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{{Short description|Ion}} |
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{{Chembox |
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| verifiedrevid = 429969980 |
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| ImageFileL1 = Oxatriquinane.svg |
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| ImageFileL1 = Oxatriquinane.svg |
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| ImageFileR1 = Oxatriquinane.png |
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| ImageFileR1 = Oxatriquinane.png |
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| PIN = (2a''s'',4a''s'',6a''s'')-Octahydro-2a<sup>1</sup>λ<sup>4</sup>-oxacyclopentapentalene-2a<sup>1</sup>(1''H'')-ylium |
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| IUPACName = (2as,4as,6as)-Octahydro-1''H''-2a<sup>1</sup>-oxacyclopentapentalen-2a<sup>1</sup>-ium |
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| OtherNames = |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| CASNo = 1056549-35-9 |
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| CASNo = 1056549-35-9 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| PubChem = |
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| PubChem = 57459997 |
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| SMILES = 123(CC2)()CC3()CC1}} |
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| SMILES = 123(CC2)()CC3()CC1 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| Section2 = {{Chembox Properties |
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| ChemSpiderID = 21402960 |
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| C=9 | H=15 | O=1 |
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| InChI = 1/C9H15O/c1-2-8-5-6-9-4-3-7(1)10(8)9/h7-9H,1-6H2/q+1/t7-,8+,9- |
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| InChIKey = BVKXDOLLNZJDKZ-AYMMMOKOBR |
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| StdInChI = 1S/C9H15O/c1-2-8-5-6-9-4-3-7(1)10(8)9/h7-9H,1-6H2/q+1/t7-,8+,9- |
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| StdInChIKey = BVKXDOLLNZJDKZ-AYMMMOKOSA-N}} |
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| C=9 | H=15 | O=1 |
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'''Oxatriquinane''' ('''oxoniaperhydrotriquinacene'''{{ref|a}}) is an alkyl ] with formula (CH<sub>2</sub>CH<sub>2</sub>CH)<sub>3</sub>O<sup>+</sup>. It has a ] backbone, with a tricoordinated ] connected to ] 1, 4, and 7, forming three fused pentagonal rings. In contrast to most trialkyloxonium ions, oxatriquinane hydrolyzes slowly. |
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== History == |
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'''Oxatriquinane''' is an alkyl ] with formula {{chem|C|9|H|15|O|+}}, remarkable for being stable in aqueous solution. It has a ] backbone, with the trivalent ] connected to ] 1,4, and 7, forming three fused pentagonal cycles. |
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Oxatriquinane was first described in 2008. Its five-step synthesis starts from ].<ref name=mascal> |
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{{cite journal |title=Oxatriquinane and Oxatriquinacene: Extraordinary Oxonium Ions |author1=Mark Mascal |author2=Nema Hafezi |author3=Nabin K. Meher |author4=James C. Fettinger |name-list-style=amp |pages=13532–13533 |doi=10.1021/ja805686u |volume=130 |year=2008 |journal=Journal of the American Chemical Society |pmid=18798616 |issue=41}} |
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Oxonium ions normally are strong ]s and are only observed in solution as ] or under extreme conditions. Oxatriquinane does not react with boiling water or with alcohols, thiols, halide ions, or amines, although it does react with stronger ]s such as hydroxide, cyanide, and azide. Oxatriquinane was first described in 2008, and was obtained after a five-step synthesis starting from ].<ref> |
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{{cite journal |title=Oxatriquinane and Oxatriquinacene: Extraordinary Oxonium Ions |author=Mark Mascal, Nema Hafezi, Nabin K. Meher, and James C. Fettinger |pages=13532–13533 |doi=10.1021/ja805686u |volume=130 |year=2008 |journal=Journal of the American Chemical Society |pmid=18798616 |issue=41}} |
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</ref><ref> |
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</ref><ref> |
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{{cite journal |date=September 29, 2008 |volume=86 |issue=39 |pages=10 |title=Taming Alkyl Oxonium Ions: Fused tricyclic structure stabilizes famously reactive alkylating agents |author=Rachel Petkewich |journal=Chemical and Engineering News |url=http://pubs.acs.org/cen/news/86/i39/8639notw6.html |doi=10.1021/cen-v086n039.p010}} |
