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Revision as of 20:43, 28 January 2011 editCheMoBot (talk | contribs)Bots141,565 edits Updating {{chembox}} (no changed fields - added verified revid - updated 'UNII_Ref', 'ChemSpiderID_Ref', 'StdInChI_Ref', 'StdInChIKey_Ref', 'ChEMBL_Ref', 'KEGG_Ref') per Chem/Drugbox validation (← Previous edit		Latest revision as of 10:58, 5 May 2024 edit undo38.131.187.233 (talk) →Barrelene reactions: In the section "Barrelene reactions", the catalyst for the third reaction was described as a Fischer carbene. The catalyst is in fact an archetypal Schrock carbene: early metal, high oxidation state, no heteroatoms on the carbene, synthesized by Dick Schrock. Additionally, the reaction in question is an olefin metathesis reaction, in which Fischer carbenes are generally inactive. Attributing an olefin metathesis reaction to a Fischer carbene is misleading.
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	{{chembox		{{chembox
			| Watchedfields = changed
	| verifiedrevid = 399156018		| verifiedrevid = 410628703
	| ImageFileL1 = Barrelene structure.png		| ImageFileL1 = Barrelene structure.png
	| ImageSizeL1 = 120px
	| ImageFileR1 = Barrelene 3D.png		| ImageFileR1 = Barrelene 3D.png
			| PIN = Bicycloocta-2,5,7-triene<ref>{{cite book |author=] |date=2014 |title=Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 |publisher=] |pages=1257 |doi=10.1039/9781849733069 |isbn=978-0-85404-182-4}}</ref>
	| ImageSizeR1 = 120px
	| IUPACName = Bicycloocta-2,5,7-triene
	| OtherNames =		| OtherNames =
	| Section1 = {{Chembox Identifiers		|Section1={{Chembox Identifiers
	| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}		| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
	| ChemSpiderID = 120100		| ChemSpiderID = 120100
	| InChI = 1/C8H8/c1-2-8-5-3-7(1)4-6-8/h1-8H		| InChI = 1/C8H8/c1-2-8-5-3-7(1)4-6-8/h1-8H
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	| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}		| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
	| StdInChIKey = RHCCUQVVABYRDN-UHFFFAOYSA-N		| StdInChIKey = RHCCUQVVABYRDN-UHFFFAOYSA-N
			| CASNo_Ref = {{cascite|correct|??}}
	| CASNo = 500-24-3		| CASNo = 500-24-3
	| PubChem =		| PubChem = 136326
	| SMILES = C1(C=C2)C=CC2C=C1		| UNII = 2P5L4Z7K7I
			| SMILES = C1(C=C2)C=CC2C=C1
	}}		}}
	| Section2 = {{Chembox Properties		|Section2={{Chembox Properties
	| C=8|H=8		| C=8 | H=8
	| MolarMass = 104.15		| MolarMass = 104.15
	| Appearance =		| Appearance =
	| Density =		| Density = 1.013 g/mL
	| MeltingPt =		| MeltingPt =
			| BoilingPtC = 153.7
	| BoilingPt =
	| Solubility =		| Solubility =
	}}		}}
	| Section3 = {{Chembox Hazards		|Section3={{Chembox Hazards
	| MainHazards =		| MainHazards =
	| FlashPt =		| FlashPt =
	| Autoignition =		| AutoignitionPt =
	}}		}}
	}}		}}
	'''Barrelene''' is a ] ] with ] C<sub>8</sub>H<sub>8</sub> and ] bicycloocta-2,5,7-triene. First synthesized and described by ] in 1960 the name derives from the obvious resemblance with a ], with the staves being three ] units attached to two ] groups. It is the formal ] adduct of ] and ]. Due to its unusual ] the compound is of considerable interest to theoretical chemists. Like ], barrelene has a set of 6 cyclic, but not planar, overlapping ]s. Because it is not possible to avoid a destabilizing overlap of opposite-sign lobes, the structure represents ].		'''Barrelene''' is a ] ] with ] C<sub>8</sub>H<sub>8</sub> and ] bicycloocta-2,5,7-triene. First synthesized and described by ] in 1960, the name derives from the resemblance to a ], with the staves being three ] units attached to two ] groups. It is the formal ] adduct of ] and ]. Due to its unusual ], the compound is of considerable interest to theoretical chemists.
		⚫	]s, with the alkene groups part of an ]s, are related compounds. It is also a starting material for many other organic compounds, such as ].
	:]
			==Synthesis==
⚫	]s, with the alkene groups part of an arene, are related compounds. It is also a starting material for many other organic compounds such as ].
