The Aromatic Ring
by Doris Kolb
"Fragrant" is its literal meaning, but aromatic has come to
we a special meaning for chemists. Early in the history of
ganic chemistry it became clear that there were certain
whon compounds that were somehow different from the rest.
heir chemical formulas suggested that their molecules were
waturated, containing several double bonds, yet their
ronerties indicated otherwise. Often thev had distinctive
Iors, and 90 they hecame known a "nrnmatic" compounds.
Hter it turned out that thme c o m ~ o u n d shad something.in
bmmon. They all seemed to be refated to benzene.
re Benzene Problem
In 1825 Michael Faraday isolated a colorless liquid with a
easant odor from a condensed portion of "illuminating gas,"
~tainedby distilling certain fats and oils and used as fuel for
mps. The liquid boiled a t 80°C and solidified a t about 5%
ater Eilhardt Mitscherlich (1834) prepared the same liquid
om henzoic acid by distilling it with lime. He called the
~hstancebenzin, which became benzene in English.
Chemical analysis showed henzene to he 92% carbon and
6 hydrogen by weight, with a molecular weight of 78. Its
olecular formula therefore was CnHn.
" " which was a t once verv
m p k and f:xtremcly mnfusing. The exwptinnally low H to
ratio in CnIlr.
- -. imsrd quite a Droblem for organic chemists.
lnce carbon was tetravhent &d hydrogen m&ovalent, most
' the structures Dro~osedfor benzene contained double
mds. An early stLuc<uresuggested by Josef Loschmidt, for
:ample, was
which the circles represented six carhon atoms. The formula
~ntainedfour double honds, hut benzene did not behave like
I olefin. It did not undergo the rapid reactions typical of
lmpounds with double bonds. Loschmidt also suggested the
rmula
his one did not have any double bonds, hut it was still in-
Impatihle with the chemical facts about henzene. Benzene
"The Aromatic Ring" is part of
a series of substantive reviews of
chemical principles taught firstin
high school chemistry courses.
Dr. Kolb received a BS degree
from the University of Louisville
and both MS and PhD degrees
from The Ohio State University.
She has been employed as a
chemist at the Standard Oil Com-
pany and as a television lecturer in
a series "Spotlight on Research."
She has served on the staffs of
Corning Community College and
Doris K0lb Bradley University. Since 1967,
Illinois Central College
she has been Professor of Chem-
East Peoria, Illinois 61635 istry at Illinois Central College.
14 1 Journal of Chemical Education
Illinois Central College
East Peoria. Illinois 61635
formed onlv one monosuhstituted nroduct and three disuh-
stituted dehvatives (e.g. with bromine). This structure would
have two mono- and four di-substituted derivatives.
Various structures for henzene were proposed, hut it was
difficult to find a structure for CsH6 that would fit the known
chemistry of henzene. By the early 1860's organic chemists had
begun to make considerable progress in the area of molecular
structure, but the structure of henzene remained a mys-
tery.
The Kekule Formula
August Kekuli. hnd originally intended to hrrome an ar-
chitect, until.lustus Liehig cxrited hisenthusinsrn for c h e n -
istry. Perhaps that accounts for his interest in the space re-
lationships of atoms in molecules and the important contri-
butions he made to the structural theory of organic chemistry.
It was Kekul6 who first recognized that the carhon atoms in
organic compounds must he connected to each other. That
idea coupled with the assumption that carhon had a valence
of 4 and hvdroaen a valence of 1 in c o m ~ o u n d sresulted
(around 1860) i'his chain-like "sausage" foimulas, in which
the valence of each atom was indicated bv the number of
"links" in its chain. One of his early attempts to represent
henzene was
(Notice that this structure can be seen as an alternating se-
auence of double and sinale honds. and if we could connect
the end carbon atoms, where the arrows are shown, the
structure would he equivalent to the Kekul6 formula that is
still being used today).
A dream of snakes wriggling around in circles is said to have
led Kekul6 (1865)to his famous hexagonal formula, along with
a triangular alternative.
