Benzvalene

Benzvalene
Names
	IUPAC name tricyclo[3.1.0.02,6]hex-3-ene
Identifiers
CAS Number	659-85-8 ;
3D model (JSmol)	Interactive image;
ChemSpider	120239 ;
PubChem CID	136470;
CompTox Dashboard (EPA)	DTXSID00216109 ;
	InChI InChI=1S/C6H6/c1-2-4-5-3(1)6(4)5/h1-6H Key: VMQPMGHYRISRHO-UHFFFAOYSA-N ; InChI=1/C6H6/c1-2-4-5-3(1)6(4)5/h1-6H Key: VMQPMGHYRISRHO-UHFFFAOYAJ;
	SMILES C1=CC2C3C1C23;
Properties
Chemical formula	C6H6
Molar mass	78.114 g·mol−1
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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	Infobox references

Benzvalene is an organic compound and one of several isomers of benzene.[1] It was first synthesized in 1971 by Thomas J. Katz et al.[2][3]

The 1971 synthesis consisted of treating cyclopentadiene with methyllithium in dimethyl ether and then with dichloromethane and methyllithium in diethyl ether at −45 °C. It can also be formed in low yield (along with fulvene and Dewar benzene) by irradiation of benzene at 237 to 254 nm.[4] The hydrocarbon in solution was described as having an extremely foul odor. Due to the high steric strain present in benzvalene, the pure compound (~71 kcal/mol higher in energy than benzene) easily detonates, for example by scratching.

The compound converts to benzene with a chemical half-life of approximately 10 days. This symmetry-forbidden transition is believed to take place through a diradical intermediate.[5]

Polybenzvalene

Benzvalene can be polymerized in a ROMP process to polybenzvalene.[6] This polymer contains highly strained bicyclobutane rings which again makes it a sensitive material. The rings can be isomerized to 1,3-dienes and for this reason polybenzvalene has been investigated as a precursor to polyacetylene.

References

Christl, M. (1981). "Benzvalene—Properties and Synthetic Potential". Angewandte Chemie International Edition in English. 20 (67): 529–546. doi:10.1002/anie.198105291.
Katz, T. J.; Wang, E. J.; Acton, N. (1971). "Benzvalene synthesis". Journal of the American Chemical Society. 93 (15): 3782. doi:10.1021/ja00744a045.
Katz, T. J.; Roth, R. J.; Acton, N.; Carnahan, E. J. (1999). "Synthesis of Benzvalene". The Journal of Organic Chemistry. 64 (20): 7663. doi:10.1021/jo990883g.
Kaplan, Louis; Wilzbach, K. E. (1968-06-01). "Photolysis of benzene vapor. Benzvalene formation at wavelengths 2537-2370 A". Journal of the American Chemical Society. 90 (12): 3291–3292. doi:10.1021/ja01014a086. ISSN 0002-7863.
Scott, Lawrence T.; Jones, Maitland. (1972). "Rearrangements and interconversions of compounds of the formula (CH)n". Chemical Reviews. 72 (2): 181. doi:10.1021/cr60276a004.
Swager, T. M.; Dougherty, D. A.; Grubbs, R. H. (1988). "Strained rings as a source of unsaturation: polybenzvalene, a new soluble polyacetylene precursor". Journal of the American Chemical Society. 110 (9): 2973. doi:10.1021/ja00217a049.

External links

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[1] Christl, M. (1981). "Benzvalene—Properties and Synthetic Potential". Angewandte Chemie International Edition in English. 20 (67): 529–546. doi:10.1002/anie.198105291.

[2] Katz, T. J.; Wang, E. J.; Acton, N. (1971). "Benzvalene synthesis". Journal of the American Chemical Society. 93 (15): 3782. doi:10.1021/ja00744a045.

[3] Katz, T. J.; Roth, R. J.; Acton, N.; Carnahan, E. J. (1999). "Synthesis of Benzvalene". The Journal of Organic Chemistry. 64 (20): 7663. doi:10.1021/jo990883g.

[4] Kaplan, Louis; Wilzbach, K. E. (1968-06-01). "Photolysis of benzene vapor. Benzvalene formation at wavelengths 2537-2370 A". Journal of the American Chemical Society. 90 (12): 3291–3292. doi:10.1021/ja01014a086. ISSN 0002-7863.

[5] Scott, Lawrence T.; Jones, Maitland. (1972). "Rearrangements and interconversions of compounds of the formula (CH)n". Chemical Reviews. 72 (2): 181. doi:10.1021/cr60276a004.

[6] Swager, T. M.; Dougherty, D. A.; Grubbs, R. H. (1988). "Strained rings as a source of unsaturation: polybenzvalene, a new soluble polyacetylene precursor". Journal of the American Chemical Society. 110 (9): 2973. doi:10.1021/ja00217a049.