CHEM 2

DISCUSSANT: ANGELICA R. GUTIERREZ

BSED 2B SCIENCE
LECTURER: MRS. ANGELICA R. RICO
 In 1931 the German physicist Erich Hückel
carried out a series of mathematical calculations
based on the kind of theory that we have just
described Hückel’s rule is concerned with
compound containing one planar ring in which
each atom has a p orbital as in benzene.
 His calculations showed that planar
monocyclic rings containing 4n + 2 π electrons, where
n = 0, 1, 2, 3, and so on (i.e., rings containing 2, 6, 10,
14, ..., etc., π electrons), have closed shells of
delocalized electrons like benzene and should have
substantial resonance energies.
 There is a simple way to make a
diagram of the relative energies of orbitals in
monocyclic conjugated systems based on
Hückel’s calculations. To do so, we use the
following procedure:

1. We start by drawing a polygon

corresponding to the number of carbons in
the ring, placing a corner of the polygon at
the bottom.
2. Next we surround the polygon with a circle
that touches each corner of the polygon.

3. At the points where the polygon touches the

circle, we draw short horizontal
lines outside the circle. The height of each line
represents the relative energy of each
π molecular orbital.
4. Next we draw a dashed horizontal line
across and halfway up the circle. The energies
of bonding π molecular orbitals are below this
line. The energies of antibonding π molecular
orbitals are above, and those for nonbonding
orbitals are at the level of the dashed line.
5. Based on the number of π electrons in the
ring, we then place electron arrows on the
lines corresponding to the respective orbitals,
beginning at the lowest energy level and
working upward. In doing so, we fill
degenerate orbitals each with one electron
first, then add to each unpaired electron
another with opposite spin if it is available.
 The word annulene is incorporated into
the class name for monocyclic compounds
that can be represented by structures having
alternating single and double bonds. The ring
size of an annulene is indicated by a number in
brackets. Thus, benzene is [6]annulene and
cyclooctatetraene is [8]annulene.
Before 1960 the only annulenes that were available to
test Hückel’s predictions were benzene and
cyclooctatetraene. During the 1960s, and largely as a
result of research by F. Sondheimer, a number of large-
ring annulenes were synthesized, and the predictions
of Hückel’s rule were verified.
After many unsuccessful attempts over
many years, in 1965 [4]annulene (or
cyclobutadiene) was synthesized by R.
Pettit and co-workers at the University of
Texas, Austin. Cyclobutadiene is a 4n
molecule, not a 4n + 2 molecule, and, as
we would expect, it is a highly unstable
compound and it is antiaromatic.
 The 1H NMR spectrum of benzene consists
of a single unsplit signal at δ 7.27. That only a single
unsplit signal is observed is further proof that all of
the hydrogens of benzene are equivalent. That the
signal occurs at relatively high frequency is, as we
shall see, compelling evidence for the assertion
that the π electrons of benzene are delocalized.
 By “deshielded” we mean that the protons
sense the sum of the two fields, and, therefore,
the net magnetic field strength is greater than it
would have been in the absence of the induced
field. This strong deshielding, which we attribute to
a ring current created by the delocalized π
electrons, explains why aromatic protons absorb at
relatively high frequency.
 In addition to the neutral molecules that
we have discussed so far, there are a number of
monocyclic species that bear either a positive or
a negative charge. Some of these ions show
unexpected stabilities that suggest that they are
aromatic ions. Hückel’s rule is helpful in
accounting for the properties of these ions as
well. We shall consider two examples: the
cyclopentadienyl anion and the
cycloheptatrienyl cation.
 Cycloheptatriene (a compound
with the common name tropylidene)
has six π electrons. However, the six π
electrons of cycloheptatriene cannot
be fully delocalized because of the
presence of the −CH2− group, a group
that does not have an available p
orbital .
 When cycloheptatriene is treated with
a reagent that can abstract a hydride ion, it is
converted to the cycloheptatrienyl (or
