In the Classroom
The Bullvalene Story. The Conception of Bullvalene,
a Molecule That Has No Permanent Structure
Addison Ault
Department of Chemistry, Cornell College, Mount Vernon, IA 52314; aault@cornell-iowa.edu
Benzene, C 6H6, and cyclooctatetraene, C8H8 (1, 2),
provide simple and familiar examples of how the properties
of a substance force us to draw important conclusions about
molecular structure. Thus the great stability of benzene and
the high reactivity of cyclooctatetraene lead us to think very
differently about the molecular natures of these substances.
Although each is customarily represented by a cyclic array
of alternating double and single bonds, we interpret these
representations quite differently, speaking of benzene as being
“aromatic” and cyclooctatetraene as being “a polyene”.
benzene cyclooctatetraene
stable reactive
“aromatic” “a polyene”
But there is yet another molecule of the general formula
(CH)n that provides a beautiful example of how the unusual
properties of a substance lead to unprecedented conclusions
about molecular structure. This molecule, of molecular formula
C10H10, is usually called “bullvalene”. Its molecular structure
has the astonishing feature of not being a structure in the con-
ventional sense. That is, bullvalene has no permanent carbon–
carbon bonds! All carbon atoms are bonded, or not bonded, to
the same extent with every other carbon atom in the molecule.
C10H10
bullvalene
no permanent carbon–carbon bonds
“a fluxional molecule”
Not only is this true without any possibility of doubt, but the
existence of such a molecule was predicted (3). Surely this
was one of the most risky predictions ever made in the history
of chemistry!
Unfortunately, none of this story is presented in any of
the “sophomore-level” organic texts on my shelf. One text
mentions bullvalene in a problem, and another reviews the
fluxional nature of the molecule but does not touch on the
thinking that led to the prediction of the existence of a
molecule of this unprecedented nature.
This prediction was made in 1963 by William Doering
and Wolfgang Roth (3), and this paper reviews the logical steps
that formed the basis for it, presenting the most important
insights and some of the most persuasive examples.
The Story
Doering and Roth started with the assumption that the
bond dissociation energy of the carbon–carbon single bond
of ethane is 347 kJ/mol.
H3C–CH3 → H3C
+
CH3 ∆H = 347 kJ/mol
924 Journal of Chemical Education • Vol. 78 No. 7 July 2001 • JChemEd.chem.wisc.edu
They then cited an activation energy of 259 kJ/mol for the
homolysis of 1-butene to form a methyl radical and an allyl
radical.


CH2=CH–CH2–CH3 → CH2=CH–CH2 +
CH3
∆E ‡ = 259 kJ/mol
The difference of 88 kJ/mol is attributed to stabilization of
the allylic radical by delocalization of the p electrons.
Doering and Roth then suggested that one might expect
an activation energy of 347 – 88 – 88 = 171 kJ/mol for the
breaking of the central bond of 1,5-hexadiene.
∆E ‡ = 171 kJ/mol
When 1,5-hexadiene is heated above 200 °C, however, it does
not dissociate into radicals but undergoes a Cope rearrangement.
210-250 °C
1,5-hexadiene 1,5-hexadiene
Since the product of this particular Cope rearrangement
cannot be distinguished from the starting material, it is called
a degenerate rearrangement. The fact that the reaction occurs,
however, is revealed by the observation that when the 1,1-di-
deutero analog is similarly treated, the deuterium atoms are
scrambled between the 1 and 3 positions.
210-250 °C
CD2 CD2
CH2 CH2
1,1-dideutero-1,5-hexadiene 3,3-dideutero-1,5-hexadiene
The rate of scrambling equals the rate of the reaction, and
the corresponding energy of activation, ∆E ‡ , was determined
to be about 146 kJ/mol (4 ). The value of 146 kJ/mol for
the Cope rearrangement indicates that the Cope transition
state is stabilized by about 171 – 146 = 25 kJ/mol. Since this
value is below that estimated for dissociation of 1,5-hexadiene
into a pair of allyl radicals, the transition state for the Cope
rearrangement appears to be stabilized somewhat by interac-
tion of the allyl fragments.
Doering and Roth also realized that a carbon–carbon single
bond could be broken more easily if it was part of a cyclopro-
pane ring, since the enthalpy of activation for the conversion of
cis-1,2-dideuterocyclopropane to trans-1,2-dideuterocyclo-
propane, assumed to occur by carbon–carbon bond breaking,
rotation, and re-closure, was about 267 kJ/mol.
 In the Classroom