		⚫	The original Zimmerman synthesis modified in 1969<ref>{{Cite journal |last=Zimmerman |first=Howard E. |last2=Grunewald |first2=Gary L. |last3=Paufler |first3=Robert M. |last4=Sherwin |first4=Maynard A. |date=April 1969 |title=Synthesis and physical properties of barrelene, a unique Moebius-like molecule |url=https://pubs.acs.org/doi/abs/10.1021/ja01037a024 |journal=Journal of the American Chemical Society |language=en |volume=91 |issue=9 |pages=2330–2338 |doi=10.1021/ja01037a024 |issn=0002-7863}}</ref> starts from ]:<ref group=note>Reaction scheme: ] of ] (1) takes place at 650&nbsp;°C with ] to give α-] (2). The reaction with ] (3) is a tandem ]/retro-Diels–Alder/Diels–Alder sequence, which yields di-] 5 as a mixture of two ]s. It is possible to convert the ] 5b to the exo isomer 5a by an ] process through the ]. The ketone groups are converted to ] groups in 6 by reaction with ] and then to the ] groups in 7 by reaction with ]. A basic ] takes the scheme to give ] 8 and its ] to the di-] 9 takes place with ]. Finally, a ] through ] 10 gives the barrelene 11.</ref>
			:]{{clear-left}}
⚫	The original Zimmerman synthesis modified in 1969<ref>''Synthesis and physical properties of barrelene, a unique Moebius-like molecule'' Howard E. Zimmerman, Gary L. Grunewald, Robert M. Paufler, Maynard A. Sherwin ]; '''1969'''; 91(9); 2330-2338. </ref> starts from ]:<ref>Reaction scheme: ] of ] (1) takes place at 650 °C with ] to α-] (2). The reaction with ] (3) is a double ] to the di-] 5 as a mixture of two ]s. It is possible to convert the ] 5b to the exo isomer 5a by an ] process through the ]. The ketone groups are converted to ] groups in 6 by reaction with ] and then to the ] groups in 7 by reaction with ]. A basic ] takes the scheme to ] 8 and its ] to di-] 9 takes place with ]. Finally a ] through ] 10 gives the barrelene 11</ref>
		⚫	Many alternative routes have been devised since then, one of them starting from ]:<ref>{{Cite journal |last=Cossu |first=Sergio |last2=Battaggia |first2=Simone |last3=De Lucchi |first3=Ottorino |date=1997-06-13 |title=Barrelene, a New Convenient Synthesis |url=https://pubs.acs.org/doi/10.1021/jo962267f |journal=The Journal of Organic Chemistry |language=en |volume=62 |issue=12 |pages=4162–4163 |doi=10.1021/jo962267f |issn=0022-3263}}</ref><ref>Step one in this reaction between ] (one of the possible ]s) with (''Z'')-1,2-bis(phenylsulfonyl)ethylene is a ]. The reagents for ] are ] and ]. The second ] takes place with ] in ] style.</ref>
	:]
			:]
⚫	many alternative routes have been devised since then, one of them starting from ]:<ref>''Barrelene, a New Convenient Synthesis'' Sergio Cossu, Simone Battaggia, and Ottorino De Lucchi ]; '''1997'''; 62(12) pp 4162 - 4163; {{DOI|10.1021/jo962267f}}</ref> <ref>Step one in this reaction between ] (one of the possible ]s) with (Z)-1,2-bis(phenylsulfonyl)ethylene is a ] reaction. The reagents for ] are ] and ]. The second ] takes place with ] in ] style.</ref>
			An alternate route that allows synthesis of the parent barrelene system and a variety of substituted barrelenes has also been reported.<ref>{{Cite journal |last=Wagaman |first=Michael W. |last2=Bellmann |first2=Erika |last3=Cucullu |first3=Michèle |last4=Grubbs |first4=Robert H. |date=1997-12-01 |title=Synthesis of Substituted Bicyclooctatrienes |url=https://pubs.acs.org/doi/10.1021/jo971039y |journal=The Journal of Organic Chemistry |language=en |volume=62 |issue=26 |pages=9076–9082 |doi=10.1021/jo971039y |issn=0022-3263}}</ref>
⚫	:]
		⚫	]
	An alternate route that allows synthesis of the parent barrelene system and a variety of substituted barrelenes has also been reported<ref>''Synthesis of Substituted Bicyclooctatrienes'' Michael W. Wagaman, Erika Bellmann, Michèle Cucullu, and Robert H. Grubbs ]; '''1997'''; 62(26) pp 9076 - 9082; {{DOI|10.1021/jo971039y}}</ref>
		⚫	==Barrelene reactions==
	]
⚫	==Barrelene Reactions==
	Barrelene is ] with hydrogen gas and ] in ] to the fully saturated -octane]]. ] with ] in ] gives a di-bromo adduct because a ] intervenes:		Barrelene is ] with hydrogen gas and ] in ] to the fully saturated -octane]]. ] with ] in ] gives a di-bromo adduct because a ] intervenes:
	:]		:]
	] of barrelene with ] gives the trioxatrishomobarrelene<ref>endo, exo,syn-3,7,10-Trioxapentacycloundecane</ref> which on ] with ] (driving force:relief of ]) converts into the trioxatrishomocubane:<ref>''4,7,11-Triheterotrishomocubanes - Propeller-Shaped Highly Symmetrical Chiral Molecules Derived from Barrelene'' Sergei I. Kozhushkov et al. European Journal of Organic Chemistry Volume '''2006''', Issue 11 , Pages 2590 - 2600 </ref>		] of barrelene with ] gives the trioxatrishomobarrelene<ref>endo, exo,syn-3,7,10-Trioxapentacycloundecane</ref> which on ] with ] (driving force:relief of ]) converts into the trioxatrishomocubane:<ref>{{Cite journal |last=Kozhushkov |first=Sergei I. |last2=Preuß |first2=Thomas |last3=Yufit |first3=Dmitrii S. |last4=Howard |first4=Judith A. K. |last5=Meindl |first5=Kathrin |last6=Rühl |first6=Stephan |last7=Yamamoto |first7=Chiyo |last8=Okamoto |first8=Yoshio |last9=Schreiner |first9=Peter R. |last10=Rinderspacher |first10=B. Christopher |last11=de Meijere |first11=Armin |date=June 2006 |title=4,7,11‐Triheterotrishomocubanes – Propeller‐Shaped Highly Symmetrical Chiral Molecules Derived from Barrelene |url=https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.200600019 |journal=European Journal of Organic Chemistry |language=en |volume=2006 |issue=11 |pages=2590–2600 |doi=10.1002/ejoc.200600019 |issn=1434-193X}}</ref>
	:]		:]
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	This compound can be envisioned as a ] with three oxygen atoms inserted into three opposite edges or as ] capped by two ] units. The molecule is ] and the separate ]s have been isolated.		This compound can be envisioned as a ] with three oxygen atoms inserted into three opposite edges or as ] capped by two ] units. The molecule is ] and the separate ]s have been isolated.
