9

15 Arenes

Compounds containing only carbon and hydrogen are called hydrocarbons. This
class of compound can be subdivided into alkanes, alkenes and arenes.

alt
15.4 Arenes

Arenes


Arenes

Bilal Hameed Arenes

 arising from the internal combustion engine and of their catalytic
removal
(ii) gases that contribute to the enhanced greenhouse effect
10
c) outline the use of infra-red spectroscopy in monitoring air pollution (see
also Section 22.2)

15.4 Arenes a) describe the chemistry of arenes as exemplified by the following

reactions of benzene and methylbenzene:

alt
(i) substitution reactions with chlorine and with bromine
(ii) nitration
(iii) Friedel-Crafts alkylation and acylation
(iv) complete oxidation of the side-chain to give a benzoic acid
(v) hydrogenation of the benzene ring to form a cyclohexane ring
b) (i) describe the mechanism of electrophilic substitution in
arenes, as exemplified by the formation of nitrobenzene and
bromobenzene
(ii) suggest the mechanism of other electrophilic substitution
reactions, given data
(iii) describe the effect of the delocalisation of electrons in arenes in
such reactions
c) interpret the difference in reactivity between benzene and
chlorobenzene
d) predict whether halogenation will occur in the side-chain or in the
aromatic ring in arenes depending on reaction conditions
e) apply knowledge relating to position of substitution in the
electrophilic substitution of arenes (see the Data Booklet Table 9)

38 www.cie.org.uk/alevel Back to contents page

Arenes Bilal Hameed

 absence of isomers of 1,2-dichlorobenzene, the equal carbon–carbon bond
lengths in benzene and also its resistance to reaction. In recent years, the
bonding between carbon atoms in benzene has been simplified to a circle
inside a hexagon:

Despite this evidence, benzene may be represented in equations or mechanisms 11

1
either by the Kekulé structure or by the simplified structure above.
Although the simplified structure allows an improved understanding of the
properties of benzene, a better insight comes from considering its electronic
and orbital structure.

10. 1 Benzene: Structure

Figure 18.1.11 shows benzene with normal covalent sigma bonds ( bonds)
between its carbon and hydrogen atoms. Each carbon atom uses three of its
electrons to form three bonds with its three neighbours. This leaves each
carbon atom with one electron in an atomic p orbital.
Benzene consists of six carbon atoms arranged in a regular hexagon, each

alt
joined to a hydrogen atom and Hto it’s neighbouring carbons
one electronon either side
Figure 18.1.11 Sigma bonds in benzene,
H p orbital
with per carbon atom
by ! bonds. H H
remaining in a p orbital.

Carbon in benzene only H makes threeH bonds instead of four. The p-oritals in
the bonds are sp2 hybridised. σ bond The remaining p-orbital is non-hybridised

and has an unpaired electron which forms part of the central delocalised
These six p electrons do not pair up to form three carbon–carbon double
electron
bonds (consistingcloud.
of a bond plus a bond) as in the Kekulé structure. delocalised electrons

Instead, they are shared evenly between all six carbon atoms, giving rise to
H
circular clouds of negative charge above and below the ring of carbon atoms
(Figure 18.1.12). This is an example of a delocalised electron system, which C C
occurs in any molecule where the conventional structure shows alternating H C C H
double and single bonds. Within the electron system, the electrons are free
C C
to move anywhere. Aromatic hydrocarbons and phenol
d (δ) is formed by direct Kekulé’s benzene structure has three double bonds, soH it wouldHbe expected
Molecules and ions with delocalised electrons, in which the charge is spread benzene
overtoa larger
haveregion
a enthalpy
than usual, change of −360 kJ mol −1, three times
18.1.12that of cyclohexane
o orbitals on adjacent carbons, are more stable than might otherwise be The result agrees reasonably closely with the delocalisation en
Figure Representation of the
expected. In benzene, this accounts for the compound being 152 kJ mol−1 obtained using enthalpy changes of hydrogenation. (See quest
g one electron, so that the because three double bonds are
more stable than expected for the Kekulé structure. hydrogenated. A theoretical
delocalised cyclic
bonding in benzene. The
of this chapter.)
sity is concentrated between circle in a benzene ring represents six
Thecompound with
development of ideas three the
concerning double
structurebonds
of benzeneisillustrates
cyclohexa-1,3,5-triene.
the delocalised electrons. This way of showing
ei. way in which theories develop and get modified as new knowledge becomes the structure explains the shape and Electron delocalisation in benzene