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{{cite journal |date=September 29, 2008 |volume=86 |issue=39 |pages=10 |title=Taming Alkyl Oxonium Ions: Fused tricyclic structure stabilizes famously reactive alkylating agents |author=Rachel Petkewich |journal=Chemical and Engineering News |url=http://pubs.acs.org/cen/news/86/i39/8639notw6.html |doi=10.1021/cen-v086n039.p010}} |
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</ref><ref> |
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</ref><ref> |
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{{cite journal |journal=Nature Chemistry |title=Oxonium ions: Ring of stability |author=Tim Reid |doi=10.1038/nchem.70 |date=3 October 2008}} |
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{{cite journal |journal=Nature Chemistry |title=Oxonium ions: Ring of stability |author=Tim Reid |doi=10.1038/nchem.70 |date=3 October 2008|pages=1 |doi-access=free }} |
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</ref> |
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</ref> The same paper also described '''oxatriquinacene''', the tri-unsaturated analog, which is of interest as a possible precursor to '''oxaacepentalene''', a neutral aromatic species. |
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Its C–O bond lengths are 1.54 Å. The C−O−C angles are acute.<ref name=mascal/> |
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== Reactions == |
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Oxonium ions normally are strong ]s and are hydrolytically sensitive. Oxatriquinane does not react with boiling water or with alcohols, thiols, halide ions, or amines, although it does react with stronger ]s such as hydroxide, cyanide, and azide.<ref name=mascal/> |
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The ability of the oxygen to enter into a fourth covalent bond has been of some theoretical interest and was achieved using ].<ref>{{cite journal|last1=Stoyanov|first1=Evgenii S.|last2=Gunbas|first2=Gorkem|last3=Hafezi|first3=Nema|last4=Mascal|first4=Mark|last5=Stoyanova|first5=Irini V.|last6=Tham|first6=Fook S.|last7=Reed|first7=Christopher A.|title=The R3O<sup>+</sup>···H<sup>+</sup> Hydrogen Bond: Toward a Tetracoordinate Oxadionium(2+) Ion|journal=Journal of the American Chemical Society|date=11 January 2012|volume=134|issue=1|pages=707–714|doi=10.1021/ja209942s|pmid=22133059|pmc=3257418}}</ref> As illustrated by the structures of most ]s, oxygen compounds routinely have bonds to >3 elements in other classes of compounds. |
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==Analogs== |
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Related species include ],<ref name=mascal /> the tri-unsaturated ], which is of interest as a possible precursor to oxaacepentalene, a neutral aromatic species. 1,4,7-Tri-''tert''-butyloxatriquinane has also been synthesized. This compound contains significant amounts of intramolecular steric strain, resulting in further bond elongation to give C–O bond lengths of 1.622 Å, the longest recorded in any species.<ref>{{cite journal|last1=Gunbas|first1=Gorkem|last2=Hafezi|first2=Nema|last3=Sheppard|first3=William L.|last4=Olmstead|first4=Marilyn M.|last5=Stoyanova|first5=Irini V.|last6=Tham|first6=Fook S.|last7=Meyer|first7=Matthew P.|last8=Mascal|first8=Mark|title=Extreme oxatriquinanes and a record C–O bond length|journal=Nature Chemistry|date=18 November 2012|volume=4|issue=12|pages=1018–1023|doi=10.1038/nchem.1502|pmid=23174982|bibcode=2012NatCh...4.1018G}}</ref> |
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<gallery> |
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<gallery> |
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File:Oxatriquinacene.svg|Oxatriquinacene |
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File:Oxatriquinacene.svg|Oxatriquinacene |
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File:Oxaacepentalene.svg|Oxaacepentalene |
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File:Oxaacepentalene.svg|Oxaacepentalene |
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</gallery> |
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</gallery> |
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==Notes== |
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:1.{{note|a}} Triquinane is more often used in the natural product literature to refer to three angularly fused cyclopentane rings sharing a common quaternary carbon in the center, a structure which contains one more carbon atom at the periphery. Moreover, substitution by O<sup>+</sup> is more properly designated by the prefix oxonia. Nevertheless, the authors who first prepared the cation called it oxatriquinane, and the name has been perpetuated in the literature. A semisystematic name in line with standard nomenclature would be 2a<sup>1</sup>-oxonia-1,2,3,4,5,6-hexahydrotriquinacene. |
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==References== |
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==References== |
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{{reflist|2}} |
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