CH 14

Chapter 14
Aromatic Compounds
Created by
Professor William Tam & Dr. Phillis Chang
Copyright © 2014 by John Wiley & Sons, Inc. All rights reserved.
About The Authors
These PowerPoint Lecture Slides were created and prepared by Professor
William Tam and his wife, Dr. Phillis Chang.
Professor William Tam received his B.Sc. at the University of Hong Kong in
1990 and his Ph.D. at the University of Toronto (Canada) in 1995. He was an
NSERC postdoctoral fellow at the Imperial College (UK) and at Harvard
University (USA). He joined the Department of Chemistry at the University of
Guelph (Ontario, Canada) in 1998 and is currently a Full Professor and
Associate Chair in the department. Professor Tam has received several awards
in research and teaching, and according to Essential Science Indicators, he is
currently ranked as the Top 1% most cited Chemists worldwide. He has
published four books and over 80 scientific papers in top international journals
such as J. Am. Chem. Soc., Angew. Chem., Org. Lett., and J. Org. Chem.
Dr. Phillis Chang received her B.Sc. at New York University (USA) in 1994, her
M.Sc. and Ph.D. in 1997 and 2001 at the University of Guelph (Canada). She
lives in Guelph with her husband, William, and their son, Matthew.
© 2014 by John Wiley & Sons, Inc. All rights reserved.

Table of Contents (hyperlinked)
1. The Discovery of Benzene
2. Nomenclature of Benzene Derivatives
3. Reactions of Benzene
4. The Kekulé Structure for Benzene
5. The Thermodynamic Stability of Benzene
6. Modern Theories of the Structure
of Benzene
7. Hückel’s Rule: The 4n + 2 p Electron Rule
8. Other Aromatic Compounds
9. Heterocyclic Aromatic Compounds
10. Aromatic Compounds in Biochemistry
11. Spectroscopy of Aromatic Compounds
Table of Contents
2. Nomenclature of Benzene Derivatives
4. The Kekulé Structure for Benzene
5. The Thermodynamic Stability of Benzene
6. Modern Theories of the Structure of
Benzene
7. Hückel’s Rule: The 4n + 2 p Electron Rule
9. Heterocyclic Aromatic Compounds
10. Aromatic Compounds in Biochemistry
11. Spectroscopy of Aromatic Compounds
In this chapter we will consider:
 The structural principles that underlie
the use of the term “aromatic”
 The initial challenge of determining the
correct structure of benzene
 A rule that helps to predict what kinds
of molecules possess the special
property of aromaticity
 Special groups of molecules that are
also aromatic
 Benzene: or
 In 1825, Faraday isolated benzene

from a compressed illuminating gas
that had been made by pyrolyzing
whale oil

 In 1834, a German chemist, Eilhardt
Mitscherlich, synthesized benzene by
heating benzoic acid with calcium oxide
COOH
heat
+ CaO + CaCO3

 In the 19th century, organic compounds
were classified as being either
aliphatic or aromatic
 Aliphatic
● The chemical behavior of a
compound was “fatlike”
 Aromatic
● The compound had a low
hydrogen-to-carbon ratio and was
“fragrant”

2. Nomenclature of Benzene
Derivatives
 Naming monosubstituted benzenes
● In many simple compounds, benzene is
the parent name and the substituent is
simply indicated by a prefix
F Cl Br NO2
Fluorobenzene Chlorobenzene Bromobenzene Nitrobenzene

● For other simple and common
compounds, the substituent and the
benzene ring taken together may form a
commonly accepted parent name
H H H CH3
CH3 O N SO3H O
Toluene Phenol Aniline Benzene- Anisole

sulfonic acid
O O
OH
Benzoic acid Acetophenone
 Naming disubstituted benzenes
● When two substituents are present,
their relative positions are indicated by
the prefixes ortho-, meta-, and para-
(abbreviated o-, m-, and p-) or by the
use of numbers
Br
Br Br
Br Br Br
1,2-Dibromobenzene 1,3-Dibromobenzene 1,4-Dibromobenzene

(o-dibromobenzene) (m-dibromobenzene) (p-dibromobenzene)
ortho meta para
● Other examples
CH3
NO2 Cl
COOH OH CH3
2-Nitrobenzoic acid 3-Methylphenol 4-Chlorotoluene

(o-Nitrobenzoic acid) (m-Methylphenol) (p-Chlorotoluene)
(1-Chloro-4-methyl-
benzene)

● The dimethylbenzenes are often
called xylenes
CH3
CH3 H3C
CH3 CH3 CH3
1,2-Dimethylbenzene 1,3-Dimethylbenzene 1,4-Dimethylbenzene