tropylium) cation. The loss of a hydride ion
from cycloheptatriene occurs with
unexpected ease, and the cycloheptatrienyl
cation is found to be unusually stable. The
NMR spectrum of the cycloheptatrienyl
cation indicates that all seven hydrogen
atoms are equivalent.
 An aromatic compound has its π electrons
delocalized over the entire ring and it is stabilized by
the π-electron delocalization. As we have seen, a
good way to determine whether the π electrons of a
cyclic system are delocalized is through the use of
NMR spectroscopy. It provides direct physical
evidence of whether or not the π electrons are
delocalized.
 One way to evaluate whether a cyclic
compound is stabilized by delocalization of π
electrons through its ring is to compare it with an
open-chain compound having the same number of π
electrons. This approach is particularly useful because
it furnishes us with models not only for annulenes but
for aromatic cations and anions, as well.
 To use this approach we do the following:
1. We take as our model a linear chain of sp2-
hybridized atoms having the same number of π
electrons as our cyclic compound.
2. Then we imagine removing a hydrogen atom from
each end of the chain and joining the ends to form a
ring.
• If, based on sound calculations or experiments, the
ring has lower π-electron energy, then the ring is
aromatic.
• If the ring and the chain have the same π-electron
energy, then the ring is nonaromatic.
• If the ring has greater π-electron energy than the
open chain, then the ring is antiaromatic.
• Cyclobutadiene - for cyclobutadiene we consider
the change in π-electron energy for the following
hypothetical transformation:
• Benzene - here our comparison is based on the
following hypothetical transformation:
• Cyclopentadienyl Anion - here we use a linear anion
for our hypothetical transformation:
• Cyclooctatetraene - for cyclooctatetraene we
consider the following hypothetical transformation:
 In addition to those that we have seen so far,
there are many other examples of aromatic
compounds. Representatives of one broad class of
benzenoid aromatic compounds, called polycyclic
aromatic hydrocarbons (PAH).
 The total number of π electrons in pyrene is 16
(8 double bonds = 16 π electrons). Sixteen is a non-
Hückel number, but Hückel’s rule is intended to be
applied only to monocyclic compounds and pyrene is
clearly tetracyclic.
 Naphthalene, phenanthrene, and
anthracene are examples of benzenoid aromatic
compounds. On the other hand, the
cyclopentadienyl anion, the cycloheptatrienyl
cation, trans-15,16-dimethyldihydropyrene, and
the aromatic annulenes (except for [6]annulene)
are classified as nonbenzenoid aromatic
compounds.
 In 1990 W. Krätschmer (Max Planck Institute,
Heidelberg), D. Huffman (University of Arizona), and
their co-workers described the first practical synthesis
of C60, a molecule shaped like a soccer ball and called
buckminsterfullerene. Formed by the resistive heating
of graphite in an inert atmosphere, C60 is a member of
an exciting new group of aromatic compounds called
fullerenes.
 Fullerenes are cage like
molecules with the geometry of a
truncated icosahedron or geodesic
dome, named after the architect
Buckminster Fuller, renowned for his
development of structures with
geodesic domes.
 Almost all of the cyclic molecules that we have
discussed so far have had rings composed solely of
carbon atoms. However, in many cyclic compounds
an element other than carbon is present in the ring.
Cyclic compounds that include an element other than
carbon are called heterocyclic compounds.
 Compounds with aromatic rings
occupy numerous and important
positions in reactions that occur in living
systems. Here are some examples
 Two amino acids necessary for protein
synthesis contain the benzene ring:
 A third aromatic amino acid,
tryptophan, contains a benzene ring fused
to a pyrrole ring. This aromatic ring system
is called an indole system.
 Heterocyclic aromatic compounds are
also present in many biochemical systems.
Derivatives of purine and pyrimidine are
essential parts of DNA and RNA:
 Nicotinamide adenine dinucleotide, one
of the most important coenzymes in biological
oxidations and reductions, includes both a
pyridine derivative (nicotinamide) and a purine
derivative (adenine) in its structure.