Benzvalene

Benzvalene is an organic compound and one of several isomers of benzene.^[1] It was first synthesized in 1967 by K. E. Wilzbach et al. ^[2] via photolysis of benzene and the synthesis was later improved by Thomas J. Katz et al.^[3][4]

Benzvalene

Names
Preferred IUPAC name Tricyclo[3.1.0.0^2,6]hex-3-ene
Identifiers
CAS Number	659-85-8^N
3D model (JSmol)	Interactive image
ChemSpider	120239^N
PubChem CID	136470
CompTox Dashboard (EPA)	DTXSID00216109
InChI InChI=1S/C6H6/c1-2-4-5-3(1)6(4)5/h1-6H^N Key: VMQPMGHYRISRHO-UHFFFAOYSA-N^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). N verify (what is ^YN ?) Infobox references

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.^[5] 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.^[6]

Polybenzvalene

Benzvalene can be polymerized in a ROMP process to polybenzvalene.^[7] 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

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. Wilzbach, K. E.; Ritscher, J. S.; Kaplan, L. (1967). "Benzvalene, the Tricyclic Valence Isomer of Benzene". Journal of the American Chemical Society. 89 (4): 1031. doi:10.1021/ja00980a053.
3. Katz, T. J.; Wang, E. J.; Acton, N. (1971). "Benzvalene synthesis". Journal of the American Chemical Society. 93 (15): 3782. doi:10.1021/ja00744a045.
4. 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.
5. 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.
6. 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.
7. 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

  Media related to Benzvalene at Wikimedia Commons