10. 2 Benzene: Structure

available. stability of benzene. The extra stability of benzene and the fact that its C − C bonds
) is formed by the sideways length can be explained using the following model.
o p orbitals on adjacent carbon + 3H2 p orbital
The carbon atoms in the benzene ring have sp2 hybrid orbitals
providing one electron.
The six spare p orbitals, one on each carbon atom,18.1.3 areDelocalisation
all parallel toHeach
(a) σ-bonded skeleton
(C
in and atoms
benzene 523
other They are bonded to one another and to their hydrogen atoms
leaves one unused p orbital on each carbon, each containing a
and
Aromatic perpendicular
hydrocarbons to
and phenol
cyclohexa-1,3,5-triene
the plane of the ring.
cyclohexane Figure 29.6
omitted for clarity) These p orbitals are perpendicular to the plane of the ring, with
and one below this plane (Figure 26.2 (a)). Each p orbital over
ring. This gives the molecule greater stability compared with The result agrees reasonably closely with the delocalisation energy of benzene with the two neighbouring orbitals to form a single π-bond ext
However,
in which the π-electrons are localised whenindividual
between benzene is hydrogenated
469983_18.1_Chem_Y1-2_519-540.indd 523
obtained using enthalpythe enthalpy
changes change(Seeisquestion
of hydrogenation. only 3 at the end 13/04/19 10:00 PM of charge above and below the plane of the molecule (Figure 2
The electrons in the π-bond do not ‘belong to’ any particular c
−208 kJ mol−1, −1
of this chapter.)
this is 152 kJ mol less than expected. This means that the Each electron is free to move throughout the entire π system,
actual structure of benzene
s called the resonance stabilisation energy. In benzene, is more
its Electron stable than
delocalisation the Kekulé structure
in benzene are said to be delocalised. It is this delocalisation that gives be
stability: any system in which electron delocalisation occurs is
(cyclohexa-1,3,5-triene). The extra stability of benzene and the fact that its C − C bonds are all of equal reason for this is not hard to see. Electrons tend to repel one a
length can be explained using the following model. system in which they are as far apart from one another as poss
p orbital
delocalised π-system is written The delocalised is to draw model
a The carbonof
10.9 benzene
in a formula atoms in the benzene ring have sp2 hybrid orbitals (Section 3.5). minimum repulsion and will therefore be stabilised.
(a) σ-bonded skeleton Figure
They are bonded Overlap of
to one another (b) σ-skeleton
and to their hydrogen atoms byπ-bonds
with σ-bonds. This
nd the atoms that are part of that system (C and H— for benzene, To conform with this model, the structural formula of benzene
hin the hexagon representing theEach p orbital overlaps equally with both its neighbours, forming a delocalised
atoms
Today’ s accepted structure p
leaves
forz -orbitals
benzene in
one unused benzene
p orbital on each carbon,
is of a delocalised each
Fig 26.2 containing
model
Bonding
whicha single
in benzene.
haselectron.
Note that the
six carbon
omitted for atoms
clarity) (Figure These p orbitals are perpendicular to the plane of the
plane ofmolecule
the ring,is perpendicular
with one lobe to the
above
kulé formulae are acceptable at A six-centre
level and atmolecular
university. !The orbital.
paper rather than . As we shall see in Section 26.4, the
the following features: and one below this plane (Figure 26.2 (a)). Each p orbital overlaps sideways
with the two neighbouring orbitals to form a single π-bond extending as a ring
e, which has no π-electrons, is drawn as in Figure 10.10b. of charge above and below the plane of the molecule (Figure 26.2 (b)). π-electrons has a profound effect on the chemical properties of
Kekulé spent years studying ● It is a planar hexagonal molecule of six carbon atoms.
The electrons in the π-bond do not ‘belong to’ any particular carbon atom. The word aromatic is used to describe any system like that in
of carbon–carbon(b)bonds. He ● All carbon–carbon bondEach lengths areis free
intermediate in length between
electron to move throughout the entire π system,that
so theof a
electrons is stabilised by a ring of delocalised π-electrons. Non-aromatic
discovered the ring shape to be delocalised. It is this delocalisation that gives benzene its extra (such as alkanes and alkenes) are called aliphatic.
C6H12 single C–C and a double C=C.
are said
ne molecule after having stability: any system in which electron delocalisation occurs is stabilised. The The structure described above means that the benzene molecu
● Each carbon uses threereason of itsforouter electrons
this is not hard to see.to formtend
Electrons three sigma
to repel bondsso a
one another,
of a snake seizing its own symmetrical and non-polar. Its lack of polarity results in benze
an ancient symbol known as to two other carbon atoms, and one hydrogen atom. This leaves each
system in which they are as far apart from one another as possible will involve at room temperature and makes it immiscible with water. Its b

10.(b)3σ-skeletonBenzene: Structure
minimum repulsion and will therefore be stabilised. 80 °C and its melting point 6 °C. The surprisingly high melting
formula for (a) benzene and (b) cyclohexanecarbon atom with one
with π-bonds electron in a p orbital.
as. To conform with this model, the structural formula of benzene is often written as the ease with which highly symmetrical benzene rings can pac
Fig 26.2 Bonding in benzene. Note that the lattice. Compare this with that of the structurally similar but le
plane of the molecule is perpendicular to the
paper compound methylbenzene C6H5CH3, which melts at –95 °C.
rather than . As we shall see in Section 26.4, the delocalisation of

π-electrons has a profound effect on the chemical properties of benzene.

