Synthesis and properties of bicyclo[2.2.

0]hexa-2,5-diene
The compound itself was first synthesized in 1962 as a tert-butylderivative[3] and then as the unsubstituted compound by E.E. van Tamelen in 1963 by photolysis of cis-1,2-dihydro derivative of phthalic anhydride followed by oxidation with lead tetraacetate.[4][5]

The conjoined cyclobutene rings that form Dewar benzene form an obtuse angle. Unlike benzene, Dewar benzene is not flat; the two cyclobutene rings make an angle. The compound has nevertheless considerablestrain energy and reverts back to benzene with a chemical half-life of two days. This thermal conversion is relatively slow because it is symmetry forbidden based on orbital symmetry arguments[6].

[edit] "Dewar benzene" and benzene

It is sometimes incorrectly claimed that Dewar proposed his structure as the true structure of benzene. In fact Dewar merely wrote the structure as one of seven possible isomers, and believed that his experiments on benzene supported the (correct)structure which had been proposed by Kekul.[2] After the development in 1928 of the valence bond theory, the three possible Dewar structures were considered as minor resonance contributors in the overall description of benzene. The major resonance contributors are of course the two possible Kekul structures. Other classic structures which have been considered as possible benzene isomer are s prismane, benzvalene and Claus' benzene. In fact prismane and benzvalene were synthesized in the 1970s, and Claus' benzene has never been synthesized.

[edit] Hexamethyl Dewar benzene

Hexamethyl ewar benzene has been prepared by bi ycl tri eri ati n of di ethylacetylene with al ini chloride.[7] t undergoes an unusual rearrangement reaction with hydrohalic acids to form a pentamethylcyclopentadiene deri ati e,[8][9] and consequently can be used as a starting material for synthesising some pentamethylcyclopentadienylorganometallic compounds.[10][11]

[edit]
The first synthesis of the Cubane structure was successfully carried out in 1964 by Philip E. Eaton and Thomas W. Cole in the Department of Chemistry at the Uni ersity of Chicago in llinois. This is shown below:

Phili E. Eaton Synthesis:

Subsequential this was improved a few years later by N.B. Chapman et al. in England, and the cubane synthesis ultimately evolved into a simple five -step process providing cubane-1,4-dicarboxylic acid in about 25% overall yield.

Improved Synthesis:

The carboxylic acid groups on cubane -1,4-dicarboxylic acid turned out to be exceedingly well behaved. For information regarding possible interconversions of the carboxylic group, see Functional Group Transformations. An alternative synthesis was proposed by James C. Barborak, L. Watts and R. Pettit in the Department of Chemistry, University of Texas, in 1966. They noted from initial experiments that the organometallic complex cyclobutadiene-iron tricarbonyl seemed to afford a useful source of the normally unstable cyclobutadiene. During the oxidative decomposition of the iron complex with ceric ion in the presence of dienophiles a molecule of cyclobutadiene can be transf erred form the iron atom to the dienophile. n order to demonstrate the general utility of the reaction they proposed the synthesis of the cubane system, in which the cyclobutadiene transfer reaction plays a key role. The reaction scheme is shown below:

James C. Barborak Synthesis:

The dibromodiketone was converted to cubane-1,4-dicarboxylic acid by the Favorskii rearrangement. Decarboxylation of cubane -1,4-dicarboxylic acid was carried out via thermal degradation of the di-t -butyl perester by heating in isopropyl benzene. t should be noted that the product of the initial reaction of the 2,5-dibromo-1,4-benzo quinone is the endo isomer due to maximum orbital overlap.

Improved Decarboxylation Method:

The original decarboxylation method via the t t-butyl perester has been superseded by a far superior pathway. This is shown below:

Availability of Cubanes.
The synthesis of cubane-1,4-dicarboxylic acid has been scaled up and is now conducted in small pilot plants by Fluorochem in California and EniChem Synthesis in Milan. t is now being made in multi -kilogram batches. Nevertheless, cubane and its derivatives are still expensive to purchase. Cubane the hydrocarbon can be easily obtained by the above improved decarboxylation on a 10 -gram scale in very nearly quantitative yield. t is beautifully crystalline; alas, the crystals are rhombohedral, not cubic.

Browse hundreds of other total syntheses. Part 1 of 1

NBS CCl4

Br2 Pentane, CH2Cl2 0 to 10 C

Et2NH Et2O -20 C, 40 % (3 steps) See the Diels-Alder Reaction

(CH2 OH)2, TsOH PhH Reflux

HCl H2 O 85 % (2 steps)

h MeOH 95 %

KOH H2 O Reflux, 95 % See the Favorskii Rearrangement

SOCl2

t-BuOOH, Pyr Et2O 95 % (2 steps)

Cumene 152 C, 55 %

H2SO4 H2 O 95 %

KOH H2 O Reflux, 55 % See the Favorskii Rearrangement

SOCl2

t-BuOOH Et2O 98 % (2 steps)

Diisopropylbenzene 150 C, 30 %