D D D D Doering and Roth would have liked to compare the

H H properties of the cis isomer of 1,2-divinylcyclopropane to
440 °C
those of the trans isomer, but the cis isomer of this compound
H H H H
H H
was not a known compound.
cis-1,2-dideutero- D H D H
cyclopropane H H

H D H D
cis-1,2-divinylcyclopropane
H H
trans-1,2-dideutero- Vogel, Ott, and Gajek (6 ) had attempted to prepare cis-1,2-di-
cyclopropane vinylcyclopropane by the Hofmann elimination of trimethyl-
∆E ‡ = 267 kJ/mol amine from the cis isomer of 1,2-bis(β-dimethylamino-
This value of 267 kJ/mol is 80 kJ/mol below the 347 kJ/mol ethyl)cyclopropane, compound 1, but the only hydrocarbon
bond dissociation energy of the carbon–carbon bond of product that could be isolated was cyclohepta-1,4-diene.
ethane, and it represents 2/3 of the strain energy, 113 kJ/mol, + +
of cyclopropane. N N NaOH

Doering and Roth then considered the consequence of 80 °C

combining the effects of allylic stabilization and the strain of
a cyclopropane ring in molecules such as the cis and trans 1 cyclohepta-1,4-diene
isomers of 1,2-divinylcyclopropane. The corresponding amine oxide gave the same result, and
both of these were interpreted as an initial elimination to give
cis-1,2-divinylcyclopropane, followed by Cope rearrangement
to cyclohepta-1,4-diene.
divinylcyclopropane
Cope
The trans isomer of divinylcyclopropane was a known substance
and was reported to rearrange to cyclohepta-1,4-diene upon
heating to 190 °C (5). cis-1,2-divinylcyclopropane cyclohepta-1,4-diene

Doering and Roth attempted to prepare cis-1,2-divinyl-

cyclopropane in another way, by the cyclopropanation of
190 °C
cis-1,3,5-hexatriene.

trans-1,2-divinylcyclopropane cyclohepta-1,4-diene

The reaction probably takes place by homolysis of the 1,2- cis-1,3,5-hexatriene

bond of cyclopropane to give a pair of resonance-stabilized
allylic radicals, which undergo a conformational change and Although several cyclopropane derivatives were formed, they
then ring closure to form the product. could detect no cis-1,2-divinylcyclopropane in the product
mixture.

CH2

-45 °C
+ + +

initial conformation
subsequent conformation
You can estimate that the activation energy for this process
should be equal to that for the homolysis of the carbon–carbon
bond of ethane minus twice the energy of stabilization of an
allyl radical minus the partial relief of the strain of a cyclo-
propane ring, or 347 – 88 – 88 – 80 = 91 kJ/mol, a little low
for a process that takes place at a reasonable rate at 190 °C.
Doering and Roth suggested that perhaps rotation into the con-
formation required for ring closure requires additional energy.
Instead of cis-1,2-divinylcyclopropane, there appeared
cyclohepta-1,4-diene plus the products of its cyclopropana-
tion. Thus it again seemed that cis-1,2-divinylcyclopropane,
once formed, quickly isomerizes via a Cope rearrangement
to cyclohepta-1,4-diene. However, Doering and Roth were able
to isolate trans-1,2-divinylcyclopropane from the mixture of
hydrocarbons that is formed in the cyclopropanation of trans-
1,3,5-hexatriene.
At this point they realized that if the rearrangement of
cis-1,2-divinylcyclopropane is indeed fast at or near room
temperature, inclusion of this feature in a ring system might
increase the speed of the process, possibly making the
isomerization fast enough to be studied by NMR methods. A
molecule that meets these requirement is bicyclo[5.1.0]octa-2,5-
diene, or 3,4-homotropilidene.