a hydrogen atom attached to each carbon atom in benzene. When

26.3
H
H The word aromatic is used to describe any system like that in benzene which
tution, a hydrogen atom is replaced by another group. Therefore, one
le molecule such as HBr, HCl or H2O.
C C is stabilised by a ring of delocalised π-electrons. Non-aromatic compounds Heading aromatic
Naming A compounds
H C (suchCas alkanes
H C are called aliphatic.
andH alkenes) C H
C CThe structure described above means C that the benzeneCmolecule is planar,
H H
symmetrical H of polarity results in benzene
and non-polar. Its lack H being a liquid
In this
at room temperature and makes it immiscible section
with you
water. Its will learn
boiling to:is
point Benzene is not the only aromatic hydrocarbon. Many others e
• Name other aromatic
80 °C and its melting point 6 °C. The surprisingly high melting point is due to either substituted forms of benzene or compounds containing
compounds
the ease with which highly symmetrical benzene rings can pack into a crystal systems. Some other aromatic hydrocarbons are discussed in S
e structures of the ethanoate, CH3COO –, ion.overlap
P orbitals Sigmalattice.
bond Compare this with that of the structurally similar butsystem
• Use a numbering less symmetrical
to The name ‘benzene’ comes from gum benzoin, a natural produc
sideways compound methylbenzene C6H5CH3, which melts
show at –95 °C. position
substituent benzene derivatives. The name phene, derived from the Greek
Delocalised electrons above light’, was at one time suggested as an alternative to ‘benzene’
and below the plane of the was originally isolated from illuminating gas by Michael Farad
carbon atoms adopted, but it survives in the word phenyl used for the C6H5
ure of arenes
nd with a benzene ring. 26.3
Figure 29.9 The formation ofNaming
the delocalised
Heading A electron
aromatic structure
compounds
488
of benzene.
phenyl group is an example of an aryl group.

The lobes of the p orbitals do not pair up to form three carbon–carbon

●
uents In this section you will learn to:
• Name other aromatic
Benzene is not the only aromatic hydrocarbon. Many others exist: they are
double bonds as in theeither
Kekulé structure,
substituted but overlap
forms of benzene sideways
or compounds todifferent
containing form aring
up replaces one hydrogen atom incompounds
a benzene ring, the name of
ring of charge above and below
systems. Somethe plane
other aromatic ofhydrocarbons
the molecule. Thisinoverlap
are discussed Section 26.8.
stem -benzene with a prefi x of• Use
theagroup or atom
numbering system entering,
produces a system of piThe
to name ‘benzene’ comes from gum benzoin, a natural product containing
bonds. The six p electrons spread over the whole
show substituent position benzene derivatives. The name phene, derived from the Greek pheno ‘I bear
ring – they delocalise and give
light’, regions
was at
Methylbenzene
one time of
was
electron
suggested density toabove
as an alternative
originally
and
‘benzene’ (benzene
was originally isolated from illuminating gas by Michael Faraday). It was not
lorobenzene. below the ring as shown in Figure
called
adopted, toluene
but 29.9.
because
it survives in theitword phenyl used for the C6H5 − group. The
methylbenzene. Bilal ●Hameed was group
Delocalisation of p electrons
phenyl first isolated
makes from of
benzene
is an example theanmore stable than Marginalizer
aryl group.
nitrobenzene. 488 resin of the South American
the theoretical molecule tree
cyclohexa-1,3,5-triene.
Tolu balsam. The enthalpy of
alled aminobenzene.
hydrogenation is 152 kJ mol−1 less than expected due to the extra stability
system is based on the Bilal Hameed
phenyl group, H5 group, thus:
−C6delocalised Arenes
of the electrons that are more spread out and so have fewer
phenol.
Computer-generated model electron–electron repulsions.
either
le phenylamine
of benzene. It is aorplanar ● The delocalisation of electrons
aminobenzene. Aminobenzenealso accounts
was called for the intermediate
 carbon atom
A linear six-carbon alkane would its neighbou
have the formula C6H14 − more than all parallel to
ch does not show the carbon or
twice the number of hydrogens overlaps equ
carbon atom and one hydrogen atom at
compared with benzene. 12 π orbital (see
2 Figure 25.4 The delocalised π bond in
tional groups (substituents) replacing benzene
atoms in its structure. Synoptic link H
10.
You4will need
Benzene:
to know theStructure
covalent
of benzene bonding studied in Topic 3.2, H C
H
benzene, C6H6, was a puzzle for a long This, therefore, results in each carbon having a bond angle of 120˚and a

alt
Covalent bonding, and bonding
use: trigonal planar shape. All carbon-carbon C equal inHlength and
H bonds are C
in alkenes studied in Topic 14.1, C C
d, it does not readily undergo addition strength,
Alkenes.as are all carbon-hydrogen bonds. H
C by theCskeletal formula
The benzene structure is normally represented
equivalent, which implied that all the H C H H

he same. H
H C H All the bond

—
H

—
C C
ular hexagon of carbon atoms, each of H C 120° H
—
0.13926_04
nm. Th
Ca
—
drogen atom. The geometry of benzene FigureC18.1.3CKekulé’s
120° 120° snake and his structural and skeletal formulae for the structure
C
of
C (0.154 nm) a
he difference between the flat benzene benzene.
C— Kekulé’s
C — formula would have the systematic name cyclohexa-1,3,5-triene.
H C H Barking
The usualD
ed cyclohexane ring (Figure 3). H C H
formula (der
—

