H2 Organic Chemistry Booklet

St. Andrew’s Junior College

H2 Chemistry 2013
Organic Chemistry Lecture Notes 5
Arenes

Assessment Objectives:
Candidates should be able to:
(a) describe the chemistry of arenes as exemplified by the following reactions of benzene and
methylbenzene:
i. substitution reactions with chlorine and bromine
ii. nitration
iii. oxidation of the side-chain to give a carboxylic acid
(b) i. describe the mechanism of electrophilic substitution in arenes, using the mono-nitration of
benzene as an example.
ii. describe the effect of the delocalisation of electrons in arenes in such reactions
(c) predict whether halogenation will occur in the side-chain or aromatic nucleus in arenes
depending on reaction conditions
(d) apply the knowledge of positions of substitution in the electrophilic substitution reactions of
mono-substituted arenes

Content:
I Benzene
1 Introduction
2 Physical Properties
3 Chemical Reactions
4 Electrophilic Substitution Mechanism and Reactions
5 Effect of Substituent on Reactivity of Benzene ring
6 Industrial Importance of Benzene

II Methyl Benzene
7 Introduction
8 Physical Properties
9 Chemical Reactions
10 Summary of Arenes
11 Comparative Study of Hydrocarbons

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H2 Organic Chemistry Booklet

I Benzene
1 Introduction
1.1 Functional Group
• Arenes are aromatic hydrocarbons. These are compounds that contain rings of delocalised
electrons. The term aromatic was originally used for naturally occurring compounds which were
sweet-smelling, i.e. compounds which had an aroma. Since this group included many compounds
with benzene rings, the term aromatic became associated with benzene rings.
Typical examples:

Benzaldehyde
C6H5CHO
Sweet-smelling (paints, furniture waxes, nail Almond oil
polish)

1.2 Structure of Benzene

• Early proposed structures are:
i) CH2=C=CH-CH=C=CH2;
ii) Kekule’s structure (1865): cyclic hexatriene

• These structures are rejected because:

a) Benzene – is less reactive than alkene
– does not react with potassium manganate (VII)
– undergoes addition reaction with difficulty
– and benzene ring is stable

b) X-ray studies also show that the C-C bond length in benzene is between that of a single C-C
bond and a C=C double bond :

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Bond type C-C C-C in benzene C=C

Bond length/nm 0.154 0.139 0.134

• In the actual structure of benzene, the bonds are neither single nor double. Each has an
intermediate bond length of approximately 1.5 bonds.
• All the C-C bonds in benzene are equal.

c) The enthalpy of hydrogenation of benzene shows that it does not contain three C=C bonds.
∆Hhydrogenation/ kJ
Compound
mol-1

-120

Cyclohexene

-360

1,3,5-Cyclohexatriene

-206
[should be about 3
x (-120) = - 360 if 3
C=C bonds are
Benzene present]

• The difference (360 – 206) = 154 kJ mol-1 is known as the resonance energy or stabilisation
energy of benzene.
• Hence benzene does not contain three C=C bonds as in cyclohexa-1,3,5-triene. Benzene is now
known to exist as a resonance structure of two forms of cyclohexa-1,3,5-triene.

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• Like ethene, the sp2 orbitals of all the C atoms are arranged in a trigonal planar shape. Two of the
sp2 orbitals of each C are used in forming σ bonds with neighbouring C atoms. The remaining sp2
orbital of each C is used to overlap with the s orbital of H atoms to form σ bonds.
• Each C still has one unhybridised pz orbital which lie perpendicular to the three sp2 hybrid orbitals.
A π bond can be formed when the pz orbitals of C1 and C2 overlap in a side-on manner. Similar π
bonds can be formed when the pz orbitals of C3 and C4 overlap, C5 and C6 overlap in a side-on
manner. These π electrons are delocalised.
• The delocalised π electron cloud is spread throughout the benzene ring. This delocalisation of
electrons minimises repulsion and hence stabilises the structure.

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• Benzene is trigonal planar with respect to each carbon atom at the corners of a regular
hexagon. All the C atoms lie on the same plane.
• Benzene molecule is symmetrical and non-polar.