JChemEd.chem.wisc.edu • Vol. 78 No. 7 July 2001 • Journal of Chemical Education 925

 In the Classroom

molecule just as a fast camera can capture the instantaneous

bicyclo[5.1.0]octa-2,5-diene
3,4-homotropilidene
The Cope rearrangement of this molecule would merely re-
generate the starting material and would lead to no other con-
stitutional isomers, just as was true of the Cope rearrange-
ment of 1,5-hexadiene.
positions of the spokes of a wheel. In contrast, NMR spec-
trometry can capture only a somewhat averaged spectrum of
a molecule, just a slow camera can show only an averaged
blur for the positions of the spokes of a wheel.
Doering and Roth then went on to point out that 3,4-
homotropilidine probably exists as rapidly interconverting
chair-like and boat-like conformational isomers.

Cope

chair-like boat-like
3,4-homotropilidene 3,4-homotropilidene lower energy higher energy
conformational isomers of 3,4-homotropilidene
Cyclopropanation of tropilidene produced the desired substance,
3,4-homotropilidene, as well as the isomeric product of mono- They also proposed that if this is true, the Cope rearrangement
cyclopropanation, 2. must take place by way of the higher energy boat-like isomer,
as indicated here.
CH2
+ Cope

tropilidene 3,4-homotropilidene 2
“boat-like” “boat-like”
The spectral properties of 3,4-homotropilidene are indeed
consistent with the notion that it can easily undergo a degener-
ate Cope rearrangement. At room temperature, the proton conformational conformational
NMR spectrum of 3,4-homotropilidine shows a featureless change change
peak in the vinyl region and an extremely broad hump between
δ = 4 and δ = 0. At ᎑ 50 °C and +180 °C, however, the spectra
are quite different, and each shows relatively sharp multiplets.
When the hot sample is again cooled, the original low-
temperature NMR spectra can again be observed. In contrast,
the infrared spectrum is the same at all temperatures.
These observations can be explained in this way. At ᎑ 50 °C,
“chair-like” “chair-like”
apparently, the Cope process is slow and the NMR spectrum
is that of individual forms of the molecule, all of which are Thus the activation energy for the Cope rearrangement would
the same. On the other hand, at +180 °C, the Cope process include the difference in energy between the two conforma-
is fast, and the proton NMR spectrum is that of an average tional isomers as well as the free energy of activation of the
form of the molecule, as indicated here, in which protons at Cope process.
positions 3 and 5 have the same, average, chemical shift, the Doering and Roth then proposed that a molecule that
methylene protons at positions 1 and 7 are equivalent, the was locked into the boat-like conformation by a third ethylene
methylene protons at positions 2 and 6 are equivalent, and bridge between the cyclopropane ring and the carbon at the
there are only 2 vinyl protons (at position 4). other end of the molecule would undergo even more facile
H2 H6
degenerate Cope rearrangements. This molecule of molecular
H1 H7
H6 H2
formula C10H10, called tricyclo[3.3.2.0]deca-2,7,9-triene or
H7 H1
H4
H5
Cope
H3
H4 “bullvalene”, is shown here.1
H3 H5

H5 H3 H5
H3

H4 H4

3,4-homotropilidene
Since, however, the only species present at all temperatures
is 3,4-homo-tropilidine, the infrared spectrum does not
change with a change in temperature.
This is a beautiful example of a concept that is often
mentioned but rarely illustrated: the difference in “shutter
speed” between IR spectrometry and NMR spectrometry. IR
spectrometry can capture an “instantaneous” spectrum of a
tricyclo[3.3.2.0]deca-2,7,9-triene
bullvalene
The astonishing, yet inevitable, consequence of rapid
Cope rearrangements would be that all 10 hydrogen atoms and
all 10 carbon atoms of the molecule would be equivalent,
with the result that the high-temperature proton NMR
spectrum of bullvalene would consist of a single line! Since 10