Kekulé’sH structure explained many of the properties of benzene. ItH was structural. Fi
a b c
▲ accepted
Figure 1 Thefor many ofyears,
geometry but still left some problems.
benzene represented
Figure 25.5 Three representations of the
(the dashed lines show the shape and detail how th
benzene molecule: a the Thiele skeletal
Cl Cl The absence of isomers of 1,2-dichlorobenzene
do not represent single bonds)
formula, b the Kekulé skeletal formula, c the Kekulé struc
26_05 Cam/Chem
structural formulaAS&A2
for benzene and Thiele s
Cl Cl ▼ Kekulé’s structurebondsuggests
Table 1 Carbon–carbon lengths that there should be two isomers of
10.1,2-dichlorobenzene,
5 Benzene: Structure
one in which the chlorine
Barking Dog Artatoms are attached to
Bond Length / nm Figure 25.6 a Ball-and-stick and b electron- a
carbon atoms linked by a single carbon–carbon bond, models
the other in which
The six-centre
C C delocalised ! bond is responsible for
0.154 the following
density physical of benzene
molecular
the chlorine
and chemical
atoms are attached
properties of benzene.
to carbon atoms linked by a double carbon–
Figure 18.1.4
▲ Figure Possible
3 The isomers of
puckered C . . . C
carbon bond (Figure 18.1.4).
0.140
1,2-dichlorobenzene.
cyclohexane ring
• In
(in benzene)
It causes all C—C bond lengths to be equal, creating a planar, regular
Cpractice,
hexagonal
it has
C shape. never been possible to separate two isomers of
0.134
zene are intermediate between those
1,2-dichlorobenzene
C C or any other 1,2-disubstituted compound of benzene.
0.120
• To
single bond and a carbon–carbon double
is intermediate between a single and a It prevents
get round benzene
this undergoing any of the
problem, Kekulé normal addition
suggested reactionsmolecules
that benzene that might
alkenes show.
somehow alternate rapidly between the two possible structures, but this
failed to satisfy his critics.
• The ! bond also makes benzene more stable than expected.
435 In the skelet
The bond lengths in benzene: X-ray atom, to whi
chlorobenze
diffraction data Cl
The Kekulé structure shows a molecule with alternating single and double
bonds. This would imply that three of the bonds are similar in length to
the carbon–carbon single bond in alkanes while the other three are similar
10.in6length
Benzene: Structure double bond in alkenes. X-ray diffraction
to the carbon–carbon
studies show that the carbon atoms in a benzene molecule are at the corners The Kekulé
Carbon–carbon
of a regularbond lengths(Figure
hexagon in ethane, ethene and
18.1.5). All benzene.
the bonds are the same length, was clearly i
shorter than single bonds but longer than double bonds (Figure 18.1.6). unsaturated
0 0.1 nm
It ought to u
inert to most
Figure 18.1.5 Electron density map of C C
C C Table 25.1 A comparison of some reactions
benzene. Reagent
of benzene and cyclohexene
0.154 nm 0.134 nm 0.139 nm shaking with
ethane
Figure ethene
18.1.6 Carbon–carbon bond benzene
lengths in ethane, ethene and benzene. shaking with
H2(g) in the p
The resistance to reaction of benzene
An inexperienced chemist looking at the Kekulé structure might expect
benzene to behave chemically like a very reactive alkene and to take part in
addition reactions with bromine, hydrogen bromide and similar reagents.
Benzene does not do this. The compound is much less reactive than alkenes
and its characteristic reactions are181333_25_A_Chem_BP_415-439.indd
substitutions, not additions. 417

520 Marginalizer
18.1 Arenes – benzene compounds Bilal Hameed

Arenes Bilal Hameed

3_18.1_Chem_Y1-2_519-540.indd 520 13/04/19 10:00 PM

 13
3

10. 7 Aromatic Compounds

Compounds that contain rings of delocalised electrons are called aromatic

alt
compounds.

The name was originally applied to certain natural products that had strong,
pleasant aromas, such as vanilla-bean oil, clove oil, almond oil, thyme oil and
oil of wintergreen.

Test yourself
ORGANIC4
ORGANIC
a) Look carefully at Figure 18.1.8. How much more stable is real
CHEMISTRY
CHEMISTRY
benzene than Kekulé’s structure for benzene?
b) Predict the enthalpy changes for the complete hydrogenation
Orthethetwo
tworings
rings couldshare
sharetwo
twocarbon
carbonatoms
atomsinincommon their π electrons),
common (withtheir
10. 8 ofAromatic Compounds your π electrons),
Or
cyclohexa-1,4-diene and ofcouldcyclohexa-1,3-diene. Justify(with
asasininnaphthalene:
naphthalene:
predictions.
ORGANIC CHEMISTRY Arenes
5 Howare does
hydrocarbons,
the model such as benzene,
of benzene methylbenzene
molecules and
with delocalised
naphthalene.
electrons They are ringfor
account compounds
the following? in which there are delocalised
electrons. The simplest arene is benzene. common (with their π electrons),
a) The
Or the twobenzene
rings ringtwo
could share is carbon
a regular
atoms inhexagon.
as in naphthalene: More rings can fuse together, giving such compounds as anthracene and pyrene:
More rings can fuse together, giving such compounds as anthracene and pyrene:
b) There are no isomers of 1,2-dichlorobenzene.
c) Benzene is less reactive than cycloalkenes.
6 When chemists thought that benzene had alternate single and double
naphthalene
bonds, it was sometimesanthracene named cyclohexa-1,3,5-triene. Why is this
pyrene
now an unsatisfactory
More rings systematic
can fuse together, giving suchanthracene
compounds
anthracene name for benzene?
as anthracene and pyrene
pyrene:
pyrene

Noticethat
Notice thatwith
witheach
eachsuccessive
successivering ringfused
fusedtogether,
together,the thehydrogen-to-carbon
hydrogen-to-carbonratio ratio
decreases,from
decreases, from11: 1: 1ininbenzene
benzenetoto55: 8: 8ininpyrene.
pyrene.Eventually,
Eventually,asasmany
manymore moreringsringsfuse
fuse

18.1.4 Naming arenes together,aasheet

together,
Manyofofthe
Many
sheetofofthe thegraphite
themultiple-ring
graphitelattice
multiple-ringarenes,
lattice(graphene)
arenes,such
(graphene)would
suchasaspyrene,
pyrene,are
wouldresult
result(see
arestrongly
(seeTopic
Topic4).
stronglycarcinogenic
carcinogenic
4).

