Chem Factsheet

September 2002 Number 39

Reactions of Benzene and its Compounds
To succeed in this topic you need to: Derivatives of benzene
• Have a good understanding of AS-level Organic Chemistry (Factsheets Derivatives of benzene are formed by substitution reactions which will be
15, 16,17, and 27); electrophilic in nature due to the high concentration of electrons in the
• Be confident in using organic nomenclature and structural formulae. delocalised system of benzene.

After working through this Factsheet you will: H

• Be able to explain the structure of benzene; H H
• Know the names and structures of common substituent products of High concentration of electrons.
benzene; Benzene attracts electrophiles. H
• Know the necessary reactions of benzene and its compounds. H
H
Benzene, C6H6, is an aromatic hydrocarbon, or an arene. When the formula
was first found, the structure proposed initially was: The group C6H5-, derived from benzene with one H atom having been
substituted, is known as the phenyl group.
H
H H Listed below are some common substituent products.

Substituent group Systematic name

H H
H Methyl -CH3 Methylbenzene
This structure would have resulted in bonds having different lengths; double Chloro -Cl Chlorobenzene
bonds are shorter than single bonds, due to the greater attractive forces. Nitro -NO 2 Nitrobenzene
Hydroxyl -OH Phenol
If this had been the correct structure, two equivalent forms would have Amino -NH 2 Phenylamine
existed: Carboxylic acid -COOH Benzenecarboxylic acid
H H
H H H H Reactions of benzene
Candidates are expected to be able to recall the following reactions, in
terms of reagents and reaction conditions.
H H H H
H H 1. Nitration of benzene.
Benzene reacts with a mixture of concentrated nitric acid and concentrated
However, where equivalent bond structures can be written for a compound
sulphuric acid (called a nitrating mixture) at 50oC to form nitrobenzene.
neither exist. Instead, all bond lengths will be equal as the available electrons
are shared equally amongst the atoms involved. NO 2
conc H2SO4
+ HNO 3 50o C + H2 O
The benzene ring consists of 6 C-C single bonds and the remaining electrons
exist in a delocalised system.
Reaction type: Substitution
Conditions: Conc. H2SO4, 50oC
The structure of benzene is often written:
Mechanism: Electrophilic

Exam Hint: - This is a commonly examined reaction. Candidates

should pay careful attention to the mechanism of this reaction – see
In this representation the H atoms need not be shown. The C-C bonds are Factsheet 40.
somewhere between single and double bonds, as illustrated by the following
bond length data:
2. Bromination of benzene.
C-C single bond length in cyclohexene = 0.15 nm Bromine reacts with benzene in the presence of an iron wire catalyst in dry
C=C double bond length in cyclohexene = 0.13 nm conditions at room temperature and pressure.
But Br
C-C bond length in benzene = 0.14 nm
Fe
+ Br 2 + HBr
Dry
Benzene is a clear colourless liquid at room temperature and pressure. It is
relatively unreactive due to the strong bonding within its structure
Reaction type: Substitution
Benzene used to be used as a non-polar organic solvent, but this is no Conditions: Fe catalyst, dry, room temp.
longer the case due to its carcenogenic (cancer causing) properties. Mechanism: Electrophilic

See Factsheet 40 for the reaction mechanism.

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 Reactions of Benzene and its compounds Chem Factsheet

3. Alkylation of benzene (Freidel-Krafts Reactions). 1. Reaction of phenol with sodium hydroxide.

Benzene reacts with chloroalkanes in the presence of anhydrous aluminium The -OH group in phenol is more acidic (proton donating) than in straight
chloride to give an alkyl benzene. chain alcohols. Phenol is not very soluble in water, but forms a colourless
C 2H 5 solution with aqueous sodium hydroxide.
AlCl3 OH O−
+ C2 H 5Cl + HCl
Dry
(s) + OH−(aq) (aq) + H2O(l)
phenate
Reaction type: Substitution
ion
Conditions: Anhydrous AlCl3, dry, possible heat under reflux.
Mechanism: Electrophilic Conditions: Aqueous NaOH at room temp.

