# Octabisvalene

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**Octabisvalene** is a [chemical compound](/source/Chemical_compound) belonging to the group of [compounds](/source/Saturated_compounds) [polycyclic](/source/Polycyclic_compound) [hydrocarbons](/source/Hydrocarbons). Along with [cubane](/source/Cubane) and [cuneane](/source/Cuneane), octabisvalene is one of the three possible saturated C8H8 hydrocarbons and a valence isomer of [cyclooctatetraene](/source/Cyclooctatetraene).[1][2]

## Representation

The preparation of the first compound possessing an octabisvalene structure was published in 1985 by Christoph Rücker and [Horst Prinzbach](/source/Horst_Prinzbach).[2] Via an initial eleven-step synthetic sequence, which was subsequently shortened to eight steps, preparatively useful quantities of (*Z*)-3,7-bis(phenylsulfonyl)octabisvalene are accessible:[3]

The reaction of *syn*-benzene trioxide **2** with [methylphenylsulfone](/source/Methylphenylsulfone) **1** and [*n*-butyllithium](/source/N-Butyllithium) yields an [intramolecular](/source/Intramolecular_reaction) [cyclization](/source/Cyclization) bisaddition product **3**, which is reacted in the subsequent step with [acetone](/source/Acetone) in the presence of [p-toluenesulfonic acid](/source/P-toluenesulfonic_acid) to afford the [acetal](/source/Acetal) **4**. The remaining [hydroxy group](/source/Hydroxy_group) is converted with [methanesulfonic acid chloride](/source/Methanesulfonic_acid_chloride) to the [mesylate](/source/Mesylate) group **5**, which undergoes cyclization with *n*-butyllithium and [diisopropylamine](/source/Diisopropylamine) in [tetrahydrofuran](/source/Tetrahydrofuran) to yield intermediate **6**. Following the cleavage of the [protecting group](/source/Protecting_group) with [hydrochloric acid](/source/Hydrochloric_acid) in [methanol](/source/Methanol) to form the [diol](/source/Diol) **7**, the two hydroxy groups are converted into the benzenesulfonic acid ester using [benzenesulfonic acid chloride](/source/Benzenesulfonic_acid_chloride) in the presence of [triethanolamine](/source/Triethanolamine). Intermediate **8** is then reacted with *n*-butyllithium in THF to give the tetracyclic compound **9**, which cyclizes with [potassium hydroxide](/source/Potassium_hydroxide) in [DMSO](/source/DMSO) to yield (*Z*)-3,7-bis(phenylsulfonyl)octabisvalene **10**.[4]

The preparation of unsubstituted octabisvalene via the reaction of (*Z*)-3,7-bis(phenylsulfonyl)octabisvalene with [sodium](/source/Sodium) in liquid [ammonia](/source/Ammonia) was described in 1987.[5] Alternatively, the compound can be prepared by an analogous reaction of a [nitrile group](/source/Nitrile_group) octabisvalene]], which in turn can be prepared via a five-step sequence from [tricyclo\[4.1.0.00,7\]hept-4-en-3-one](/source/Tricyclo(4.1.0.0(2,7))hept-4-en-3-one).[6]

## Properties

The octabisvalene molecule features [Schoenflies symbolism](/source/Schoenflies_symbolism) and exhibits high [ring tension](/source/Ring_tension) due to its two bicyclo[1.1.0]butane units. An [MM2 force field calculation](/source/Force_field_(chemistry)) of octabisvalene yields a ring strain energy of 644 kJ/mol, a value intermediate between the ring strain of cubane (694 kJ/mol) and cuneane (571 kJ/mol). Octabisvalene is thermally inert up to a temperature of 140 °C.[5]

According to IUPAC nomenclature, the 7- and 8-positions of octabisvalene are indistinguishable. Consequently, there are two stereoisomers for 3,7-disubstituted octabisvalene derivatives, for which the designations (*Z*)- and (*E*)-isomer have been proposed based on the [cis-trans isomerism](/source/Cis-trans_isomerism) of [alkenes](/source/Alkenes).[7]

In 1991, the syntheses of heterocyclic octabisvalene derivatives, namely (*Z*)-7-cyano-3-azaoctabisvalene and (*Z*)-3,7-diazaoctabisvalene, were published.[8]

## References

1. Nadia El-Karzazi, Markus Möbs, Peter Hilmi Rösch (2007-01-31). ["Octabisvalen - Art or Science?"](http://office.oc.chemie.tu-darmstadt.de/DaMocles/files/molecule065.pdf). Retrieved 2022-07-27.