1.3 Nomenclature
a) Mono-substituted benzene derivatives
(i) Taking benzene ring as parent
Substituent group IUPAC Structure
CH3

alkyl (e.g. CH3) methylbenzene (toluene)

Cl

halogen (e.g. Cl) chlorobenzene

-NO2 nitrobenzene

-OCH3 methoxybenzene

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(ii) Special names

Substituent group IUPAC Structure

benzoic acid
-CO2H (carboxyl)

benzaldehyde
-CHO (carbonyl)

-NH2 (amine) phenylamine (aniline)

-OH (hydroxyl) phenol

(iii) More than one substituent: di-, tri- substituted

The relative positions must be indicated.
CH3

CH3

1,2-dimethylbenzene 1,3-dimethylbenzene

1-bromo-2-chlorobenzene 3–bromobenzoic acid

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2 Physical Properties
• Colourless liquid
• b.p = 80 °C; m.p = 5.5 °C
• Sparingly soluble in water
forms the upper layer (less dense than water)
• Very toxic, carcinogenic

3 Chemical Reactions
3.1 Combustion
• Like all hydrocarbons, benzene undergoes combustion to form carbon dioxide and water.
C6H6(l) + 15/2 O2(g) 6CO2(g) + 3H2O(l)

3.2 Oxidation
• Unlike alkenes, benzene does not undergo oxidation. Hence benzene has no reaction with
acidified potassium manganate (VII) or acidified potassium dichromate(VI) solutions.

3.3 Addition
• Although benzene does undergo addition reactions similar to alkenes, it does not do so as readily
as alkenes.
• This is due to the tendency of benzene to retain the delocalised π electron cloud or aromatic ring
which gives it its stability.
• Addition reactions involving the benzene ring generally require harsher conditions as the
aromacity of the ring is lost.

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(i) Halogenation - With chlorine in the presence of sunlight or U.V. light at high temperature and
pressure.
Cl

Cl
Cl
high temp &
+ 3Cl 2(g) pressure
Cl Cl

Cl

(ii) Hydrogenation - With hydrogen in the presence of catalysts such as Ni and Pt at high
temperature and pressure.

3.4 Electrophilic Substitution

To retain the aromatic ring, the typical reaction which benzenes undergo is electrophilic
substitution as the delocalised π electrons in the benzene ring make it ‘electron-rich’ and attracts
electrophiles readily.

In these substitution reactions, the hydrogen atom(s) of the benzene ring is/are substituted by
electrophile(s).

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4 Electrophilic Substitution Mechanism and Reactions

Candidates should be able to:
(a) describe the chemistry of arenes as exemplified by the following reactions of benzene and
methylbenzene:
i. substitution reactions with chlorine and bromine
ii. nitration
iii. oxidation of the side-chain to give a carboxylic acid

(b) i. describe the mechanism of electrophilic substitution in arenes, using the mono-nitration of
benzene as an example.
ii. describe the effect of the delocalisation of electrons in arenes in such reactions.

4.1 Nitration
Overall Equation:

Electrophilic substitution mechanism:

Important Notes:
• When ‘describing’ or ‘outlining’ a mechanism, one is not expected to write too many words.
Remember to include the following:
o Name of the mechanism
o Steps in sequential order
o Curved arrows (representing the flow of electrons)
o Labels (slow, fast, δ+, δ-, lone pair of electrons)
o Identify the intermediates and major products if applicable.
• Do not memorise mechanisms by rote. Identify the functional group(s) and the nature of the
reactant(s) to select the appropriate mechanism.

Concentrated sulfuric acid, being a stronger acid, donates a proton to concentrated nitric acid
which loses water molecule to give NO2+ (electrophile).

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The full arrow shows the movement of 2 electrons.

This is a typical reaction of aromatic compounds where there is an overall retention of aromatic
character, i.e. the aromatic ring is retained.

Continuous nitration yields 1, 3-dinitrobenzene.

4.2 Halogenation
• When benzene is mixed with bromine or chlorine in the dark, no reaction occurs.
• But when a catalyst such as a halogen carrier like anhydrous AlBr3, AlCl3, FeCl3 or FeBr3 or Al
or Fe is present and heating with reflux is carried out, benzene can undergo electrophilic
substitution.

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H2 Organic Chemistry Booklet

Overall equation:

Electrophilic Substitution Mechanism:

In the presence of the anhydrous halogen carrier, chlorine forms an electrophile Cl+.

• Prolonged halogenation results in a mixture of 1, 2- and 1, 4- dichlorobenzene.

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4.3 Friedel-Crafts Alkylation

• One or more hydrogen atoms on the benzene are replaced by alkyl groups when benzene reacts
with alkyl halide in the presence of a catalyst (anhydrous halogen carrier, AlCl3, AlBr3, FeCl3 and
FeBr3).

NOTE: The electrophile is the R+, e.g. CH3+; C2H5+ produced from RX +
halogen carrier.

4.4 Friedel-Crafts Acylation

• One or more hydrogen atoms on the benzene are replaced by acyl groups when benzene reacts
with acyl halide in the presence of a catalyst (anhydrous halogen carrier, AlCl3, AlBr3, FeCl3 and
FeBr3).

NOTE: The electrophile is the RCO+, e.g. CH3CO+; C2H5CO+ produced from
RCOX + halogen carrier.

