Organic Chemistry

BKF1323
Chapter 2
2.5 Aromatic Compounds
 Benzene and Aromatic Compounds
Background

Benzene (C6H6) is the simplest aromatic hydrocarbon (or

arene).
Benzene has four degrees of unsaturation, making it a
highly unsaturated hydrocarbon.
Whereas unsaturated hydrocarbons such as alkenes,
alkynes and dienes readily undergo addition reactions,
benzene does not.
 Benzene and Aromatic Compounds
Background
These structures are known as Kekul structures.

Although benzene is still drawn as a six-membered ring with

alternating bonds, in reality there is no equilibrium between the
two different kinds of benzene molecules.
Current descriptions of benzene are based on resonance and
electron delocalization due to orbital overlap.
In the nineteenth century, many other compounds having
properties similar to those of benzene were isolated from natural
sources. Since these compounds possessed strong and
characteristic odors, they were called aromatic compounds. It
should be noted however, that it is their chemical properties, and
not their odor, that make them special.
 Benzene and Aromatic Compounds
The Structure of Benzene
Any structure for benzene must account for the following facts:
1. It contains a six-membered ring and three additional
degrees of unsaturation.
2. It is planar.
3. All CC bond lengths are equal.
The Kekul structures satisfy the first two criteria but not the
third, because having three alternating bonds means that
benzene should have three short double bonds alternating with
three longer single bonds.
 Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives
To name a benzene ring with one substituent, name the
substituent and add the word benzene.

Many monosubstituted benzenes have common names

which you must also learn.
 Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives
There are three different ways that two groups can be
attached to a benzene ring, so a prefixortho, meta, or
paracan be used to designate the relative position of
the two substituents.

ortho-dibromobenzene meta-dibromobenzene para-dibromobenzene

or or or
o-dibromobenzene m-dibromobenzene p-dibromobenzene
or 1,2-dibromobenzene or 1,3-dibromobenzene or 1,4-dibromobenzene
 Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives
If the two groups on the benzene ring are different,
alphabetize the names of the substituents preceding the
word benzene.
If one substituent is part of a common root, name the
molecule as a derivative of that monosubstituted
benzene.
 Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives
For three or more substituents on a benzene ring:
1. Number to give the lowest possible numbers around the ring.
2. Alphabetize the substituent names.
3. When substituents are part of common roots, name the
molecule as a derivative of that monosubstituted benzene. The
substituent that comprises the common root is located at C1.
 Benzene and Aromatic Compounds
The Criteria for AromaticityHckels Rule
Four structural criteria must be satisfied for a compound
to be aromatic.
[1] A molecule must be cyclic.

To be aromatic, each p orbital must overlap with p orbitals

on adjacent atoms.
 Benzene and Aromatic Compounds
The Criteria for AromaticityHckels Rule
[2] A molecule must be planar.
All adjacent p orbitals must be aligned so that the
electron density can be delocalized.

Since cyclooctatetraene is non-planar, it is not aromatic,

and it undergoes addition reactions just like those of other
alkenes.
 Benzene and Aromatic Compounds
The Criteria for AromaticityHckels Rule

[3] A molecule must be completely conjugated.

Aromatic compounds must have a p orbital on every atom.
 Benzene and Aromatic Compounds
The Criteria for AromaticityHckels Rule
[4] A molecule must satisfy Hckels rule, and contain
a particular number of electrons.
Hckel's rule:

Benzene is aromatic and especially stable because it

contains 6 electrons. Cyclobutadiene is antiaromatic
and especially unstable because it contains 4 electrons.
 Reactions: Electrophilic Aromatic Substitution
Background
The characteristic reaction of benzene is electrophilic aromatic
substitutiona hydrogen atom is replaced by an electrophile.
 Electrophilic Aromatic Substitution
Background
Regardless of the electrophile used, all electrophilic aromatic
substitution reactions occur by the same two-step mechanism
addition of the electrophile E+ to form a resonance-stabilized
carbocation, followed by deprotonation with base, as shown
below:
 Electrophilic Aromatic Substitution
1. Halogenation
In halogenation, benzene reacts with Cl2 or Br2 in the
presence of a Lewis acid catalyst, such as FeCl 3 or
FeBr3, to give the aryl halides chlorobenzene or
bromobenzene respectively.
Analogous reactions with I2 and F2 are not synthetically
useful because I2 is too unreactive and F2 reacts too
violently.
 Electrophilic Aromatic Substitution
1. Halogenation
Chlorination proceeds by a similar mechanism.
 Electrophilic Aromatic Substitution
2. Nitration and Sulfonation
Nitration and sulfonation introduce two different functional
groups into the aromatic ring.
Nitration is especially useful because the nitro group can be
reduced to an NH2 group.
 Electrophilic Aromatic Substitution
2. Nitration and Sulfonation
Generation of the electrophile in both nitration and sulfonation
requires strong acid.
 Electrophilic Aromatic Substitution
3. Friedel-Crafts Alkylation and Friedel-Crafts
Acylation
In Friedel-Crafts alkylation, treatment of benzene with an
alkyl halide and a Lewis acid (AlCl3) forms an alkyl
benzene.
 Electrophilic Aromatic Substitution
3. Friedel-Crafts Alkylation and Friedel-Crafts
Acylation
In Friedel-Crafts acylation, a benzene ring is treated with
an acid chloride (RCOCl) and AlCl3 to form a ketone.
Because the new group bonded to the benzene ring is
called an acyl group, the transfer of an acyl group from
one atom to another is an acylation.
 Electrophilic Aromatic Substitution
3. Friedel-Crafts Alkylation and Friedel-Crafts
Acylation

