CHEM 40: Basic Organic Chemistry

Module 4b: Unsaturated Hydrocarbons – Aromatics

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Module 4b. Unsaturated Hydrocarbons – Aromatics

Introduction

Almost all of you have experienced smelling bathroom fresheners in public lavatories. They
have a typical strong scent that sometimes make you feel dizzy. Dichlorobenzene is the
component in a typical brand of bathroom freshener and this compound contains a benzene ring
in its structure. The name of the class of this compound is called the aromatics or aromatic
compounds. They are named as such because of the distinct strong aroma of the first compounds
discovered under this class. Aromatic compounds are usually stable because of the structural
features they have which will be discussed in this module.

Learning Outcomes

At the end of this module, the student should be able to

• Distinguish benzenoid and non-benzenoid aromatic structures from non-aromatic structures

• write the structures and give the IUPAC names of aromatic hydrocarbons and derivatives
given their molecular formula
• predict the physical and chemical properties and chemical reactivity from their molecular
structures
• predict the effect of substituents on the reactivity and orientation in EAS
• identify the organic starting material, organic product and/or necessary reagents for chemical
reactions of aromatic hydrocarbons and derivatives
• understand the outcome of reactions based on the mechanism
• plan strategies for the synthesis of aromatic compounds

4b.1. The Benzene Ring

The simplest aromatic compound is the benzene ring. It is a cyclic structure composed of
six carbons and six hydrogen atoms. A very intriguing story about the idea of the structure is an
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This module is intended only for your personal use in connection with the course you are enrolled in. It
is not for distribution or sale. Permission should be obtained from the Organic Chemistry and Natural
Products Division for any use other than for what it is intended.
CHEM 40: Basic Organic Chemistry
Module 4b: Unsaturated Hydrocarbons – Aromatics

account by August Kekule where he dozed off (some versions said in a train) and dreamt of a
snake biting its own tail. The clue of a cyclic structure of the benzene was somehow shown in his
dream. The structure of benzene and other features of this compound can be seen in this resource
– Benzene Ring. Note that the six pi electrons are delocalized in the electron cloud of the ring
and the resonance forms of this ring makes the structure relatively stable.

4b.2.Aromaticity and Physical Properties of Aromatic Compounds

Benzene ring is the simplest aromatic compound. There are a lot of compounds that are
also aromatic. Some compounds can have more than 1 ring while others can have heteroatoms.
A simple way to determine if a compound is aromatic or not is by using the Huckel Rule. This
resource – Aromaticity and the Huckel Rule will guide you in using the rule to check whether
some simple compounds can either be aromatic or not. For the physical properties of aromatics,
read this resource – Physical Properties of Arenes.

SAQ 4b.2.

Using the Hückel rule, determine whether each of the following structures is aromatic or
not.

a. b. c. d.

4b.3. Nomenclature of Aromatic Compounds

Naming aromatic compounds parallels naming of cycloalkanes – lowest possible number

combination for the locants of the substituents (if present). The names of benzenoid compounds
usually end by the suffix -benzene or the parent name can be the common name of a mono-
substituted compound. Browse through the IUPAC rules and examples in this resource –
Nomenclature of Benzenoid Compounds and answer the SAQ 4b.3. for your practice.

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This module is intended only for your personal use in connection with the course you are enrolled in. It
is not for distribution or sale. Permission should be obtained from the Organic Chemistry and Natural
Products Division for any use other than for what it is intended.
CHEM 40: Basic Organic Chemistry
Module 4b: Unsaturated Hydrocarbons – Aromatics

SAQ 4b.3.

1.Give the IUPAC names for the following compounds.

a. b. c.

d. e. f.