(o-xylene) (m-xylene) (p-xylene)

 Naming benzene rings with more than
two groups
● If more than two groups are present on
the benzene ring, their positions must
be indicated by the use of numbers
● The benzene ring is numbered so as to
give the lowest possible numbers to
the substituents
Cl Br
1 1
2 Cl 2 Br
6 6
5
3
5
3 1,2,4-Tribromobenzene
4 Cl 4 (not 1,3,4-Tribromobenzene)
1,2,3-Trichlorobenzene Br
● When more than two substituents
are present and the substituents
are different, they are listed in
alphabetical order
Cl
1
2 F
6
3
5
4
Br
4-Bromo-1-chloro-2-fluorobenzene
● When a substituent is one that,
together with the benzene ring
gives a new base name, that
substituent is assumed to be in
position 1 and the new parent
name is used
Cl COOH
3 1
H3C 2
4 2 6
5 1
3
5
Cl 6 OH 4 Br
3,5-Dichlorophenol 5-Bromo-2-methylbenzoic acid
● When the C6H5 group is named as a
substituent, it is called a phenyl
group
● A hydrocarbon composed of one
saturated chain and one benzene
ring is usually named as a
derivative of the larger structural
unit. However, if the chain is
unsaturated, the compound may be
named as a derivative of that chain,
regardless of ring size
● Examples
Butylbenzene Isopropylbenzene
2 4
1 3 5 7
1 3 2 4 6 8
trans-1-Phenyl-1-butene (R)-3-Phenyloctane
● Benzyl is an alternative name for
the phenylmethyl group. It is
sometimes abbreviated Bn.
Cl
The benzyl group Benzyl chloride

(the phenylmethyl group) (phenylmethyl chloride
or BnCl)

Br
Br2
CCl 4
Br
Br2
No Reaction
CCl 4

OH
1. OsO4
2. NaHSO3
OH
1. OsO4
No Reaction
2. NaHSO3

OH
H+
H2O
H+
No Reaction
H2O

H2/Ni
25oC, 1 atm
H2/Ni
high temperature
and pressure

 Benzene undergoes substitution, but
not addition
Br
Br2
(an addition)
CCl 4
Br
(C6H10) (C6H10Br2)
H Br
Br2
(a substitution)
FeBr3
(a Lewis acid)
(C6H6) (C6H5Br)
4. The Kekulé Structure for
Benzene
H
H C H
C C
or
C C
H C H
H
The Kekulé formula for benzene

6 6
1 Br 1 Br
5 5
and
4 2 4 2
3
Br 3
Br
These 1,2-dibromobenzenes
do not exist as isomers
6 6
1 Br 1 Br
5 5
4 2
X 4 2
3
Br 3
Br
There is no such equilibrium between

benzene ring bond isomers
Br2
No Reaction
Br
Br2
Br

5. The Thermodynamic Stability
of Benzene
 Since p bonds are formed from side-way overlap of
p orbitals, p electron clouds are above & below the
plane of the double bond
p-electrons above
and below ring

6. Modern Theories of the
Structure of Benzene
6A. The Resonance Explanation of the
Structure of Benzene
 All C C bond lengths the same (1.39 Å)

(compare with C—C single bond 1.54 Å, C=C
double bond 1.34 Å)
 Extra stabilization due to resonance 
aromatic
 3-D structure
p-electrons above
and below ring
● Planar structure
● All carbons sp2 hybridized
6B. The Molecular Orbital Explanation
of the Structure of Benzene

7. Hückel’s Rule: The (4n + 2) p
Electron Rule
 Hückel’s rule is concerned with
compounds containing one planar ring in
which each atom has a p orbital as in
benzene
 Planar monocyclic rings containing (4n + 2)
p electrons, where n = 0, 1, 2, 3, and so on
(i.e., rings containing 2, 6, 10, 14 . . . etc. p
electrons), have closed shells of delocalized
electrons like benzene and have substantial
resonance energies
 Hückel’s rule states that planar
monocyclic rings with 2, 6, 10, 14 .
. . delocalized electrons should be
aromatic

7A. How To Diagram the Relative
Energies of p Molecular Orbitals in
Monocyclic Systems Based on
Hückel’s Rule
antibonding  orbitals
nonbonding  orbital
bonding  orbitals
Polygon in circle Energy levels of MOs Type of  orbital

