1.

3 Aromatic Hydrocarbons
Michael Faraday (1791–1867) was the first person to isolate and identify benzene
from a mixture of oils in 1825 (Figure 1). Since then, benzene has been used in many
commercial products. One of its first uses was as an aftershave in the nineteenth and
early twentieth centuries. In 1903, benzene was used to decaffeinate coffee. It was
also used as an anti-knock additive in gasoline to control the ignition of the fuel until
the 1950s, when it was replaced by tetraethyl lead. Benzene is also widely used in
industry as a solvent in chemical reactions. Testing has identified benzene as a car-
cinogen and implicated it in other health problems. As the hazards of benzene have
become known, many of its commercial uses have been discontinued.

What Is an Aromatic Hydrocarbon?

An aromatic hydrocarbon is an unsaturated hydrocarbon that has a ring structure and a
bonding arrangement that causes it to be chemically stable. Benzene, C6H6, is a flat 6-carbon
ring with a hydrogen atom bonded to each carbon atom (Figure 2). It is the simplest aro-
matic hydrocarbon. The structural diagram often shows benzene as having three double
bonds alternating with three single bonds. Measurements of the bond length between
carbon atoms, however, have shown that all six bond lengths are equal. If benzene actu-
ally had three double bonds, then those bonds would be shorter than the other three. To
Figure 1  Michael Faraday (left) working
in his chemistry lab
indicate that all six bonds are identical, the structure is shown as alternating between two
arrangements of double bonds (Figure 2(b)) or as a hexagon with a circle inside (Figure
aromatic hydrocarbon  an unsaturated 2(c)). The hexagon with the circle indicates that the electrons in the bonds are shared
cyclic hydrocarbon with a pattern of equally between all 6 carbon atoms.
bonding that makes it chemically stable
H
6 120˚ 120˚
1 Cl H C H
5
C C
120˚
2
4 C C
3
Cl H C H
1,2-dichlorobenzene (a) H (b) (c)

CH2CH3 Figure 2  (a) The structure of benzene, a planar ring system in which all bond angles are 120°
(b) Two structural formulas implying that the structure of benzene is a combination of them both
1
together (c) The common representation of benzene
6 2

5
4
3
Naming Aromatic Compounds
CH3 There are two conventions for naming compounds that include a benzene ring.
1-ethyl-4-methylbenzene Which one we use depends on the structure of the other part of the compound.
Figure 3  Substituted benzenes We use the first convention when naming aromatic compounds that have non-
carbon substituents or a small alkyl group. In this case, the benzene ring is generally
considered to be the parent molecule. The attached functional groups are named as
phenyl group  a benzene ring (minus substituents to benzene. If a single group is attached to a benzene ring, we put the name
1 hydrogen atom) that behaves as a of the group before the root -benzene. For example, chlorobenzene, C6H5Cl, has one
substituent in an organic compound chlorine atom replacing a hydrogen atom on the benzene ring. Compounds made up
of a benzene ring with one or more halogen atoms attached are called aromatic halides.
If two or more substituents are bonded to the benzene ring, we number the carbon
CH3 CH2 CH2 CH CH2 atoms of the benzene ring starting with the first substituent (alphabetically) and
continue numbering in the direction of the next closest substituent. Figure 3 shows
Chemistry 12
some examples.
0176504524 In the second naming convention, the benzene ring is considered to be a substituent
FN onC01-F74-OC12USB
a hydrocarbon chain. A benzene ring that has lost 1 hydrogen atom is called a phenyl
CO
Figure 4  Benzene as a substituent group , just as aGroup
CrowleArt methyl group is like a methane molecule that has lost 1 hydrogen atom.
group in 4-phenylpent-1-ene The compound
Deborah Crowle is named using “phenyl” as the substituent (Figure 4).  WEB LINK
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 Tutorial 1  Naming and Drawing Aromatic Compounds
Aromatic hydrocarbons with one or more simple substituents are named by adding
the substituent name(s) to the root “benzene.” If the substituent is complex, such as a
hydrocarbon chain with a multiple bond, consider this the parent group and the benzene
ring the substituent. In this tutorial, you will recognize when to use each convention, and
practise naming and drawing compounds using both conventions.