	Certain barrelenes have been used as a ] in a ] :<ref>''Synthesis of Poly(1,4-naphthylenevinylenes): Metathesis Polymerization of Benzobarrelenes'' Lin Pu, Michael W. Wagaman, and ] ]; '''1996'''; 29(4) pp 1138 - 1143; (Article) {{DOI|10.1021/ma9500143}}</ref> <ref>''Synthesis of Organic and Water Soluble Poly(1,4-phenylenevinylenes) Containing Carboxyl Groups: Living Ring-Opening Metathesis Polymerization (ROMP) of 2,3-Dicarboxybarrelenes'' Michael W. Wagaman, and ] ]; '''1997'''; 30(14) pp 3978–3985; (Article) {{DOI|10.1021/ma9701595}}</ref>		Certain barrelenes have been used as a ] in a ]:<ref>{{Cite journal |last=Pu |first=Lin |last2=Wagaman |first2=Michael W. |last3=Grubbs |first3=Robert H. |date=1996-01-01 |title=Synthesis of Poly(1,4-naphthylenevinylenes): Metathesis Polymerization of Benzobarrelenes |url=https://pubs.acs.org/doi/10.1021/ma9500143 |journal=Macromolecules |language=en |volume=29 |issue=4 |pages=1138–1143 |doi=10.1021/ma9500143 |issn=0024-9297}}</ref><ref>{{Cite journal |last=Wagaman |first=Michael W. |last2=Grubbs |first2=Robert H. |date=1997-07-01 |title=Synthesis of Organic and Water Soluble Poly(1,4-phenylenevinylenes) Containing Carboxyl Groups: Living Ring-Opening Metathesis Polymerization (ROMP) of 2,3-Dicarboxybarrelenes |url=https://pubs.acs.org/doi/10.1021/ma9701595 |journal=Macromolecules |language=en |volume=30 |issue=14 |pages=3978–3985 |doi=10.1021/ma9701595 |issn=0024-9297}}</ref>
	:]		:]
	The catalyst is a ] (a ''molybdenum bis-(hexafluoro-tert-butoxy) carbene catalyst'') and the long alkyl chain attached to the monomer is required for solubility. Oxidation of the polymer with ] affords the naphthalene pendant of ].		The catalyst is a ] (a ''molybdenum bis-(hexafluoro-tert-butoxy) carbene catalyst'') and the long alkyl chain attached to the monomer is required for solubility. Oxidation of the polymer with ] affords the naphthalene pendant of ].
	] solutions of barrelene undergo ] ] when ] is added as a ] to produce ]. Prolonged irradiation results in further isomerisation to form ].<ref>		] solutions of barrelene undergo ] ] when ] is added as a ] to produce ]. Prolonged irradiation results in further isomerisation to form ].<ref>
	{{cite journal |doi= 10.1021/ja00953a045 |last1= Zimmerman|first1= H. E.|last2= Grunewald|first2= G. L.|year= 1966|title= The Chemistry of Barrelene. III. A Unique Photoisomerization to Semibullvalene|journal= ]|volume= 88|issue= 1|pages= 183–184|url= http://pubs.acs.org/doi/abs/10.1021/ja00953a045}}</ref>		{{cite journal |doi= 10.1021/ja00953a045 |last1= Zimmerman|first1= H. E.|last2= Grunewald|first2= G. L.|year= 1966|title= The Chemistry of Barrelene. III. A Unique Photoisomerization to Semibullvalene|journal= ]|volume= 88|issue= 1|pages= 183–184}}</ref>
			:]
			==Notes==
			{{reflist|group=note}}
	==References==		==References==
	<references/>		<references/>
	]		]
			]
	]
	]
	]