2. Draw structures corresponding to the following IUPAC names.

a. p-Bromochlorobenzene
b. p-Bromotoluene
c. m-Chloroaniline
d. 1-Chloro-3,5-dimethylbenzene

4b.4. Reactions of Aromatic Compounds

The main reaction of aromatic compounds is via electrophilic aromatic substitution (EAS).
Even though benzene contains double bonds, they do not readily follow the reactions of alkenes
– electrophilic addition where alkene’s double bond is converted to single bond. In the case of
aromatics, the double bond is reformed to preserve the stable structure of the aromatic ring. We
will focus on the reactions – nitration, halogenation, sulfonation, Friedel-Crafts alkylation and
Friedel-Crafts acylation. To know more about each of this reactions, look into this resource –
Reactions of Aromatic Compounds. The reactions are easy specially if only benzene is the starting
material. In the case of substitute benzenes undergoing EAS reactions, the kind of substituents
play an important role in the reactivity of the ring ang the position of the incoming substituent in
the ring. A table of substituents is found in the resource. Fill up the table below to help you
analyze the structural features of these substituents and why they are grouped as such.

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This module is intended only for your personal use in connection with the course you are enrolled in. It
is not for distribution or sale. Permission should be obtained from the Organic Chemistry and Natural
Products Division for any use other than for what it is intended.
CHEM 40: Basic Organic Chemistry
Module 4b: Unsaturated Hydrocarbons – Aromatics

Electron Releasing Electron Withdrawing

Groups (ERG) Groups (EWG)
Are there lone electron pair(s) on the atom of the group directly
attached to the ring? (Y or N)
What are the charges of the atom of the group directly bonded
to the ring? (positive, negative, partial positive, partial negative)
Does this group have a tendency to donate lone pairs? (Y or N)
Does this group have a tendency to accept electrons? (Y or N)
Will this group make the ring more reactive? (Y or N)
Hint: if the ring is more “negative” it is more reactive towards
EAS (faster reaction)

Halogens on the other hand are deactivating (electron withdrawing – they have lone pairs,
but they don’t donate). The high electronegativity of halogens makes them withdraw electrons
from the ring, but they are ortho and para directors. This can be explained by the
stabilizing effect of the halogen on the carbocation formed when the substituent is in the ortho
or para position.

SAQ 4b.3.

1. Predict the major product/s of the following reactions:

a. nitration of bromobenzene
b. bromination of nitrobenzene
c. chlorination of phenol
d. bromination of aniline

2. Predict the major product/s of nitration of the following substances.

a. bromobenzene
b. benzonitrile
c. benzoic acid

3. Identify the carboxylic acid chloride that might be used in a Friedel–Crafts acylation
reaction to prepare each of the following acylbenzenes

a. b.

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This module is intended only for your personal use in connection with the course you are enrolled in. It
is not for distribution or sale. Permission should be obtained from the Organic Chemistry and Natural
Products Division for any use other than for what it is intended.
CHEM 40: Basic Organic Chemistry
Module 4b: Unsaturated Hydrocarbons – Aromatics

SAQ 4b.3.

4. Propose a stepwise process for the synthesis the following aromatic compounds from
benzene.

a. b.

References:

Brown, W. H., Foote, C. S., Iverson, B. L., & Anslyn, E. (2011). Organic Chemistry (William H. Brown
and Lawrence S. Brown) (6th ed.). 20 Davis Drive Belmont, CA 94002-3098, USA: Brooks Cole.

McMurry, J. E. (2011). Organic Chemistry (8th ed.). 20 Davis Drive Belmont, CA 94002-3098, USA:
Cengage Learning.

Wade, L.G. (2012). Organic Chemistry (8th Edition) (8th ed.). Illinois, United States of America: Pearson.

https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Map%3A_Organic_Chemistry_(W
ade)/17%3A_Aromatic_Compounds/17.05%3A_Aromatic%2C_Antiaromatic%2C_and_Nonarom
atic_Compounds

https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Book%3A_Basic_Principles_of_Or
ganic_Chemistry_(Roberts_and_Caserio)/22%3A_Arenes%2C_Electrophilic_Aromatic_Substituti
on/22.02%3A_Physical_Properties_of_Arenes

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This module is intended only for your personal use in connection with the course you are enrolled in. It
is not for distribution or sale. Permission should be obtained from the Organic Chemistry and Natural
Products Division for any use other than for what it is intended.