0
He later added the alternatina double and single bonds in
order to satisfy the valence of t&e carhon atoms,kven though
the chemical properties of henzene indicated that no double
honds were a&&y present
d b
Among the dozens of other structures that were later sug-
gested as possible models for the henzene molecule, the fol-
lowing seem to have been considered most seriously.
C l a w (1867) Dewar (1867) Ladenburg (1869)
The centric formulas of Claus, Armstrong, and Baeyer were
essentiallv identical with one valence from each carbon atom
directed &ward the center of the ring.
 Although James Dewar first mentioned the structure that
hears h ~ name,
r he did not artually propose it as the correct
tormula for ben7enc. since he arcenred th*, Kekul6 formula.
It was a group of othkrs who argued the case for the "Dewar"
structure. One of the most interesting structures proposed for
henzene was Ladenburg's "prism." For many years this was
considered to be the orimarv alternative to the Kekul6 for-
mula for benzene. A compound of that structure, called
prismane, was finally synthesized in 1973.
Chemists eventually adopted the simple Kekul6 formula,
even though they knew that benzene was not really cyclo-
hexatriene. There are two equivalent Kekul6 structures
0 0
and henzene was generally thought to be a mixture of the two
in a state of very rapid equilibrium. KekuU bad postulated
an "oscillation" between the two structures in 1872. As re-
cently as the 1920's chemists were still trying to isolate those
two individual forms for certain henzene derivatives.
The Aromatic Sextet
It soon became clear that aromatic properties were not
limited to henzene and its derivatives. There were other
com~oundsthat shared benzene's hieh deeree of unsaturation
and its tendency to undergo substitGion rkher than addition
reactions. Thev mainlv seemed to be 5- and 6-membered rines "
containing at ieast one atom that was not carbon.
p~ridine furan thiophene
E u ~ e n~ a m h e r z e(1890)
r used the Baever-Annstrone centric
formula to point out that aromatic character seemed require
a hexacentric system of "potential valences" or "affini-
ties."
His potential valences nrver did become popular, Itut his idea
-
Illat 6 was the "niaaic" nllmht:r for un aromatic ring would be
proposed again 35iears later.
Meanwhile Johannes Thiele (1899) tried to explain the
stahility of the aromatic ring with his "partial valence" theory.
Partial valence (shown by dotted lines) was attributed to
multiple bonds, and the partial valences overlapped in the case
of conjugated systems (alternating double and single bonds)
so that 1,4 addition usually occurred.
Completely conjugated ring systems would have overlapping
valences all around the ring, thus giving the ring aromatic
stability.
According to Thiele's hypothesis, any ring system with a
completely conjugated set of double bonds (resulting in partial
valences all around the ring) should be aromatic. Thus he
exoected both cvclobutadiene and cvclooctatetraene (with 2
ani1.l ronj11~m.4 double bonds, reipe>tivclv) to have ar;,miltic
ch:~r;wter.\\'hen Willstarter was unahle to svntheiize cvclo-
hutadiene, and when upon preparing cycl&ctatetraene he
showed that it was totally lacking in aromatic properties,
not aromatic aromatic not aromatic
support for Thiele's theory largely disappeared.
During the early 1920's Armit and Robinson noted that it
was only those conjugated cyclic systems with six multiple
bonding electrons that seemed to have special stability. Their
"aromatic sextet" was really just a revival of Bamberger'n
hexacentric theory, but when stated in terms of electrons in-
stead of valences, the idea was much more successful. Soon
the aromatic sextet of electrons was being seen as the essential
ingredient for ring aromaticity.
Resonance
The resonance concept, first introduced by Heisenberg
(1926) in connection with the quantum states of the helium
atom, was later (1930's) applied to problems of chemical
bonding by Linns Pauling and others. The resonance theory
is a mathematical approach to describing the electrons in
chemical bonds. wine the fundamental eouations of anantum
mechanics and assuming that the stationary quantim state
of lowest energy is the most stable. For conjugated system
maximum stability exists when certain electrons are "delo-
calized," or smeared out over the entire area of coniueation.