(cancerproducing).
(cancer producing).Even Evenbenzene
benzeneitselfitselfisisaahighly
highlydangerous
dangeroussubstance,
substance,causingcausing
The name ‘benzene’
anthracene comesanaemia
anaemia
fromand
gumonon
andcancer
cancer
pyrene benzoin,
prolongedaexposure
prolonged
natural
exposure product
totoitsitsvapour.
containing
vapour.InInthethepast
pastititwas wasusedusedasas
benzene derivatives. These
Notice that with each successive
aalaboratory
ring
derivatives
laboratory
fused
solvent,but
solvent,
together, the
ofhydrogen-to-carbon
butitsits usebenzene
use isisnow
nowseverely
severelyare named
restricted,
restricted,
ratio
either
although
although asadded
ititisisstill
still addedtoto
somebrandsbrandsofofunleaded
unleadedpetrol petroltotoincrease
increasetheir theiranti-knock
anti-knockrating.
rating.
substituted products
decreases, from of some
1 : 1 in benzene benzene
to 5 : 8 in pyrene.or as compounds
Eventually, as many more containing
rings fuse the phenyl
group, C 6H Physical
Physical properties
properties of
of arenes
arenes
5 –. The names and(graphene)
structures ofresult
some derivatives of benzene are
together, a sheet of the graphite lattice would (see Topic 4).
10. 9
shown in Naming Arenes
Many of the multiple-ring arenes,
Table 18.1.1.
(cancer producing). Even benzene
Benzene
Benzene
such and
and
as most
pyrene, are stronglyare
alkylbenzenes
most alkylbenzenes
itself iswith,
a highly dangerous
carcinogenic
stronglyoily-smelling
are strongly
substance,
oily-smellingcolourless
colourlessliquids,
liquids,
immiscible
immiscible with, and andless
lessdense
densethan, water.causing
than,water. Theyare
They arenon-polar,
non-polar,andandthe theonly
only
anaemia and cancer on prolonged exposure to its vapour. In to
thethepast it was dipoles
used as of van der Waals’ forces. Their
The names
Tablea 18.1.1and
laboratoryThestructures
names
solvent, and
but its ofboiling
use some
intermolecular
intermolecular
structures
is nowpoints derivatives
severelyof
bonding
bonding
aresome
is of
isdue
due
benzene
to
derivatives
restricted,
similarto
the
although
tothose
those
induced
induced
itof are shown
dipoles
benzene.
isequivalent
still added to below.(see Table 25.3), and
of van der Waals’ forces. Their
boiling points are similar ofofthe
the equivalent cycloalkanes
cycloalkanes (see Table 25.3), and
some brands of unleaded petrol to increase
increasesteadily their
steadilywith anti-knock
withrelative rating.
relativemolecular
molecularmass massasasexpected.
expected.
increase
Systematic
Physicalname
propertiesSubstituent
of arenesgroup Structure
Table 25.3 Boiling points of some
Table 25.3 Boiling points of some Compound Formula Boiling Compound Formula Boiling
cyclohexanes andBenzene
arenes and most alkylbenzenes Compound Formula colourless
are strongly oily-smelling Boiling liquids,
Compound Formula Boiling
cyclohexanesChlorobenzene
and arenes Chloro, Cl – point/°C
C
point/°C6
immiscible with, and less dense than, water. They are non-polar, and the only
H5 Cl – point/°C
point/°C
cyclohexane C H12 81 benzene CH 80
intermolecular bonding is due cyclohexane C6H6 12
to the induced dipoles 81Waals’ forces.
of van der benzene
Their C6H6 6 6 80
Nitrobenzene Nitro,
methylcyclohexane
methylcyclohexane
boiling points are similar to those
–
NO2 CCcycloalkanes
of the equivalent 7H14
7H14
100 C H5 NO
100(see6Table
methylbenzene
2 and
methylbenzene
25.3),
– CH
C7H7 8 8
111
111
increase steadily with relative molecular mass as expected. ethylbenzene C8H10 136
ethylbenzene C8H10 136
Methylbenzene Methyl, CH3 – C6H5 CH3
propylbenzene
– CH 159
propylbenzene C9H9 1212 159
Table 25.3 Boiling points of some
Compound Formula Boiling Compound Formula Boiling
cyclohexanes and arenes Phenol Hydroxy,
point/°C OH – C H OH
6 5point/°C –
cyclohexane
Phenylamine
methylcyclohexane
C6H12
C7H14
25.2
81
25.2 –Isomerism
benzene
Amine, Isomerism
100
NH2
CH
and
and
methylbenzene C H
nomenclature
80
5– NH2
C6Hnomenclature
111
6 6

