- Bullvalene
Bullvalene is a
hydrocarbon with thechemical formula C10H10 with the unusual property that thechemical bond s making up the molecule are constantly rearranging as influxional molecule s. For this reason bullvalene is extensively studied inorganic chemistry . The name "bullvalene" is derived from the nickname of one the scientists who predicted its properties in 1963, William "bull" Doering ["The Bullvalene Story. The Conception of Bullvalene, a Molecule That Has No Permanent Structure" Ault, Addison.J. Chem. Educ. 2001 78 924. [http://www.jce.divched.org/Journal/Issues/2001/Jul/abs924.html Abstract] ] [Author Ault (2001) also suggests the name stems from BS because of an unimpressed grad student] and the underlying concept ofvalence tautomerism .Bullvalene
The bullvalene molecule is a
cyclopropane platform with threevinyl arms connecting with amethine group. Within a specific temperature range the molecule is subject to rapid degenerateCope rearrangement s with the result that all carbon atoms and hydrogen atoms are equivalent and that none of the carbon-carbon bonds is permanent. The number of possiblevalence tautomer s is 10!/3 = 1,209,600. The rearrangements displayed in "scheme 2" are only 5 of them.The compound was first synthesised in 1963 by G. Schröder by
photolysis of a dimer ofcyclooctatetraene with expulsion ofbenzene .The unusual dynamic properties of bullvalene show up in
proton NMR . In a spectrum taken at room temperature a broad peak is visible representing many different protons. The spectrum at 120°C on the other hand shows just one peak at 4.2 ppm. At this temperature the bullvalane protons are rearranging faster than the NMR can resolve resonances, this is largely due to theHeisenberg Uncertainty Principle (energy/time formulation).Bullvalones
In bullvalones one vinyl group in one of the arms in bullvalene is replaced by a
ketone group. In this way it is possible to activate the fluxional state by adding base and deactivate it again by removing the base: ["Synthesis of Oligosubstituted Bullvalones: Shapeshifting Molecules Under Basic Conditions" Alex R. Lippert, Juthanat Kaeobamrung, and Jeffrey W. BodeJ. Am. Chem. Soc. ; 2006; 128(46) pp 14738 - 14739; (Communication) DOI|10.1021/ja063900+]Compound 1 in "scheme 2b" is not a fluxional molecule but by adding base (
sodium methoxide inmethanol ) the ketone converts to theenolate 2 and the fluxional state is switched on.Deuterium labeling is possible forming first 3 a then a complex mixture with up to 7 deuterium atoms, compound 4 being just one of them.emibullvalene
In semibullvalene (C8H8), one ethylene arm is replaced by a single bond. The compound was first prepared by
photolysis ofbarrelene intoluene withacetone as aphotosensitizer ["The Chemistry of Barrelene. III. A Unique Photoisomerization to Semibullvalene" Howard E. Zimmerman, Gary L. GrunewaldJ. Am. Chem. Soc. ; 1966; 88(1); 183-184. [http://pubs.acs.org/cgi-bin/abstract.cgi/jacsat/1966/88/i01/f-pdf/f_ja00953a045.pdf Abstract] ] in 1966.Semibullvalene exists only as two valence tautomers (2a and 2b in "scheme 3") but in this molecule the Cope rearrangement takes place even at -110°C, a temperature at which this type of reaction is ordinarily not possible.
One insight into the
reaction mechanism for this photoreaction is given by anisotope scrambling experiment. ["Mechanistic organic photochemistry. XXIV. The mechanism of the conversion of barrelene to semibullvalene. A general photochemical process" Howard E. Zimmerman, Roger W. Binkley, Richard S. Givens, Maynard A. SherwinJ. Am. Chem. Soc. ; 1967; 89(15); 3932-3933. [http://pubs.acs.org/cgi-bin/abstract.cgi/jacsat/1967/89/i15/f-pdf/f_ja00991a064.pdf Abstract] ] The 6 vinylic protons in barrelene 1 are more acidic than the two bridgehead protons and therefore they can be replaced bydeuterium with "N-deuteriocyclohexylamide". Photolysis of 2 results in the initial formation of anbiradical intermediate with a cyclopropane ring formed. This product rearranges to a second intermediate with a more favorableallyl ic radical as twomesomer s.Intersystem crossing and radical recombination results in equal quantities of semibullvalenes 3 and 4. The new proton distribution with allylic, vinylic and cyclopropanyl protons determined with proton NMR confirms this model.A new synthetic procedure for alkylated semibullvalenes published in 2006 is based on cyclodimerization of a 1,4-dilithio-1,3-diene with
copper(I) bromide . ["Metal-Mediated Efficient Synthesis, Structural Characterization, and Skeletal Rearrangement of Octasubstituted Semibullvalenes" Chao Wang, Jian Yuan, Guotao Li, Zitao Wang, Shiwei Zhang, and Zhenfeng XiJ. Am. Chem. Soc. ; 2006; 128(14) pp 4564 - 4565; [http://dx.doi.org/10.1021/ja0579208 Abstract] ] At 140°C the ethylated semibullvalene isomerises to thecyclooctatetraene .Barbaralane
In barbaralane one ethylene arm is replaced by a
methylene group and the dynamics are comparable to that of semibullvalene.References
External links
Wikimedia Foundation. 2010.