Sample Problem 1: Naming Aromatic Compounds

Name the compounds represented by the following structural formulas:
(a) CH2CH3   (b)  H3C CH2 CH CH2 CH2 CH3
CH3

CH3 CH2CH3
Solution (a) 1 CH3
6 2
The structure has three simple substituents, so can be named as a Learning Tip
5 3
substituted benzene. Number the carbon atoms to give the substituents 4
the lowest numbers. Traditional Names for Aromatic
Hydrocarbons
This compound is 1-ethyl-2,4-dimethylbenzene. CH3 An older naming convention for
substituted aromatic compounds used
Solution (b) the Greek prefixes ortho-, meta-,
Treat the benzene ring as the substituent. The alkane chain is a hexane and the benzene and para- to indicate the positions
ring is bonded to the third carbon atom in the chain. Therefore, this compound is of substituents. Ortho substituents
3-phenylhexane. are on adjacent carbon atoms in
1,2 positions. Meta substituents
Sample Problem 2: Drawing Aromatic Compounds are separated by 1 carbon atom in
Draw the structural formula for each of the following compounds: 1,3 positions. Para substituents are
located on opposite sides of the
(a) 1-bromo-2-chloro-4-ethylbenzene 6-carbon ring in 1,4 positions.
Chemistry 12
(b) 4,6-diphenyloct-2-ene
0176504524
Br
FN Solution (a) C01-F81-OC12USB
1
CrowleArt
CO First, draw the benzene Group
ring and number the carbon atoms. Cl
6
2
OC12USB Next, add the substituents
Deborah as indicated in the name: a bromine
Crowle
t Group Pass atom on carbon1st 1, apass
chlorine atom on carbon 2, and an ethyl 5 3

Crowle group on carbon 4. 4

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CH2CH3
Solution
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Chemistry 12
0176504524
First, draw the parent alkene, oct-2-ene. Next, add the benzene rings to the fourth and
sixth carbon
FN atoms. C01-F80-OC12USB
CO CrowleArt Group
Deborah Crowle
Pass 1st pass
1 2 3 4 5 6 7 8
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 Practice
1. Name each of the following compounds:  K/U
(a) CH2CH3   (b) CH3  
CH3CH2CHCHCH3

CH3  

2. Draw the structural formulas of the following compounds:  T/I C

(a) 1-fluoro-3-methylbenzene (b) 2-phenylbut-2-ene

CH3
Properties of Aromatic Hydrocarbons
Many aromatic hydrocarbons are liquids at room temperature, while others are crys-
talline solids. Their symmetrical structure causes them to be non-polar unless they
contain an electronegative substituent, so they are generally insoluble in water. From
its discovery and well into the second half of the twentieth century, benzene was
toluene
widely used as a solvent in industrial processes and for dry cleaning clothes. Since the
discovery that benzene is carcinogenic, other chemicals have replaced benzene in
Figure 5  Toluene (methylbenzene) is a
the workplace. One replacement compound is methylbenzene, commonly known as
substituted benzene compound with one
methyl group substituted for a hydrogen toluene, C6H5CH3 (Figure 5).
atom.
Reactions of Aromatic Compounds
Chemistry 12Unit TASK BOOKMARK Chemistry 12
Its unusual bonding makes the benzene ring behave quite differently from an unsatu-
0176504524 rated hydrocarbon. Unsaturated hydrocarbons easily undergo addition reactions.
Aromatic compounds tend to be quite0176504524
FN volatile, C01-F87-OC12USB
which means that they easilyFN However, C01-F88-OC12USB
benzene does not because its bonds are not really alternating double and
CO evaporate CrowleArt
and disperseGroup
in the air. YouCO single bonds. Each bond in benzene is identical and they are much more stable than
CrowleArt Group
may consider the properties of aromatic a carbon–carbon double bond. Bond strength is between that of a single and that of a
Deborah Crowle Deborah Crowle
compounds as you work on the Unit double bond. In general, therefore, aromatic compounds are much less reactive than
Pass 1st pass Pass 1sthydrogenation
alkenes. The pass of benzene to form cyclohexane requires high tempera-
Task, described on page 116.
Approved tures and a catalyst. Benzene does undergo substitution reactions in which hydrogen
Approved
Not Approved atoms are replaced by other atoms, such as halogens (Figure 6).
Not Approved
Substitution reactions are characteristic of saturated hydrocarbons, and addition
reactions are characteristic of unsaturated ones. Benzene reacts more like a saturated
Cl hydrocarbon because of the specialized bonding in the benzene ring (Figure 7).