7 8
Aromaticcompounds
compounds withmore
ethylbenzene moreCthan
than one substituent onthe
thebenzene
benzenering
ringcan
canexist
exist
Aromatic with 8H10 one substituent
136 on
The names used for asaspositional
positionalisomers.
compounds
isomers.There
with
Thereare
a benzene
propylbenzene
arethree
threedichlorobenzenes:
dichlorobenzenes:
C H ring can 159 be confusing. The
9 12

phenyl group C6H5 – is used to Cl name

Cl many compounds Cl
Cl in which one Cl of the
Cl
hydrogen atoms in benzene has been Cl
Cl replaced by another atom or group.
25.2 Isomerism and nomenclature
The use of phenyl in this way dates back to the first studies of benzene. At
compounds with more than one substituent on the benzene ring Cl
this Aromatic
time ‘phene’ was suggested as an alternative name
as positional isomers. There are three dichlorobenzenes:
can exist
Cl for benzene, based
Cl
on a Greek word for ‘giving light’. The name ‘phene’ was suggestedClbecause
Cl Cl
benzyl’ has been used to benzene hadCl been discovered 1,2-dichlorobenzene
in the tar formed
1,2-dichlorobenzene
1,3-dichlorobenzene 1,4-dichlorobenzene
on heating coal1,4-dichlorobenzene
1,3-dichlorobenzene to produce
Cl
gas for lighting.
he group C6H5CH2– as in Bilal Hameed The terms ortho-, meta- and para- are
The terms ortho-, meta- and para- are sometimes usedasMarginalizer
sometimesused asprefi
prefi xestotorepresent
xes representthe
the
relativeorientations
orientationsofofthe
thegroups
groups(see
(seeTable
Table25.4).
25.4).
oride, C6H5CH2Cl. Good relative
When more than one hydrogen atom Cl is substituted, numbers are used to
ow avoids this by using the 420 420
Bilal Hameed indicate the positions of substituents on the benzene Cl ring (Figure 18.1.13). The Arenes
name for this compound,
ring is numbered
1,2-dichlorobenzene to get the lowest possible 1,4-dichlorobenzene
1,3-dichlorobenzene numbers. In phenyl compounds,
hyl)benzene, to remove any
with phenyl.
suchThe as420
181333_25_A_Chem_BP_415-439.indd
181333_25_A_Chem_BP_415-439.indd
phenol
420
terms ortho-,and phenylamine,
meta- the –OH
and para- are sometimes used as and –NH
prefixes 2 groups
to represent the are assumed to 10/10/14 8:32 PM
10/10/14 8:32 PM
 14
4

10. 10 Naming Arenes

When more than one hydrogen atom is substituted, numbers are used to

alt
indicate the positions of substituents on the benzene ring. The ring is
numbered to get the lowest possible numbers.

Cl Cl Cl NH2 OH
25 Arenes and phenols
25 Cl Arenes and phenols Cl

CH3 Br NO2
Table 25.4 Orientations of substituents on Orientation Prefix
Abbreviation Example
Table
the 25.4 ring
benzene Orientations of substituents on Orientation Prefix
Abbreviation Example Cl
the benzene ring 1,2-dichlorobenzene 1,2- ortho-
o- 1-bromo-3-chlorobenzene
1-chloro-3-methylbenzene CH3 3-nitrophenylamine 2,4-dichlorophenol
1,2- o- ortho- CH3
Figure 18.1.13 Naming disubstituted
products of benzene, phenylamine and
Test yourself NO2 phenol.
NO2
1,3- compoundmeta-
7 Why is the middle in Figurem-
18.1.13 named Cl CO2H
1,3-
1-bromo-3-chlorobenzene meta-
and m-
not 1-chloro-3-bromobenzene?Cl CO2H

8 An old bottle of chemical was found with the label m-dinitrobenzene. Tip
Draw the structure and give the systematic name of this compound. The prefixes ortho-, meta- and para-, or
1,4- para- p-
9 Name each of1,4-
these disubstituted
para- arenes.
p- their abbreviations o-, m- and p-, were
CH3 NH2
CH3 traditionally
NH 2
used to name, respectively,
a) b) c) d) 1,2- 1,3- and 1,4-disubstituted

10. 11 Naming Arenes

If the twoBrsubstituents are different, one ofOH
them is definedbenzene
as the compounds.
‘root’ group, in the
So the first
If the two substituents are different, one of them is definedcompound
as the ‘root’ group,
in Figure in used
18.1.13 the to
CH3following order of precedence COOH OH
following order of precedence beCHcalled ortho-dichlorobenzene or