Whenever rwo or more structures can be drawn forsthesame
molecule, alike in their arrangement of atoms and different
only in their arrangement of el&trons, the molecule is capable
of resonance. Consider these two Lewis electronic formulas
for benzene.
I,:?
!!
'''C'CH - H
tI:C'"" " C : t l
. &I
H :
r " c:ll H:c :
:
C'
H H
They correspond to the two Kekul6 formulas:
The double-headed "resonance arrow" does not sienifv ~ " an ~
~ ~ ~ ~
equilibrium nmdition in which the two structures are very
r;~pidls
. . ihiftina bark and forth (as once was thoueht to he the
cnse~.Instead it means that the henzene molecule is not like
eithrr of thr tw~rKckuli. structures but is sumerhine in be.
tween, a resonance hybrid of the two. (The length > a car-
bon-carbon double bond is 1.33 A, and a single bond measures
1.54 A. X-ray analysis shows that in benzene all the C-C
bond distances are identical, and equal to 1.40 A). Perhaps the
benzene ring might best be represented as
The simple circle-inscribed hexagon a t the right has become
a popular alternative to the classical Kekul6 formula and is
probably the henzene formula most widely used today.
How aromatic a particular ring system is can be assessed
by determining its "resonance energy." One way to do this is
to measure its heat of hydrogenation. When hydrogen is added
to a double bond, the heat of reaction is about 120 kilojoules
per mole.
(3+- - 0 R, AH = -119.6 kJ
If benzene were really cyclohexatriene, its heat of hydroge-
nation should be about three times that of cvclohexane. or
The actual heat of hydrogenation for benzene, is only 204.8
kJ/mol. This is 150 kJ/mol less than we would expect i t to he
if the molecule really contained 3 double bonds. The 150
kJ/mol is a measure of the extra stability that benzene has
because its r electrons are delocalized and is referred to as the
stabilization energy of benzene.
Hiickel's Rule
Rewnnnce was useful for describing the aromatic ring, but
it could not explain why benzene was anmatic while s~milar
conjugated rings with 201 4 double bonds were not. The mo-
Volume 56, Number 5, May 1979 / 335
lecular-orbital method provided a key for solving that proh-
lem. Following the lead of Edward Condon and others who had
used a molecular-orbital approach to describe the bonding in
the hydrogen molecule (19271, Erich Huckel applied the
molecular orhital theory to conjugated ring systems. By cal-
culating a-orbital energies for various monocyclic conjugated
systems, he was able to develop an explanation for the stability
of henzene and certain other "aromatic" compounds. Huckel's
+
rule can he expressed as 4n 2, which represents thenumber
of ?r electrons that impart aromatic stahility to an unsaturated
planar ring. Since n may equal 0,1,2,3,. . .etc., a monocyclic
aromatic system might have 2, 6, 10, 14,. . . etc. a electrons
according to Huckel's rule. For henzene, and its simple de-
rivatives and analogs, n = 1 and 4n + 2 = 6, the aromatic
sextet.
Polycyclic Aromatic Compounds
Huckel's calculations were made for monocyclic conjugated
systems, so his rule is not generally applicable to polycyclic
systems. Even though many polycyclic aromatic compounds
do follow Huckel's rule
naphthalene phenanthrene chrylene
(n = 2) (n = 3) (n = 4)
4n+2=10 4n+2=14 4n+2=18
others do not. Pyrene and coronene, for example, have 16 and
24 a electrons, respectively, and therefore do not ohey
Huckel's rule, hut both are aromatic.
pyrene
In polycyclic aromatic systems it often happens that one
ring has more aromatic character than another. In phenan-
threne. for examole. the center rinz has less electron delo-
calizathn, and t h i s less aromaticity,ihen the two rings on the
ends. This is easiest to understand by considering the 5 con-
tributing resonance structures for phenanthrene.
