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MBMB 1212: General Chemistry

Chapter 2: Resonance and Aromatic compounds

September– December 2022

Chapter 2A: Resonance

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The Inadequacy of Bond-Line Structures

• We have seen that bond-line structures are generally
the most efficient and preferred way to draw the
structure of an organic compound. Nevertheless, bond-
line structures suffer from one major defect.
Specifically, a pair of bonding electrons is always
represented as a line that is drawn between two atoms,
which implies that the bonding electrons are confined
to a region of space directly in between two atoms.

The Inadequacy of Bond-Line Structures

• In this case, the π electrons are in fact located where
they are drawn, in between the two central carbon
atoms. But in other cases, the electron density is spread
out over a larger region of the molecule. For example,
consider the following ion, called an allyl carbocation

• It might seem from the drawing above that there are

two π electrons on the left side and a positive charge on
the right side. But this is not the entire picture, and the
drawing above is inadequate. Let’s take a closer look
and first analyze the hybridization states
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The overlapping p orbitals of an allylic

carbocation
Look at the continuous system
of p orbitals, which functions
as a “conduit,” allowing the two
π electrons to be associated
with all three carbon atoms.
Valence bond theory is
inadequate for analysis of this
system because it treats the
electrons as if they were
confined between only two
atoms

Resonance
• Resonance is the use of two or more valid (or contributing) Lewis
structures to represent the covalent bonding in a molecule. The
valid structures are referred to as resonance structures. It is now
understood that the actual structure of a molecule which displays
resonance is that of an average or a hybrid of all the
valid resonance structures

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Resonance
The approach that chemists use to deal with the inadequacy of bond-
line structures is called resonance. According to this approach, we
draw more than one bond-line structure and then mentally meld
them together

These drawings are called resonance structures, and they show

that the positive charge is spread over two locations. Notice that
we separate resonance structures with a straight, two-headed
arrow, and we place brackets around the structures. The arrow and
brackets indicate that the drawings are resonance structures of one
entity. This one entity, called a resonance hybrid, is not flipping
back and forth between the different resonance structures 7

The allyl carbocation

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Resonance

A person who has never before seen a nectarine asks a farmer to

describe a nectarine. The farmer answers:
• Picture a peach in your mind, and now picture a plum in your
mind. Well, a nectarine has features of both fruits: the inside
tastes like a peach, the outside is smooth like a plum, and the
color is somewhere in between the color of a peach and the
color of a plum. So take your image of a peach together with
your image of a plum and meld them together in your mind
into one image. That’s a nectarine

Resonance hybrid
• Because neither of the contributors exists the average
or hybrid is much more appropriate

vs.
δ+ δ+

resonance hybrid

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Delocalized and Localized Lone Pairs

Delocalized Lone Pairs

Recall the lone pair that is allylic to a π bond. Such a lone pair
will participate in resonance and is said to be delocalized. When
an atom possesses a delocalized lone pair, the geometry of that
atom is affected by the presence of the lone pair. As an example,
consider the structure of an amide:

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Delocalized Lone Pairs

The rules we learned would suggest that the nitrogen atom

should be sp3 hybridized and trigonal pyramidal, but this is not
correct. Instead, the nitrogen atom is actually sp2 hybridized and
trigonal planar. The lone pair is participating in resonance and is
therefore delocalized:

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Delocalized Lone Pairs

In the second resonance structure above, the nitrogen atom

does not bear a lone pair. Rather, the nitrogen atom bears a p
orbital being used to form a π bond. In that resonance structure,
the nitrogen atom is clearly sp2 hybridized. This creates a
conflict: How can the nitrogen atom be sp3 hybridized in one
resonance structure and sp2 hybridized in the other structure?
That would imply that the geometry of the nitrogen atom is
flipping back and forth between trigonal pyramidal and trigonal
planar. This cannot be the case, because resonance is not a
physical process
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The planar structure of an amide

Recall that peptide bonds are amide linkages and that amides
have a significant resonance structure that endows the C-N bond
with some double-bond character

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The Geometry of Peptide Bonds

• As a result, the nitrogen atom is sp2 hybridized and planar
(Figure 25.5). Peptide bonds are simply amides, and therefore
exhibit double-bond character just like regular amides. As
such, a peptide bond experiences restricted rotation, giving
rise to two possible conformations called s-trans and s-cis

• The s-trans conformation is usually more stable because it

lacks steric hindrance that is present in the s-cis conformation

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The Geometry of Peptide Bonds

• In a polypeptide, each peptide bond will show a preference for
adopting an s-trans conformation. Nevertheless, polypeptides are
not entirely planar, because they still possess σ bonds that
experience free rotation. Only the peptide bonds experience
restricted rotation
• As a result, polypeptides can assume a variety of conformations