Three additional facts about Friedel-Crafts alkylation

should be kept in mind.
[1] Vinyl halides and aryl halides do not react in Friedel-
Crafts alkylation.
 Electrophilic Aromatic Substitution
3. Friedel-Crafts Alkylation and Friedel-Crafts
Acylation
[2] Rearrangements can occur.

These results can be explained by carbocation

rearrangements.
 Electrophilic Aromatic Substitution
Friedel-Crafts Alkylation and Friedel-Crafts Acylation
[3] Other functional groups that form carbocations can
also be used as starting materials.
 Electrophilic Aromatic Substitution
Substituted Benzenes
Many substituted benzene rings undergo electrophilic
aromatic substitution.
Each substituent either increases or decreases the
electron density in the benzene ring, and this affects the
course of electrophilic aromatic substitution.
 Electrophilic Aromatic Substitution
Substituted Benzenes

These compounds represent examples of the general

structural features in electron-donating and electron
withdrawing substituents.
 Electrophilic Aromatic Substitution
Electrophilic Aromatic Substitution and Substituted
Benzenes.
Electrophilic aromatic substitution is a general
reaction of all aromatic compounds, including
polycyclic aromatic hydrocarbons, heterocycles, and
substituted benzene derivatives.
A substituent affects two aspects of the electrophilic
aromatic substitution reaction:
1. The rate of the reaction A substituted benzene
reacts faster or slower than benzene itself.
2. The orientation The new group is located either
ortho, meta, or para to the existing substituent. The
identity of the first substituent determines the
position of the second incoming substituent.
 Electrophilic Aromatic Substitution
Electrophilic Aromatic Substitution and Substituted
Benzenes.

All substituents can be divided into three general types:

 Electrophilic Aromatic Substitution
Electrophilic Aromatic Substitution and Substituted
Benzenes.
 Electrophilic Aromatic Substitution
Electrophilic Aromatic Substitution and Substituted
Benzenes.
Consider tolueneToluene reacts faster than benzene in
all substitution reactions.
The electron-donating CH3 group activates the benzene
ring to electrophilic attack.
Ortho and para products predominate.
The CH3 group is called an ortho, para director.
 Electrophilic Aromatic Substitution
Electrophilic Aromatic Substitution and Substituted
Benzenes.
Consider nitrobenzeneIt reacts more slowly than
benzene in all substitution reactions.
The electron-withdrawing NO2 group deactivates the
benzene ring to electrophilic attack.
The meta product predominates.
The NO2 group is called a meta director.
 Electrophilic Aromatic Substitution
Oxidation and Reduction of Substituted Benzenes
Ketones formed as products of Friedel-Crafts acylation can be
reduced to alkyl benzenes by two different methods:
1. The Clemmenson reductionuses zinc and mercury in the
presence of strong acid.
2. The Wolff-Kishner reductionuses hydrazine (NH2NH2) and
strong base (KOH).
 Electrophilic Aromatic Substitution
Oxidation and Reduction of Substituted Benzenes
We now know two different ways to introduce an alkyl group on a
benzene ring:
1. A one-step method using Friedel-Crafts alkylation.
2. A two-step method using Friedel-Crafts acylation to form a
ketone, followed by reduction.
 Electrophilic Aromatic Substitution
Oxidation and Reduction of Substituted Benzenes
Although the two-step method seems more roundabout, it must be
used to synthesize certain alkyl benzenes that cannot be prepared
by the one-step Friedel-Crafts alkylation because of
rearrangements.
 Electrophilic Aromatic Substitution
Oxidation and Reduction of Substituted Benzenes

A nitro group (NO2) that has been introduced on a benzene

ring by nitration with strong acid can readily be reduced to
an amino group (NH2) under a variety of conditions.
 Ex 1: Draw the structures of
the following
1. 2,4-dinitrophenol
2. p-bromotoluene
3. m-chlorobenzaldehyde
4. 1,2-diphenylethane
5. 2,4,6-tribromoaniline
6. 2-chloro-4-cyclohexylanisole
7. 3,5-dimethoxybenzaldehyde
8. 1,4-diphenyl-1,3-butadiene
 Ex 2
1. Show the mechanism for benzene nitration
2. Starting from benzene, show how to synthesize,
i. m-chloronitrobenzene
ii. p-chlorobenzoic acid
iii. 3-bromonitrobenzene
iv. 4-nitroethylbenzene
3. Suggest the reaction mechanism for benzene
with
i. Acethyl chloride / AlCl3
ii. Isobutyl bromide / AlBr3
THANK YOU