Tricyclobutabenzene

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Tricyclobutabenzene
Tricyclobutabenzene-from-xtal-1994-3D-balls.png
Identifiers
PubChem 143698
ChemSpider 126777 YesY
Jmol-3D images Image 1
Properties
Molecular formula C12H12
Molar mass 156.22 g mol−1
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Tricyclobutabenzene is an aromatic hydrocarbon consisting of a benzene core with three cyclobutane rings fused onto it. This compound and related compounds are studied in the laboratory because they are often display unusual conformations and because of their unusual reactivity. Tricyclobutabenzenes are isomers of radialenes and form an equilibrium with them.

The parent tricyclobutabenzene (C12H12) was first synthesised in 1979 [1] via a procedure depicted in Scheme 1.[2][3] This compound is stable up to 250 °C.

Scheme 1. Synthesis of tricyclobutabenzene

A polyoxygenated tricyclobutabenzene with an extraordinary bond length of 160 pm for the bond connecting two carbonyl groups [1] was synthesized according to scheme 2.[4]

Scheme 2. Polyoxygenated tricyclobutabenzene

An ordinary bond of this type is only 148 pm and for comparison the C-C bond in isatin is 154 pm long. On the other hand, no change is recorded in the aromatic bond length alternation.

Similar chemistry yielded the six-fold ketone hexaoxotricyclobutabenzene C12O6, which happens to be a novel oxide of carbon.[5] A key starting material is the iodo triflate depicted below which is a benzotriyne synthon.

Scheme 3 Benztriyne synthon

See also[edit]

References[edit]

  1. ^ Tricyclobutabenzene Wutichai Nutakul, Randolph P. Thummel, Austin D. Taggart J. Am. Chem. Soc.; 1979; 101(3); 770-771. Abstract
  2. ^ Reaction sequence: coupling reaction of cyclobutene Grignard reagents followed by Diels-Alder reaction with dimethylcyclobutene-1,2-dicarboxylate, followed by ester hydrolysis to dicarboxylic acid with potassium hydroxide in methanol followed by decarboxylation and aromatization with lead tetraacetate
  3. ^ Poly-Oxygenated Tricyclobutabenzenes via Repeated [2 + 2] Cycloaddition of Benzyne and Ketene Silyl Acetal Toshiyuki Hamura, Yousuke Ibusuki, Hidehiro Uekusa, Takashi Matsumoto, and Keisuke SuzukiJ. Am. Chem. Soc.; 2006; 128(11) pp 3534 - 3535; Abstract
  4. ^ Reaction sequence: the key step is a [2+2]cycloaddition between an aryne formed from the iodotriflate by action of n-butyllithium and a ketene silyl acetal. The silyl acetal is then converted to a ketone group by hydrofluoric acid and the remaining acetal groups by reaction with boron trifluoride
  5. ^ Dodecamethoxy- and Hexaoxotricyclobutabenzene: Synthesis and Characterization Toshiyuki Hamura, Yousuke Ibusuki, Hidehiro Uekusa, Takashi Matsumoto, Jay S. Siegel, Kim K. Baldridge, and Keisuke Suzuki J. Am. Chem. Soc.; 2006; 128(31) pp 10032 - 10033; (Communication) doi:10.1021/ja064063e