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Delocalized Lone Pairs

The nitrogen atom is actually sp2 hybridized and trigonal planar in
both resonance structures. How? The nitrogen atom has a
delocalized lone pair, and it therefore occupies a p orbital (rather
than a hybridized orbital), so that it can overlap with the p orbitals of
the π bond. Whenever a lone pair participates in resonance, it will
occupy a p orbital rather than a hybridized orbital, and this must be
taken into account when predicting geometry

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Localized Lone Pairs

A localized lone pair, by definition, is a lone pair that does not
participate in resonance. In other words, the lone pair is not allylic to
a π bond:

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Localized Lone Pairs

In some cases, a lone pair might appear to be delocalized even
though it is actually localized. For example, consider the structure of
pyridine:

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Localized Lone Pairs

In this case, the lone pair on the nitrogen atom is actually not
participating in resonance, even though it is next to a π bond. Recall,
that in order for a lone pair to participate in resonance, it must
occupy a p orbital that can overlap with the neighboring p orbitals,
forming a “conduit”

In the case of pyridine, the nitrogen atom is already using a p orbital

for the π bond. The nitrogen atom can only use one p orbital to join
in the conduit, and that p orbital is already being utilized by the π
bond

As a result, the lone pair cannot join in the conduit, and therefore it
cannot participate in resonance. In this case, the lone pair occupies
an sp2-hybridized orbital, which is in the plane of the ring
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Localized Lone Pairs

As a result, the lone pair cannot join in the conduit, and therefore it
cannot participate in resonance. In this case, the lone pair occupies
an sp2-hybridized orbital, which is in the plane of the ring

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Localized Lone Pairs

Here is the bottom line: Whenever an atom possesses both a π
bond and a lone pair, they will not both participate in resonance.
In general, only the π bond will participate in resonance, and the
lone pair will not

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Exercise
1. Histamine is a compound that plays a key role in many
biological functions. Most notably, it is involved in immune
responses, where it triggers the symptoms of allergic
reactions:

Each nitrogen atom exhibits a lone pair. In each case, identify

whether the lone pair is localized or delocalized, and then use
that information to determine the hybridization state and
geometry for each nitrogen atom in histamine

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Exercise
2. Nicotine is a toxic substance present in tobacco leaves

There are two lone pairs in the structure of nicotine. In general,

localized lone pairs are much more reactive than delocalized
lone pairs. With this information in mind, doyou expect both
lone pairs in nicotine to be reactive? Justify your answer

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Exercise
3. Isoniazid is used in the treatment of tuberculosis and
multiple sclerosis. Identify each lone pair as either localized
or delocalized. Justify your answer in each case

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Chapter 2B: Aromatic compounds

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Introduction to Aromatic compounds

• AROMATIC compounds or ARENES include benzene and
benzene derivatives

• Coal contains aromatic rings fused together and joined

by nonromantic moieties

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Introduction to Aromatic compounds

• Many derivatives of benzene were originally isolated
from the fragrant balsams obtained from trees and
plants, and these compounds were therefore described
as being aromatic in reference to their pleasant odors

• Over time, chemists discovered that many derivatives of

benzene are, in fact, odorless. Nevertheless, the term
“aromatic” is still used to describe all derivatives of
benzene, regardless of whether they are fragrant or
odorless
• The aromatic moiety—the benzene ring—is a
particularly common structural feature in drugs. In fact, 8
of the 10 best-selling drugs in 2007 contained the
benzene-like aromatic moiety (highlighted in red)
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Introduction to Aromatic compounds

• The aromatic moiety—the benzene ring—is a
particularly common structural feature in drugs. In fact, 8
of the 10 best-selling drugs in 2007 (over $38 billion in
global sales) contained the benzene-like aromatic moiety
(highlighted in red)

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Introduction to Aromatic compounds

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Nomenclature of Benzene Derivatives

Benzene is generally the parent name for
monosubstituted derivatives

Nomenclature of Benzene Derivatives

• Many benzene derivatives have common names
• For some compounds, the common name becomes the
parent name

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Nomenclature of Benzene Derivatives

• If the substituent is larger than the ring, the substituent
becomes the parent chain

• Aromatic rings are often represented with a Ph (for

phenyl) or with a φ (phi) symbol

Nomenclature of Benzene Derivatives

• The common name for dimethyl benzene derivatives is
XYLENE

• What do ORTHO, META, and PARA mean?

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Nomenclature of Benzene Derivatives

1. Identify the parent chain (usually the benzene ring,
perhaps including one of its substituents)
2. Identify and name the substituents
3. Number the parent chain and assign a locant (and
prefix if necessary) to each substituent
– Give the substituent that determines the root name
the lowest number possible
4. List the numbered substituents before the parent
name in alphabetical order
– Ignore prefixes (except iso) when ordering
alphabetically

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Nomenclature of Benzene Derivatives

Locants are required for rings with more than 2 substituents
1. Identify the parent chain (generally the aromatic ring):
– A common name can be the parent chain

2. Identify and name the substituents

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Nomenclature of Benzene Derivatives

3. Number the parent chain and assign a locant (and
prefix if necessary) to each substituent.
– A substituent that is part of the parent
name must be assigned locant NUMBER 1