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5 Effect of Substituent on Reactivity of Benzene Ring

Candidates should be able to:
(d) apply the knowledge of positions of substitution in the electrophilic substitution reactions of
mono-substituted arenes.

The reactivity of the benzene is influenced by the presence of a substituent, X.

• If X = Activating group (usually electron donating group), benzene ring is made more
reactive. Hence, the reaction conditions required would be milder.

• If X = Deactivating group (usually electron withdrawing group), benzene ring is made less
reactive. Hence, the reaction conditions required would be harsher.

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General guide:
Activating Groups: Deactivating Groups:
electron-donating electron-withdrawing
-R -F - NO2

- OH - Cl -C≡N

- OR - Br - CHO

- NH2 -I - COR

- NHR - COOH

- NR2 - SO2OH

Contain only single bonds Contain multiple bonds

Example:
For nitration of benzene to occur, the temperature required is about 55oC.

Consider the nitration of:

i. Methylbenzene
• The substituent is the methyl group (-CH3) which is activating as it donates electrons into the ring.
Hence when methylbenzene undergoes nitration, milder conditions are required. The temperature
required for this reaction is 30°°C.

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ii. Phenol
• The substituent is the -OH group which is an activating group, thus, phenol undergoes nitration
under even milder conditions. Dilute nitric acid and room temperature is used for the nitration of
phenol.

Point of Note
-OH is considered an EDG when it is attached to a benzene ring due to the delocalisation of
lone pair of electrons on O into the benzene ring.

But when –OH is attached to an alkyl group, it is considered an EWG due to the
electronegativity of O atom.
iii. Nitrobenzene
iii. Nitrobenzene
• The substituent is the nitro group (-NO2) which is deactivating. Hence when nitrobenzene
undergoes nitration, harsher conditions are required. The temperature required for this
reaction is > 55°°C.

5.1 Position of subsequent substitution on the benzene ring

• The presence of substituent also affects the position of subsequent substitution at the benzene
ring.

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General guide:
Activating Groups: Deactivating Groups:
electron-donating electron-withdrawing
-R -F - NO2

- OH - Cl 2, 4 - -C≡N
directors
- OR 2, 4 – - Br - CHO 3-
directors directors
- NH2 -I - COR

- NHR - COOH

- NR2 - SO2OH

Contain only single bonds Contain multiple bonds

E.g. In methylbenzene, the -CH3 group is 2, 4-directing; it causes attack to occur mainly at 2- and 4-
positions with respect to CH3. Hence in nitration of methylbenzene, the nitro group is substituted
mainly at the 2 and 4 positions.

E.g. In nitrobenzene, the nitro group is 3-directing; it causes attack to occur at 3-position with respect to
NO2. In further nitration of nitrobenzene, the -NO2 group is substituted in the 3-position.

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Exercise 1:
Determine the best sequence of reactions to obtain the organic compound F from
benzene.

O 2N CH3

Br

Compound F
A Step 1. Nitration with conc. HNO3. B Step 1. Alkylation with CH3Cl
Step 2. Alkylation with CH3Cl Step 2. Bromination with Br2.
Step 3. Bromination with Br2. Step 3. Nitration with conc. HNO3.
C Step 1. Alkylation with CH3Cl D Step 1. Bromination with Br2.
Step 2. Nitration with conc. HNO3. Step 2. Alkylation with CH3Cl
Step 3. Bromination with Br2. Step 3. Nitration with conc. HNO3.

6 Industrial Importance of Benzene

• Benzene is the starting material for the production of phenol and propanone.
• Benzene is also used for making phenylamine.

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II Methylbenzene
7 Introduction
• Methylbenzene has a side chain, the methyl group, attached to the benzene ring:

Molecular formula = C7H8

• The C atom of the methyl group uses sp3 orbitals to form 4 σ bonds. Hence 4 bond pairs form a
tetrahedral shape with bond angle of 109.50.

• The 7 carbons and the 5 H atoms of the ring lie on the same plane but the 3 H atoms of the methyl
group lie in a different plane.

8 Physical Properties
• colourless liquid
• b.p = 111°C; m.p = - 95°C;
• less toxic than benzene and more useful as solvent

9 Chemical Reactions
Methylbenzene undergoes two types of reactions:
1) Side chain reactions
2) Electrophilic substitution of benzene ring

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9.1 Side Chain Reactions

Candidates should be able to:

(a) describe the chemistry of arenes as exemplified by the following reactions of benzene and
methylbenzene:
i. substitution reactions with chlorine and bromine
ii. nitration
iii. oxidation of the side-chain to give a carboxylic acid

9.1.1 Oxidation
• Although benzene is resistant to oxidation, the methyl side chain in methyl benzene is oxidised
easily by refluxing with acidified or alkaline potassium manganate(VII) solution.