Arenes
CH3 ¬CO2H > ¬OH > ¬CH Cl
3 > ¬halogen > ¬NO2
3
(NO 2 is called the nitro
o-dichlorobenzene. The usegroup)
of these
¬CO2H > ¬OH > ¬CH 3 > ¬halogen > ¬NO2
COOH (NO2 is called the nitro group)
and the ring carbons numbered from the carbon atom holding prefixes
that isgroup.
still seen
Forin the name of
example:
NO2 OH carbons numbered from the carbon atom holding
and the ring compounds such as
that group. Forparacetamol
example:(see
10 Draw and nameCH
Cl the Activity
Cl in Section 18.2.3).
the3isomers of C6H4Cl2, C6H3Cl3, C6H2Cl4 and
CH 3
C6HCl5.methylbenzene CO2H 1,3-dichlorobenzene
(Beware of duplicates!) is 2-methylbenzoic acid
(no number is required CO H (count anticlockwise to get
1-chloro-3-methylbenzene
(if the two substituents are different
is 2-methylbenzoic
as there is only one hydrogen 2 the lowest possible numbers)
acidalphabetically chloroTip
gets precedence over methyl)
substituted and all positions
are equivalent) Take care with the number of hydrogen
18.1.5 The
CH properties and reactions
OH 3
atoms when writing the formulae of
Cl benzenes. Chlorobenzene
CH substituted
of benzene
Cl and
Cl arenes 3
CH
is 3-bromomethylbenzene 3 is C6H5Cl, dichlorobenzene
Br is C6H4Cl2
Arenes are non-polar compounds with isweak 3-bromomethylbenzene
London forces between their and trichlorobenzene is C6H3Cl3.
molecules. The boiling temperatures of arenes depend on the size of the
Br
molecules. The bigger the molecules,
Br the higher
H3C the boiling
NH2 temperatures.
Cl Cl
Benzene and methylbenzeneNO2 are liquids at room temperature, while
naphthalene is a solid NO
2,4,6 -trichlorophenol
(Figure
2 and
(phenol takes precedence 18.1.14). 3,5-dimethylphenylamine
(phenylamine takes precedence and
2,5 -dichloro-1-bromobenzene
(alphabetically bromine takes position1
does not need a number: it is does not need a number: it is and the Cl are numbered to give the lowest
assumed the OH is at position 1) is 4-nitrochlorobenzene.
assumed the NH2 is at position 1) numbers)
CH3 is 4-nitrochlorobenzene. Figure 18.1.14 Three arenes: benzene,
Figure 7.7 A range of aromatic compounds, illustrating naming conventions.
methylbenzene and naphthalene.

Cl Test yourself
Cl
1 Describe, with the aid of suitable labelled diagrams:
benzene Worked example
methylbenzene naphthalene
a) the Kekulé model of benzene
Worked example b) the delocalised model of benzene.
Draw out all possible positional isomers of C6H3Br2OH and name them.

10. 12 Isomers ofa)C2,6-dibromophenol

6H3Br2OH
2 Draw
Draw out all possible the following
positional arenes:
isomers of C6H3Br2OH and name them.
Tip Answer
Answer
Benzene is toxic. It isThere
also aare
carcinogen. Because
six isomers. of this,
Their names benzene is banned from
and formulae
b) 2,4,6-trinitromethylbenzene are as follows:
teaching laboratories. There
Areneare six isomers.
reactions
OH Their names
mayc)be1,3–dimethyl
studied and
using other
OH formulae
compoundsare
benzene asas
such follows: OH
methylbenzene or methoxybenzene,OH C6H5OCH .
d) 3phenylethene. OH OH
Br Br Br
Br Br Br
18.1.5 The properties and reactions of benzene and arenes 525
Electrophilic
Br substitution Br
AsBrdiscussed on page 145, benzene does not readily
Br react with and
Br
decolourise bromine. However,
Br it does react with bromine in the presence
Tip
469983_18.1_Chem_Y1-2_519-540.indd of a
2,3-dibromophenol
525 suitable catalyst.
2,4-dibromophenol 2,5-dibromophenol 13/04/19 10:00 PM
2,3-dibromophenol 2,4-dibromophenol 2,5-dibromophenol
An electrophile is a species that OH Analysis of the productOshows H that benzene undergoesOsubstitution
H
can accept an electron pair, OH reactions rather than addition
OH reactions. OH
Br Br
resulting in the formationBrof a Br
Benzene is stable and retains the π-delocalised ring. The product is formed
(dative) covalent bond. by replacing one (or more) of the hydrogen atoms in C6H6, so that the
Now try this product is of the form C6H5X, where
Br X is an electrophile. Br
Now try this Br +
Br
Br
How many isomers are Tip
there of The most common electrophile
Br is H but it is Br
clearly pointless reacting
How many isomers are there
trichloromethylbenzene, C6H2of
Cl 3(CH3)? benzene, C6H6, with H . Br
+
Catalysts are used to generate different
trichloromethylbenzene,
What C6H2Cl
are their names? Metal 3(CH
ions 2,6-dibromophenol
3)? as Na+ cannot
such 3,4-dibromophenol
electrophiles such as NO2+, Cl+, Br+ and +CH3.3,5-dibromophenol
What are their names? behave as electrophiles 2,6-dibromophenol
because
3,4-dibromophenol 3,5-dibromophenol
The general equation is:
they do not form covalent bonds.
C6H6 + X+ → C6H5X + H+ 421
421
where X+ is the electrophile.

181333_25_A_Chem_BP_415-439.indd 421
Nitration 10/10/14 8:32 PM
181333_25_A_Chem_BP_415-439.indd 421 Nitroarenes are versatile compounds that are used in the preparation of 10/10/14 8:32 PM
drugs and dyes. The explosive trinitrotoluene, TNT, is made by the nitration
of methylbenzene (toluene is the old name for methylbenzene). 147

Marginalizer Bilal Hameed

Arenes Bilal Hameed

 15
5

RGANIC CHEMISTRY
10. 13 Naming
If the benzene ring is a ‘substituent’ on an alkyl or alkenyl chain, it is given

alt
If the benzene ring is a ‘substituent’ on an alkyl or alkenyl chain, it is given the name
the name phenyl:
phenyl:

CH2CO2H
C
C
H Cl

phenylethanoic acid 2,2-diphenylchloroethene

25.3 Reactions of arenes

Combustion
Benzene and methylbenzene (whose old name, toluene, is still in use) are

10. 14 completely
Physical Properties
components of many brands of unleaded petrol. In sufficient oxygen, they burn
to carbon dioxide and steam:

Benzene andCmost
6H6 + alkylbenzenes
1
are
7 2 O2 → 6CO2 + 3Hstrongly
2O oily-smelling colourless
liquids.
If liquid arenes are set alight in the laboratory, they burn with very smoky flames.
They areMuch
non-polar,
soot is and the only
produced intermolecular
because bonding
there is insuffi is duefor
cient oxygen to complete
the combustion.
A smoky flame is an indication of a compound with a high C : H ratio.
induced dipoles of van der Waals’ forces.
1
C6H6 + 1 O2 → 6C (s) + 3H2O
Because they are non-polar
2
in nature, they do not mix with water but are
soluble in non-polar
Just solvents suchthe
as with hydrogenation, asenthalpy
cyclohexane.
of combustion of benzene is less exothermic
than expected, because of the stability due to the six delocalised π electrons.