 The p molecular orbitals that cyclooctatetraene
would have if it were planar. Notice that, unlike
benzene, this molecule is predicted to have two
nonbonding orbitals, and because it has eight p
electrons, it would have an unpaired electron in
each of the two nonbonding orbitals. Such a
system would not be expected to be aromatic.
 The bonds of cyclooctatetraene are
known to be alternately long and short;
X-ray studies indicate that they are
1.48 and 1.34 Å, respectively, and that
the molecule has a tub-like shape
7B. The Annulenes
 Hückel’s rule predicts that annulenes
will be aromatic if their molecules have
(4n + 2) p electrons and have a planar
carbon skeleton

 All these (4n + 2) p, planar
annulenes are aromatic
(4n + 2)  Benzene [14]Annulene

planar annulenes: [6]Annulene (aromatic)
[18]Annulene
(aromatic)

 Non-planar (4n + 2) p annulenes are
non-aromatic
H
H
[10]Annulenes
(None are aromatic
because none are planar)

 (4n) p non-planar annulenes are
antiaromatic
Cyclobutadiene [8]Annulene [16]Annulene

[4]Annulene

7C. NMR Spectroscopy: Evidence for
Electron Delocalization in
Aromatic Compounds
 The 1H NMR spectrum of benzene
consists of a single unsplit signal at
d 7.27
 The signal occurs at relatively high
frequency, which is compelling
evidence for the assertion that the p
electrons of benzene are delocalized
 The circulation of p electrons in
benzene creates an induced magnetic
field that, at the position of the
protons, reinforces the applied
magnetic field. This reinforcement
causes the protons to be strongly
deshielded and to have a relatively
high frequency (d ~ 7) absorption

H H
(d 9.3)
H H
H
H H H H
(d -3.0)
H H H H
H
H H
H H
7D. Aromatic Ions
pka = 36
pka = 16
H H
H H

H
H H
Bu Li
(a strong base)
6 p electrons
 aromatic
H strong
base H
H
sp3 sp2
H H
- H+
8  electrons
(antiaromatic)
H H
- H
6  electrons
(aromatic)
7E. Aromatic, Antiaromatic, and
Nonaromatic Compounds
 An aromatic compound has its p
electrons delocalized over the entire
ring and it is stabilized by the p-
electron delocalization

 One way to evaluate whether a cyclic
compound is stabilized by
delocalization of p electrons through its
ring is to compare it with an open-
chain compound having the same
number of p electrons

 Based on sound calculations or
experiments
● If the ring has lower p-electron
energy, then the ring is aromatic
● If the ring and the chain have the
same p-electron energy, then the
ring is nonaromatic
● If the ring has greater p-electron
energy than the open chain, then
the ring is antiaromatic
 Cyclobutadiene
-electron
+ H2
energy increases
1,3-Butadiene Cyclobutadiene
4  electrons 4  electrons
(antiaromatic)
 Benzene
-electron
+ H2
energy decreases
1,3,5-Hexatriene Benzene
6  electrons 6  electrons
(aromatic)
8A. Benzenoid Aromatic Compounds
 Benzenoid polycyclic aromatic hydrocarbons
consist of molecules having two or more
benzene rings fused together
8 1 8 9 1
2 2
Naphthalene 7 7 Anthracene
C10H8 3 3
C14H10
6 6
5 4 5 10 4
6 9 8
5 7 10 7
4
8 6
3
Phenanthrene 1 Pyrene
C14H10 C16H10
2 9 2 5
1 10 3 4

8B. Nonbenzenoid Aromatic
Compounds
(Azulene)

8C. Fullerenes

9. Heterocyclic Aromatic
Compounds
 Cyclic compounds that include an element
other than carbon are called heterocyclic
compounds
4 4 3 4 3 4 3
5 3
5 2 5 2 5 2
6 2
N1 O1 S1
N
1 H
Pyridine Pyrrole Furan Thiophene
(electronically
related to
benzene) (electronically related to
cyclopentadienyl anion)
NH2
 Examples of useful heterocyclic
aromatic compounds HO
HOOC H
N N
S
Serotonin H
(neurotransmitter)
O N
S O O
Penicillin COOH
H
(antibiotic) N
O N
N
O
N
N H
N N
O2N
O
O O S N N
Nitrofurantoin
"Viagra"
(urinary antibacterial) O
 Aromaticity
X X = O, S N
H
X N H
6 e: aromatic

 Aromaticity
● Evidence: 1H NMR shift
H H
H H
Z Z
(2.5 ppm) (3.4 ppm)
H
Z  (ppm)  (5.5 ppm)
O 7.3 6.2
NH 6.4 6.2
H  (7.4 ppm)
S 7.1 7.0

 Basicity of nitrogen-containing
heterocycles
N
Order of Basicity: > > >
N N N N
H H H
pKa of the
conjugate acid: 11.2 7 5.2 0.4
(c.f. Et3N, pKa of the conjugate acid = 9.7)