926 Journal of Chemical Education • Vol. 78 No. 7 July 2001 • JChemEd.chem.wisc.edu

 In the Classroom

points cannot be symmetrically placed on the surface of a sphere,
the 10 carbon atoms of bullvalene would not be stationary,
but would move about on the surface of a sphere in such a
way that their relationships to one another would be, on the
average, the same. Each carbon atom would be bonded (or
not bonded) to every other carbon atom to the same extent.
Bullvalene, a solid of melting point 96 °C, decomposes only
at temperatures approaching 400 °C. And sure enough, whereas
at 15 °C its proton NMR spectrum shows one extremely
broad hump, at 120 °C the proton NMR spectrum consists of
exactly one sharp singlet at δ = 4.2! Similarly, at 141 °C the
1H-noise-decoupled 13C spectrum of bullvalene shows only

Some of the 10!/3 or 1,209,600 contributors to this unique, one sharp singlet at δ = 86.4, and at ᎑60 °C the spectrum
unprecedented, and at that time unknown “fluxional” structure consists of four sharp singlets at δ = 128.5, 128.3, 31.0, and
are shown here. 21.0 with relative intensities of 3:3:1:3 (8).

9 10 9 10 Summary
8 8
1
2 3 4 1
3 4 5 In this paper I have reviewed and summarized the logical
process through which Doering and Roth conceived of the
5 6
7
6
2
7
possible existence of an isomer of molecular formula C10H10
that has a “fluxional” structure; that is, a structure in which
−(1-7)
every carbon atom is equally bonded, or not bonded, to every
−(10-4)
+(3-5) +(2-8) other carbon atom. Although in the early part of 1963 this
molecule existed only as a concept in the minds of Doering and
9 10 8 9
Roth, it was prepared before the year had ended. The evidence
10
8
1 4
−(7-8)
1
for its “fluxional” structure is that it gives a sharp singlet in its
3 +(5-10) 2 4
2 3 proton NMR spectrum. In order for the 10 protons, each
7
5 7 5
bonded to a carbon atom, to be chemical-shift equivalent,
6 6 “all ten carbon atoms [must] inevitably wander over the surface
−(1-8) −(4-5)
of a sphere in ever changing relationship to each other” (3).
+(3-10) +(2-7)

Acknowledgment
8 9 8 9

10 1
I thank the reviewer who drew my attention to ref 8.
7 2 4 10
1 2 3 3
Note
6 4 5
7
5 6 1. The origin of the name bullvalene is not known for sure.
Some say that the name is based on Professor Doering’s nickname,
Within the year, Gerhard Schröder (7), who had deter- “Bull” Doering; others say that the name was supplied by an
mined the structures of two of the dimers of cyclooctatetraene irreverent and skeptical graduate student: Bull-valene.
(C16H16), announced the formation of bullvalene (C10H10)
and benzene (C6H6) by photolysis of the dimer of cycloocta- Literature Cited
tetraene that melts at 76 °C.
1. Samet, C. J. Chem. Educ. 1993, 70, 291.
2. Ault, A. J. Chem. Educ. 2000, 77, 55.
3. Doering, W. von E.; Roth, W. Tetrahedron 1963, 19, 715.
4. Doering, W. von E.; Gilbert, J. C. Tetrahedron Supplement 1966,
light 7, 397.
5. Vogel, E. Angew. Chem. 1960, 74, 4.
6. Vogel, E.; Ott, K.-H.; Gajek, K. Liebigs Ann. 1961, 644, 172.
7. Schröder, G. Angew. Chem., Int. Ed. Eng. 1963, 2, 481.
8. Oth, J. F. M.; Müllen, K.; Gilles, J.-M.; Schröder, G. Helv.
mp 76 °C bullvalene and benzene Chim. Acta 1974, 57, 1415.

JChemEd.chem.wisc.edu • Vol. 78 No. 7 July 2001 • Journal of Chemical Education 927