1. Christoph Rücker, Horst Prinzbach (1985), "(Z)-3,7-Bis(phenylsulfonyl)pentacyclo-[5.1.0.02,4.03,5.06,8]octan, ein Octabisvalen-Derivat", *[Angewandte Chemie](/source/Angewandte_Chemie_(Zeitschrift))*. Vol. 97, no. 5, pp. 426–427, [doi:10.1002/ange.19850970529](https://doi.org/10.1002/ange.19850970529)

1. Christoph Rücker, Horst Prinzbach, Hermann Irngartinger, Reiner Jahn, Hans Rodewald (1986), "(Z)-3,7-bisphenylsulfonyl-octabisvalene improved synthesis and X-ray structure analysis", *[Tetrahedron Letters](/source/Tetrahedron_Letters)*. Vol. 27, no. 14, pp. 1565–1568, [doi:10.1016/S0040-4039(00)84314-2](https://doi.org/10.1016/S0040-4039(00)84314-2)

1. Christoph Rücker (1987), "Phenylsulfonylsubstituierte Octabisvalene, Synthesen und Reaktionen", *[Chemische Berichte](/source/Chemische_Berichte)*. Vol. 120, no. 10, pp. 1629–1644, [doi:10.1002/cber.19871201006](https://doi.org/10.1002/cber.19871201006)

1. Christoph Ruecker, Bjoern Trupp (1988), "Pentacyclo[5.1.0.02,4.03,5.06,8]octane (octabisvalene)", *[Journal of the American Chemical Society](/source/Journal_of_the_American_Chemical_Society)*. Vol. 110, no. 14, pp. 4828–4829, [Bibcode:1988JAChS.110.4828R](https://ui.adsabs.harvard.edu/abs/1988JAChS.110.4828R). [doi:10.1021/ja00222a051](https://doi.org/10.1021/ja00222a051)

1. Björn Trupp, Dirk-Rainer Handreck, Hans-Peter Böhm, Lothar Knothe, Hans Fritz, Horst Prinzbach (1991), "Funktionalisierte Octabisvalene", *Chemische Berichte*. Vol. 124, no. 8, pp. 1757–1775, [doi:10.1002/cber.19911240814](https://doi.org/10.1002/cber.19911240814)

1. Christoph Rücker,Gunter Haftstein (2004), ["*E*/*Z* Isomerism Without a Double Bond – an Unusual Type of Stereoisomerism, and an Unprecedented Isomerisation in a Bicyclobutane"](https://hrcak.srce.hr/file/151150), *[Croatica Chemica Acta](/source/Croatica_Chemica_Acta)*. Vol. 77, no. 1–2, pp. 237–241

1. Björn Trupp, Hans Fritz, Horst Prinzbach, Hermann Irngartinger, Uwe Reifenstahl (1991), "3-Aza- und syn-3,7-Diazaoctabisvalen Synthesen, Röntgenstrukturanalysen, neue Heterocyclen", *Chemische Berichte*. Vol. 124, no. 8, pp. 1777–1794, [doi:10.1002/cber.19911240815](https://doi.org/10.1002/cber.19911240815)

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Adapted from the Wikipedia article [Octabisvalene](https://en.wikipedia.org/wiki/Octabisvalene) by Wikipedia contributors ([contributor history](https://en.wikipedia.org/wiki/Octabisvalene?action=history)). Available under [Creative Commons Attribution-ShareAlike 4.0 International](https://creativecommons.org/licenses/by-sa/4.0/). Changes may have been made.