& B h &
Each of the end rings has a 3-double-bond "Kekul6" ar-
rangement in 4 out of 5 of the structures, hut only 2 structures
show that condition for the middle ring. I n 4 of the 5 structures
a double hond appears in the 9,10 position (top middle),
suggesting that this is a largely localized hond. This is con-
firmed experimentally by the fact that addition readily occurs
across this 9,10 double hond, whereas the end rings undergo
typical aromatic suhstitution.
Polycyclic aromatic compounds need not he henzenoid.
Purine is one of the multi-ring heterocyclic compounds that
exhibit aromatic properties.
ty; 11
punne
Another polycyclic compound worthy of special mention is
azulene.
anzulene
Named for its deep blue color, azulene is a completely conju-
gated hicyclic molecule with one 5- and one 7-memhered ring
fused together. Although not as stable as its isomer naph-
336 / Journal of Chemical Education
thalene, azulene is still decidedly aromatic. I t is one of a
zrowing numher of what might he called non-classical aro-
matic compounds.
Non-Classical Aromatic Compounds
Cyclopentadiene as early as 1901 had been recognized as
an acidic hydrocarbon. In 1928 Ingold suggested that this
curious acidity was due to the stahility of the cyclopentadienyl
anion because of its aromatic sextet of electrons.
lJ1,> - fl* + OorO
This was the first instance of aromatic character being at-
tributed to such an unusual kind of ring. Among the fasci-
nating derivatives that have been made from this very stahle
carbanion are the organometallic "sandwich" molecules such
as ferrocene (discoveredin 1951) and other metallocenes.
It was not until 1945 that M. J. S. Dewar, in working with some
natural products with 7-membered rings, suggested that a
similar type of aromaticity should exist for the tropylium ion
(the cation derived from cycloheptatriene),
a fact confirmed in 1954 hy Doering and Knox. Since then the
di-anion of cyclohutadiene and the di-cation of cyclooctate-
traene have also been shown to exhibit aromaticity.
All four of these aromatic ions are. like benzene., .
~ l a n acvclic
r
systems with 6 ff electrons. According to Huckel's rule the
cation of cvcloorooene should also he aromatic (n = 0: 4n +
Breslow and others have established that cvclooronenium
derivatives do indeed have aromatic properties. ~ h ~ ~ l a n a r
anion of cvclononatetraene and the di-anion of cvclooctate-
traene wo&d also he expected to have aromatic itability (n
=2;4n+2=10)
and both of them do.
In addition, Huckel's rule predicted aromatic stahility for
some macrocvclic
" oolvenes
. called annulenes. Sondheimer and
others have prepared and studied a numher of these conju-
gated rings and have found that (181-annulene (a fully con-
jugated ring with 18 carbon atoms) does have aromatic
properties, especially a t lower temperatures. [14]-Annulene
is less stahle, hut still aromatic
m
w
[ I 81-annulcne
'-=v-'
1141-annulene
and so is [22]-annulene. These rings contain 14,18, and 22 a
+
electrons, which represent values of 4n 2 where n = 3,4, and
5. The [12]-, [16]-, [20]-,and [24]-annulenes, on the other hand,
do not ohey Huckel's rule and are not aromatic.
All of the aromatic rings mentioned thus far have been
planar, fully conjugated systems. But since 1962 Pettit and
others have nreoared some homoaromatic comoounds, in
which the r i n g are not cvmpletely planar and the& is definite
inwrruptiun oft he conjugatum pattern. (This kind of aromatic
system had, in fact, been predicted by Winstein). When cy- such as longer wavelength absorption bands in the ultraviolet.
clooctatetraene is treated with acid, for example, the An aromatic compound also has diamagnetic anisotropy; in
"homotropylium" ion is formed other words, its magnetic susceptibility is much greater along
CH. one axis (of a single crystal) than along the other two axes.