A similar reaction takes place with acid chlorides, benzene and aluminium Note how phenol has acted as an acid, donating a proton to neutralise the
chloride to give ketones. hydroxide ion.
CH 3 O
C
O
AlCl 3 2. Reaction of phenol with bromine water.
+ CH 3 C Dry + HCl
Cl Substitution of the hydrogen atoms on the benzene ring is made easier by
the presence of the -OH group.
Reaction type: Substitution
Conditions: Anhydrous AlCl3, dry, possible heat under reflux. OH OH
Mechanism: Electrophilic Br Br
(aq) + 3Br2(aq) (s) + 3HBr(aq)
Again, see Factsheet 40 for the reaction mechanism.
Br

Reaction type: Substitution

4. Oxidation of side chains on arenes. Conditions: Bromine water added - no catalyst required.
If an arene (i.e. benzene) with a carbon-containing side chain (with the C Mechanism: Electrophilic
atom bonded directly to the ring structure) is heated under reflux with
alkaline potassium manganate (VII) solution, benzenecarboxylic acid is This reaction is easily observed as the red/brown bromine water decolourises
formed. and a white precipitate is formed.
CH3 COOH
KMnO4
+ H2O 3. Reaction of phenol with acid chlorides.
OH−
Phenol reacts with acid chlorides to form esters, but alkaline conditions are
necessary as phenol does not react as readily as straight chain alcohols.
CH2CH2OH COOH O
KMnO4 CH 3 C
OH−
+ CO2 + 2H2O O
OH
O
+ CH 3 C + HCl
CH2COOH COOH Cl
KMnO4
+ CO2 + H2O Conditions: Aqueous NaOH
OH −

The carbon-containing side chain (whatever it is) is oxidised to –COOH.

Nitrobenzene
Reaction type: Oxidation Nitrobenzene C6H5NO2 is another common benzene derivative.
Conditions: KMNO4 in alkali, heat under reflux NO 2

Reactions of phenol. The reduction of nitrobenzene to an amine using tin and

Phenol, C6H5OH is a common derivative of benzene. concentrated hydrochloric acid.
OH Tin and concentrated hydrochloric acid are used as reagents to form an
intermediate tin complex, then large quantities of alkali are required to
release the amine after the initial reaction.
+ +
Phenol is an alcohol, but whereas straight chain alcohols have just the -OH NO 2 NH 3 NH 3 NH 2
2−
functional group, phenol has the -OH group and the electron- rich benzene Sn NaOH
ring. 2 conc HCl
SnCl6 2

Care must be taken when using phenol, a white crystalline solid, as it is

both corrosive and an anaesthetic. Reaction type: Reduction
Conditions: Tin, conc. HCl, then large quantities of NaOH.

Note: This reaction will work for other aromatic nitro-compounds.

Other reducing agents (e.g. LiAlH4) can work.
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Reactions of Benzene and its compounds Chem Factsheet

Phenylamine Answers.
Phenylamine C6H5NH2 is produced from nitrobenzene, as described above.
1. Strong carbon-carbon bonds due to delocalised system of electrons
NH 2 througfhout the ring structure.

2. Electrophiles. They are attracted to the electron rich delocalised system.

Amines, being basic, usually react with acids to form salts. The following 3. Benzene is carcenogenic.
reaction, however, is different.
4. (a) reagents: conc. HNO3
(i) The reaction between phenylamine and nitrous acid conditions: conc. H2SO4, 500C
First the unstable nitrous acid (HNO2) is produced in situ by reacting
sodium nitrite with hydrochloric acid. (b) reagents: Br2 (l)
conditions: Fe catalyst, dry
NaNO2 (aq) + HCl(conc.) ! HNO2 (aq) + NaCl(aq)
(c) reagents: CH3Cl
conditions: anhydrous AlCl3, dry, heat under reflux
(ii) The diazotisation reaction
Phenylamine then reacts with the nitrous acid and HCl to form 5. Phenol is more acidic than ethanol, it donates protons more readily.
benzenediazonium chloride.
+ − O
N NCl 6.
NH 2 CH 3 C
low temp OH O
+ HNO2 + HCl + 2H2O O
+ CH3 C + HCl
Diazonium ions are important intermediates. Cl

(iii) The coupling reaction of benzenediazonium ions with phenol.

Azo-dyes are formed as diazonium salts react with phenol.
+ −
N NCl OH
low temp
+ N N OH + HCl
yellow precipitate
(diazo compound)
There are many diazo compounds with different colours, and they can be
used in textile dyes.

Questions

1. Explain the stability of the benzene ring structure.

2. State what sort of species will attack the benzene ring, and why.

3. State why care should be taken when handling benzene.

4. Give reagents and conditions for the following conversions:

(a) (b) (c)

NO 2 Br CH 3
Acknowledgements:
This Factsheet was researched and written by Kieron Heath
5. State why phenol reacts more readily with sodium hydroxide than Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
B18 6NF
ethanol. ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
6. Show how phenol can be used to form an ester. No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136