catalyst Cl
12USB  Cl2  HCl light
 Cl2  HCl
(a)
Group (a)
owle
NO2
Cl
catalyst catalyst
 HNO3  H2O  Cl2  HCl
(b) (b)
CH3
Cl
catalyst  Cl2
 CH3Cl  HCl (c) Cl
(c)
Figure 6  Substitution reactions of benzene. (a) Reaction with Figure 7  Reactions of cyclohexane, benzene, and cyclohexene with chlorine.
chlorine, Cl2, produces chlorobenzene (an aromatic halide) and (a) Cyclohexane reacts with chlorine in a substitution reaction. A hydrogen
hydrogen chloride. (b) Reaction with nitric acid, HNO3, produces atom is lost as the chlorine atom is gained. (b) Benzene reacts with chlorine
nitrobenzene and water. (c) Reaction with chloromethane, CH3Cl, in a substitution reaction, like cyclohexane. (c) Cyclohexene reacts with chlorine
produces toluene and hydrogen chloride. in an addition reaction: no atoms are lost from the organic compound.

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 1.3 Review
Summary
• Aromatic hydrocarbons are a class of cyclic unsaturated hydrocarbons that
have a ring structure and bonding that causes them to be chemically stable.
• Measurements show that the bonds in a benzene ring are all equal in length.
• Naming aromatic compounds with one or more simple substituents requires
just the addition of the substituent group name. Naming aromatic compounds
with a more complex substituent requires treating the benzene ring, named
“phenyl,” as a substituent on a carbon chain.
• Benzene is less reactive than alkenes. Since it participates in substitution
reactions, benzene behaves more like an alkane.
Questions
1. Name the compounds represented by the following 5. Mothballs are small lumps of pesticide that
structural formulas:  K/U discourage moths from damaging woollen
(a) Cl clothing. The main component of mothballs is
paradichlorobenzene.  T/I C A
(a) What is the proper IUPAC name for this
compound? (See the Learning Tip on page 29.)
(b) CH3   (b) Draw the structure of paradichlorobenzene.
(c) When you order this chemical from a company,
the label says “paradichlorobenzene” even
though that is not the correct IUPAC name.
Why do you think the compound is labelled
(c) CH CH2 this way? Do you think it is a good idea, or
should all products be labelled with their
IUPAC name? Explain your reasoning.
6. (a) Predict the products of reactions involving the
following reactants:
(d) CH3 (i)  cyclohexene and hydrogen bromide
(ii)  benzene and chloroethane
(b) Explain how these two reactions are different,
and the reason for the differences.  K/U T/I
CH3 7. One aromatic compound that has been the subject
(e) Br of many studies is bisphenol-A. This chemical was
used as a hardener in many plastics, but studies have
uncovered a possible link to adverse health effects.
(CH2)4CH3
As a result, Canada has now banned some products,
2. Draw the structural formula for each of the
including baby bottles, containing bisphenol-A. Find
92-OC12USB following compounds:  K/U C
out more about this substance and the decision to
leArt Group (a) 1,3-dichloro-4-ethylbenzene restrict its use. Create a graphic organizer showing
rah Crowle (b) 1-bromo-3-phenylhept-5-yne the pros and cons of banning products containing
pass 3. (a) Draw the chemical equation for the reaction bisphenol-A.  T/I C A

between benzene and bromine, Br2. Is this 8. Benzene has, in the past, been used as a solvent in
-OC12USB reaction likely to occur? Explain why or why not. the dry-cleaning industry. Research this use, discover
Art Group (b) How would your answer to (a) be different if why its use is being phased out, and find out what
h Crowle the organic reactant were cyclohexene instead “greener” alternatives are now used for dry cleaning.
of benzene?  T/I Present your findings in an attention-grabbing format
s
4. Draw structural formulas representing the reaction that for your stated target audience.  T/I C A

-OC12USB produces iodobenzene. Label the reactants and classify

WEB LINK
Art Group the reaction as addition or substitution.  K/U T/I C
h Crowle 1.3 Aromatic Hydrocarbons   31
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