Acidic Oxidation
• On oxidation by refluxing with acidified KMnO4, the –CH3 group is oxidised to –COOH.

• Observation: Purple KMnO4 decolourised and white ppt of benzoic acid formed.

Alkaline oxidation
• The -CH3 group is oxidised by refluxing with alkaline KMnO4, forming the carboxylate anion due to
the alkaline medium used.
• On acidifying, -COOH is obtained.

• Observation: Purple KMnO4 decolourised and brown ppt of MnO2 formed.

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• In general, one alkyl group (CH3 - or C2H5 - ) is oxidised to one acid group.

NOTE:
• Acidified K2Cr2O7 is NOT strong enough to be used here.
• Side-chain oxidation only occurs if there is at least a benzylic H present.

• With acidified MnO2, mild oxidation occurs, and benzaldehyde is formed.

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Exercise 1: Write down the formulae of the organic products when the
compounds below are boiled with acidified potassium manganate
(VII) solution for some time:

Structure Answer

No reaction (due to absence of

benzylic H)

9.1.2 Halogenation
Candidates must be able to:
(c) predict whether halogenation will occur in the side-chain or aromatic nucleus in arenes
depending on reaction conditions.

• Like the alkanes, the methyl group can be halogenated by halogens in the presence of sunlight or
at boiling temperature by a free radical substitution mechanism.

9.2 Electrophilic Substitution of Benzene Ring

• Like benzenes, methylbenzene can also undergo ring substitution such as nitration and
halogenation.
• Methylbenzene is more reactive than benzene as the methyl group donates electrons into the ring
making it more susceptible to electrophilic attack (activating). The activating –CH3 group is 2, 4-
directing, so the 2- and 4- positional isomers are formed. (Refer: Section 5.1).

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a) Nitration
• Methylbenzene can also be nitrated like benzene. The products are also 2 and 4 substituted
products. The conditions required are milder.

CH3

NO2
With concentrated nitric acid and concentrated O2N
sulfuric acid at higher temperature, the tri-substituted
product of 2,4,6-trinitromethylbenzene is formed.

NO2
b) Halogenation 2, 4, 6 -trinitromethylbenzene
• The benzene ring of methylbenzene can be chlorinated by bubbling chlorine through the liquid
methylbenzene in the presence of catalyst such as anhydrous halogen carrier like AlBr3, AlCl3,
FeCl3 and FeBr3, at room temperature. A mixture of 2-chloromethylbenzene and 4-
chloromethylbenzene are formed.

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10 Summary

Reddish brown Br2 decolourised,

white misty HBr fumes seen.

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11 Comparative Study of Hydrocarbons

Reaction Alkane Alkene Benzene Methylbenzene
Substitution Free radical No substitution at the C= C 1. Electrophilic substitution at 1. Free radical substitution at
substitution bond. the ring the side chain
i) Nitration
Free radical substitution on alkyl ii) Halogenation 2. Electrophilic substitution at
groups iii) Friedel Craft’s alkylation the ring. (same as in benzene)
Addition No reaction Electrophilic addition across the Free radical addition.
C= C bond e.g. with chlorine in sunlight - Same as in benzene
forms hexachlorocyclohexane
Oxidation No reaction Give carboxylic acids / carbonyl No reaction Oxidation at the side chain to
compounds / CO2 depending on give –COOH group.
(with acidified oxidising agents and the Purple MnO4- decolourised
KMnO4 and position of C=C. Formation of white ppt.
reflux) Purple MnO4- decolourised. No effect on the ring.
Combustion Burns to Burns to form CO2 and H2O Burns to form CO2 and H2O. Same as in benzene
form CO2
and H2O Smoky flame

Hydrogenation No reaction Forms alkanes Forms cyclohexane Forms methylcyclohexane

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Reaction Alkane Alkene Benzene Methylbenzene

Bromination Conditions: Conditions: Room Conditions: Halogen Carrier, Heat Conditions: U.V light or heat. (NO
U.V light. temperature. with reflux. No UV light. Halogen Carrier)
Observation: Observation: Observation: Observation:
1) Reddish 1) Reddish brown 1) Reddish brown liquid bromine 1) Reddish brown liquid bromine
brown liquid liquid bromine decolourised. decolourised.
bromine decolourised. 2) White fumes of HBr. 2) White fumes of HBr.
decolourised Or
2) White 2) Orange aqueous
fumes of HBr. bromine decolourised.

Decolourised in U.V. light at high Conditions: Anhydrous halogen

temperature and pressure. No
Carrier, room temperature. No UV
halogen carrier.
light.
Observation:
1) Reddish brown liquid bromine
decolourised.
2) White fumes of HBr. CH3
CH3

Br

OR

Br
2-bromomethylbenzene OR
4-bromomethylbenzene

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~~~ THE END ~~~

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