOI|10.1021/ja00728a051}}</ref>		Other reactions of cyclopropanones take place through this intermediate. For instance ] (+)-''trans''-2,3-di-tert-butylcyclopropanone ] when heated to 80&nbsp;°C.<ref>{{Cite journal | doi = 10.1021/ja00728a051| title = Thermal reactions of a cyclopropanone. Racemization and decarbonylation of trans-2,3-di-tert-butylcyclopropanone| journal = Journal of the American Chemical Society| volume = 92| issue = 25| pages = 7488| year = 1970| last1 = Greene| first1 = Frederick D.| last2 = Sclove| first2 = David B.| last3 = Pazos| first3 = Jose F.| last4 = Camp| first4 = Ronald L.}}</ref>
	An oxyallyl intermediate is also proposed in the ] conversion of a 3,5-dihydro-4H-pyrazole-4-one with expulsion of nitrogen to an ]:<ref>''First Direct Detection of 2,3-Dimethyl-2,3-diphenylcyclopropanone'' Andrey G. Moiseev, Manabu Abe, Evgeny O. Danilov, and Douglas C. Neckers, '']''; '''2007'''; 72(8) pp 2777 - 2784; (Article) {{DOI|10.1021/jo062259r}}</ref>		An oxyallyl intermediate is also proposed in the ] conversion of a 3,5-dihydro-4H-pyrazole-4-one with expulsion of nitrogen to an ]:<ref>{{Cite journal | doi = 10.1021/jo062259r| pmid = 17362038| title = First Direct Detection of 2,3-Dimethyl-2,3-diphenylcyclopropanone| journal = The Journal of Organic Chemistry| volume = 72| issue = 8| pages = 2777–2784| year = 2007| last1 = Moiseev| first1 = Andrey G.| last2 = Abe| first2 = Manabu| last3 = Danilov| first3 = Evgeny O.| last4 = Neckers| first4 = Douglas C.}}</ref>
	]		:]
	In this reaction oxyallyl intermediate '''A''', in ] with cyclopropanone '''B''' attacks the ] ring through its ] forming a transient ]{{Disambiguation needed|date=June 2011}} '''C''' (with UV trace similar to ]) followed by rearomatization. The energy difference between A and B is 5 to 7 ]/] (21 to 29 ]/mol).		In this reaction oxyallyl intermediate '''A''', in ] with cyclopropanone '''B''' attacks the ] ring through its ] forming a transient ] '''C''' (with UV trace similar to ]) followed by rearomatization. The energy difference between '''A''' and '''B''' is 5 to 7 ]/] (21 to 29 ]/mol).
			===Coprine===
			The cyclopropanone derivative 1-aminocyclopropanol occurs naturally by ] of ], a toxin in some mushrooms. 1-Aminocyclopropanol is an ] of the enzyme ].<ref name=mechanism>{{cite journal |last1=Wiseman |first1=Jeffrey S. |last2=Abeles |first2=Robert H. |title=Mechanism of inhibition of aldehyde dehydrogenase by cyclopropanone hydrate and the mushroom toxin coprine |journal=Biochemistry |date=May 2002 |volume=18 |issue=3 |pages=427–435 |doi=10.1021/bi00570a006|pmid=369602}}</ref>
			]
	==See also==		==See also==
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	{{reflist}}		{{reflist}}
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