 Basicity of nitrogen-containing
heterocycles
H
+ H+
N N N H
H H
H H
(loss of aromaticity)
H H H
N N N N
+ H+
N N N N
H Imidazole H H H
(a very common base (still aromatic)
in organic synthesis)
Non-basic
nitrogen
X H N H N H+ X
N N
H
5 (aromatic) (aromatic)
4
1
N H
N
3 2
H
X H N H N + X
N N H
(aromatic) (non-aromatic)
basic 6  electrons 4  electrons
nitrogen
10. Aromatic Compounds in
Biochemistry
 Two amino acids necessary for protein
synthesis contain the benzene ring
O O
O O
NH3 NH3
HO
Phenylalanine Tyrosine

 Derivatives of purine and pyrimidine
are essential parts of DNA and RNA
7
6 4
1 3
5 N 5
N N
8
2 3 6 1 2
N
4 N9 N
H
Purine Pyrimidine

 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
O Nicotinamide Adenine NH2
H2N N
  N
O O
N O P O P O N N
O O O
OH HO
Pyrophosphate
Ribose
O
Ribose
OH OH
11. Spectroscopy of Aromatic
Compounds
11A. 1H NMR Spectra
 The ring hydrogens of benzene derivatives
absorb downfield in the region between d
6.0 and d 9.5 ppm
11B. 13C NMR Spectra

 The carbon atoms of benzene rings
generally absorb in the d 100–170 ppm
region of 13C NMR spectra
N N N N
(d)
(d)
(c) (c)
H O H O H O H O
A B C D

N N N N
(d) (d)
(c) (c)
H O H O H O H O
E F G H

11C. Infrared Spectra of Substituted
Benzenes

11D. Ultraviolet–Visible Spectra of
Aromatic Compounds
Octyl-4-N,N-dimethylaminobenzoate
(Padimate O)
O
max 310 nm
Me2N
2-Ethylhexyl-4-methoxycinnamate
(Parsol MCX)
max 310 nm O
MeO
O OH O
O
H
OMe OH
2-Hydroxy-4-methoxybenzophenone Homomenthyl salicylate
(Oxybenzone) (Homosalate)
max 288 and 325 nm max 309 nm
O
NC
O
2-Ethylhexyl 2-cyano-
3,3-diphenylacrylate
(Octocrylene)
max 310 nm
11E. Mass Spectra of Aromatic
Compounds
CH2
R
m/z = 91 m/z = 91
m/z = 77
 END OF CHAPTER 14 

CH 14

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Chapter 14

© 2014 by John Wiley & Sons, Inc. All rights reserved.

 In 1825, Faraday isolated benzene

© 2014 by John Wiley & Sons, Inc. All rights reserved.

© 2014 by John Wiley & Sons, Inc. All rights reserved.

© 2014 by John Wiley & Sons, Inc. All rights reserved.

Fluorobenzene Chlorobenzene Bromobenzene Nitrobenzene

© 2014 by John Wiley & Sons, Inc. All rights reserved.

Toluene Phenol Aniline Benzene- Anisole

1,2-Dibromobenzene 1,3-Dibromobenzene 1,4-Dibromobenzene

2-Nitrobenzoic acid 3-Methylphenol 4-Chlorotoluene

© 2014 by John Wiley & Sons, Inc. All rights reserved.

CH3 CH3 CH3

1,2-Dimethylbenzene 1,3-Dimethylbenzene 1,4-Dimethylbenzene

© 2014 by John Wiley & Sons, Inc. All rights reserved.

The benzyl group Benzyl chloride

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© 2014 by John Wiley & Sons, Inc. All rights reserved.

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There is no such equilibrium between

© 2014 by John Wiley & Sons, Inc. All rights reserved.

© 2014 by John Wiley & Sons, Inc. All rights reserved.

 All C C bond lengths the same (1.39 Å)

© 2014 by John Wiley & Sons, Inc. All rights reserved.

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Polygon in circle Energy levels of MOs Type of  orbital

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(4n + 2)  Benzene [14]Annulene

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Cyclobutadiene [8]Annulene [16]Annulene

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© 2014 by John Wiley & Sons, Inc. All rights reserved.

© 2014 by John Wiley & Sons, Inc. All rights reserved.

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(c.f. Et3N, pKa of the conjugate acid = 9.7)

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11B. 13C NMR Spectra

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© 2014 by John Wiley & Sons, Inc. All rights reserved.

© 2014 by John Wiley & Sons, Inc. All rights reserved.

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