4. List the numbered substituents before the parent

name in alphabetical order:
– Complete the name for the molecule above

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Exercise
Name the following molecules

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The structure of Benzene

• In 1866, August Kekulé proposed that benzene is a ring
comprised of alternating double and single bonds

• Kekulé suggested that the exchange of double and

single bonds was an equilibrium process
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“Again the atoms were

gamboling before my eyes. …
My mental eye, rendered more
acute by repeated visions of
the kind, could now distinguish
larger structures, of manifold
conformation: long rows,
sometimes more closely fitted
together; all twining and
twisting in snake-like motion.
But look! What was that? One
of the snakes had seized hold of
its own tail, and the form whirled
mockingly before my eyes. As if
by a flash of lightning I awoke; Friedrich August
and this time also I spent the Kekulé von Stradonitz
rest of the night in working out (1829-1896)
the consequences of the 40
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hypothesis.”

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Structure of Benzene
• We now know that the aromatic structures are
resonance contributors rather than in equilibrium

• HOW is resonance different from equilibrium?

• Sometimes the ring is represented with a circle in it,
but you can’t do this when drawing mechanisms

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Stability of Benzene
• The stability that results from a ring being aromatic is
higher than what would be expected from simple
resonance
• Recall that in general, alkenes readily undergo addition
reactions

• Aromatic rings are stable enough that they do not

undergo such reactions

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Stability of Benzene
• Heats of hydrogenation can be used to quantify
aromatic stability

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Stability of Benzene
• Molecular orbital theory can help us explain aromatic
stability
• The six atomic p orbitals of benzene overlap to make six
molecular orbitals
• The delocalization of the six pi electrons in the three
bonding molecular orbitals accounts for the stability of
benzene

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Hückel’s Rule

• Benzene is aromatic because it has 3 pairs of  electrons

• The requirement for an odd number of electron pairs is called

Hückel’s rule. Specifically, a compound can only be aromatic if
the number of π electrons in the ring is 2, 6, 10, 14, 18, and so
on. This series of numbers can be expressed mathematically
as 4n + 2, where n is a whole number

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The Criteria for Aromaticity

Benzene is not the only compound that exhibits aromatic
stabilization. A compound will be aromatic if it satisfies the
following two criteria;

1. The compound must contain a ring comprised of

continuously overlapping p orbitals
2. The number of π electrons in the ring must be a Hückel
number

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The Criteria for Aromaticity

Compounds that fail the first criterion are called
nonaromatic. Below are three examples, each of which fails
the first criterion for a different reason

The first compound (1,3,5-hexatriene) is not aromatic, because it

does not possess a ring. The second compound is not aromatic
because the ring is not a continuous system of p orbitals (there is
an intervening sp3-hybridized carbon atom). The third compound
is not planar, and the p orbitals do not effectively overlap

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Aromatic Heterocycles
• Cyclic compounds containing heteroatoms (such as S, N,
or O) are called heterocycles. Below are two examples of
nitrogen-containing heterocycles

• Both of these compounds are aromatic, but for very

different reasons. We will discuss them first separately,
and then compare them to each other

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Aromatic Heterocycles

• Pyridine exhibits a continuous system of overlapping p

orbitals and therefore satisfies the first criterion for
aromaticity. The nitrogen atom is sp2 hybridized, and the
lone pair on the nitrogen atom occupies an sp2-hybridized
orbital, which is pointing away from the ring. This lone pair is
not part of the conjugated system and therefore is not
included when we count the number of π electrons
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Aromatic Heterocycles
In this case, there are six π electrons, so the compound is
aromatic. Since the lone pair of pyridine does not participate in
resonance or aromaticity, it is free to function as a base

Pyridine can function as a base because protonation of the

nitrogen atom does not destroy aromaticity

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Aromatic Heterocycles

Now let’s analyze the structure of pyrrole. Once again, the

nitrogen atom is sp2 hybridized, but in this case, the lone
pair occupies a p orbital. In order for the pyrrole ring to
achieve a continuous system of overlapping p orbitals, the
lone pair of the nitrogen atom must occupy a p orbital

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Aromatic Heterocycles
• With six π electrons (four from the π bonds and two from
the lone pair), this compound is aromatic. In this case, the
lone pair is crucial in establishing aromaticity
• The delocalized nature of the lone pair explains why
pyrrole does not readily function as a base. Protonation of
the lone pair on nitrogen effectively destroys the p orbital
overlap, thereby destroying aromaticity

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Aromatic Heterocycles
The difference between pyridine and pyrrole can be seen in
their electrostatic potential maps

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Polycyclic Aromatic Compounds

Hückel’s rule (4n + 2) can only be applied to compounds that
exhibit a single ring of overlapping p orbitals (monocyclic
compounds). Nevertheless, many polycyclic aromatic
hydrocarbons (PAHs) are known to be stable and have been
thoroughly studied:

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