Today i t is probably most convenient to define aromaticity
in terms of how well a rine of a electrons can sustain an in-
duced "ring current," as measured by nuclear magnetic res-
onance. If the protons attached to an unsaturated ring are
It has six a electrons spread around a 7-membered planar ring shifted downfield in the nmr spectrum (from where they
that is interrupted a t one point by a CH2 group lying in a would be if the ring contained double bonds), the system is
perpendicular plane. I n spite of the discontinuity, the said to be diatropic. A ring exhibits this low field chemical
homotropylium ion is aromatic. shift (down to around 7-8 ppm) because its a electrons are
What is Aromaticity? delocalized. A diatropic ring is therefore aromatic.
I t may be impossible to state a concise definition for aro- Mystified by its unsaturation,
maticity that would he completely acceptable to everyone. At Chemists long had pursued information
one time the "aromatic" label applied only to benzene and its On the benzenoid classification.
derivatives. Then its meaning was broadened to include any Benzene has been quite problematic.
compounds that were benzene-like. Chemical activity was the After much structure argumentation,
criterion for decidine whether a substance was aromatic, Kekuli: made his recommendation-
benzene being the chemical standard. Many chemists still The hexagonal representation,
tend to think of aromatic molecules as very stable unsaturated However. its form was not static.
rings that react by substitution rather than addition. Were there two farms in swift oscillation?
Followina the formulation of the electronic theory of va- Rapid shifting of ring conjugation?
lence arouna 1920, aromaticity began to be viewed as a special Instantaneous eauilihration? . . .
The subject remained enigmatic.
kind of molecular bonding. Aromatic compounds have been
defined as cyclic molecules in which all the atoms in the ring Now at last there is sound explanation
Far this special ring stabilization:
are involved in a single conjugated bonding system. Aromatic Pi electron delocalization
rings may also be described as planar cyclic systems with Is what makes a ring aromatic.
circular clouds of delocalized a electrons. For some the aro-
~ ~~~~ ~
-~~
matic rine is best defined as a cvclic unsaturated svstem that
is stabilized by resonance. An aromatic ring might even he
Some General References
described as a fully conjugated monocyclic system that has Rsdger. G. M., "Ammatie Character and Aromstieity."Cambridge Univenity Press. London.
+
4n 2 a electrons, in keeping with Hiickel's rule.
1969.
Garratt, P. J., "Aromaticity."McGrau-Hill, London, 1971.
Perhaps the most practical way to define aromaticity is i n & C. K., ''Structure and Mechanism in Organic Chemistry." 2nd 4.Cornell
. Univenity
Press. Ithaca, New Ynrk. 1969.
according to whatever parameter is being used to measure it. "KekuI6Centennial." ACS Symposium, Advances in Chemistry Series No. 61. ACS Puhli-
Thus. an unsaturated rina is aromatic if its bond distances cations, Washington. D.C. 1966.
March, J., "Advanced Organic Chemistry."2nd ed.. Chapter 2, McGrau-Hill. New Yurk.
show "niformity, as determined hy X-ray analysis, microwave ."...
ow7
spectroscopy, or electron diffraction. Or, an unsaturated ring Pauling. I,.,"TheNatureofthechemieslBond,"3rd ed.. Cornell U n i w r i t y Prers, Ithaca.
compound is aromatic if its heat of combustion or heat of NPWYork, 1960.
Snyder. J. P. (Edit",) "Nonhenzenoid Aromatics." organic Chemistry Monograph No. 16.
hydrogenation (as measured calorimetrically) is considerably 2 unlumer, Academic P r e . New York. 1969.
less than would be expected if the ring contained true double Sulomona, T. W. G.,"Organic Chemistcy." Chapter 12. John Wiley & Suns. Near York.
bonds. If a cyclic compound is aromatic, there are certain 1976.
Whelsnd. G. W.. -RPsonance in organic Chemirtry." Jnhn Wiley & sons, New Yurk,
characteristic features that show up in its electronic spectra, 1965.

Solar Energy Potential

The following solar energy diagram was prepared hy J. C. White. former Head ol'the Electrc,chemistry Branch ol'the
Chemistry Division oI The Naval Research Laboratory. It was provided hy .Jeanne Burhank, Southern Arizona Sect.ion,
ACS.

Vo'olume56. Number 5. May 1979 1 337