Electrophilic substitution in benzene

In a similar way to the π bond in alkenes, the delocalised π bond in benzene is an
area of high electron density, above and below the six-membered ring. Benzene
therefore reacts with electrophiles. Because of the extra stability of the delocalised
electrons, however, the species that react with benzene have to be much more
powerful electrophiles than those that react with ethene. Bromine water and aqueous
acids have no effect on benzene.
The electrophiles that react with benzene are all positively charged, with a strong
10. 15 electron-attracting
Physical Properties
tendency. The other major difference between benzene and
alkenes is what happens after the electrophile has attacked the π bond. In alkenes, an
Their boiling
anionpoints aretosimilar
‘adds on’ to those of
the carbocation the equivalent
intermediate. cycloalkanes,
In benzene, and hand, the
on the other
increase steadily with relative molecular mass as expected.
carbocation intermediate loses a proton, so as to re-form the ring of π electrons. This
demonstrates how stable the delocalised system is.
Benzene and methylbenzene are liquids at room • Br
temperature, while
naphthalene is a solid as it has stronger Vander Waals forces.
•

•
CH 2 CH 2 Br • Br CH2 CH 2 Br Br CH2 CH2 Br
carbocation intermediate

H Br Br
Br
•
•

–H

carbocation
intermediate

22

hem_BP_415-439.indd 422
Bilal Hameed Marginalizer 10/10/14 8:32 PM

Bilal Hameed Arenes

 16
6

10. 16 Reactivity
In a similar way to the ! bond in alkenes, the delocalised ! bond in benzene

alt
is an area of high electron density, above and below the six-membered ring.

Hence it attracts electrophiles and reacts with them.

Electrophilic substitution by bromine can occur (Figure 18.1.17) but, as
But because of the extra stability
in allofelectrophilic
the delocalised electrons, however,
substitution reactionsthe
of benzene, the first step of the
species that react with benzene have involves
reaction to be much
usemore powerfulto produce a stronger electrophile.
of a catalyst
electrophiles than those that react with ethene.
H Br
Bromine water and aqueous acids, thus, have no effect on benzene.
H C H H C H
C C C C
+ Br2 warm with + HBr
C C Fe or FeBr3 C C
H C H H C H

H H
bromobenzene
Figure 18.1.17 The reaction of benzene with bromine.
10. 17 Reactivity
The electrophiles that react with benzene are all positively
When benzene charged,
is warmed withbromine
with a strong in the presence of iron filings, the
electron-attracting tendency. bromine first reacts with the iron to form iron(iii) bromide.
by bromine can occur (Figure 18.1.17) but, as
Key terms
on reactions of benzene, the first step of theThe other major difference between2Fe(s)
benzene +and
3Bralkenes
2(l) →is2FeBr
what happens
3(s) after the
electrophile has attacked the ! bond.

€If
alyst to produce a stronger electrophile.
:÷ aftp.A
H H
Electrophilic substitutionThe iron(iii) bromide then acts as a catalyst for the reaction of bromine with
reactions ...
.

In alkenes, an anion
in arenes ‘adds
involve theon’ to the carbocation
benzene
replacement of by intermediate.
polarising further bromine molecules until a positive Br + ion is
Br
formed.
hydrogen atom following attack by anThis ion acts as the electrophile.
In benzene, on the other hand, the carbocation intermediate loses a proton, so as to re-
H C H electrophile.
form the ring of ! electrons. δ+ δ−
C C

:
warm with Chemists sometimes use the term ........FeBr3 → Br+ + FeBr4
+ HBr Br−Br
This demonstrates how stable the delocalised system is. + FeBr3 → Br−Br
Fe or FeBr3 C C halogen carrier to describe substances Brst |•
H C H such as iron(iii) bromide and Br+ ion is a reactive electrophile, which is strongly attracted to the
Thealuminium
+
thedelocalised
reaction of electrons in benzene. As it approaches the benzene ring, the Br
€
If
chloride which catalyse
:÷ftp.A
H H
...
.

ion forms a covalent bond to one of the carbon atoms using two electrons
.

H
,

benzene with chlorine or bromine.

bromobenzene from the π system (Figure 18.1.18). This step produces an intermediate cation.
F
nzene with bromine.
t
Tip Y¥ **I t
th bromine in the presence of iron filings, the10. 18 Electrophilic
Brst |•t.ae#.l*F
Mechanisms :

t.rs
:
In these intermediate cations, the positive charge is delocalised over five carbons. The
iron to form iron(iii) bromide.
other carbon, the one at which substitution
% occurs, is attached to four atoms, so it is
Alkenes react by electrophilic addition. Arenes react by electrophilic
.

s) saturated and therefore not part of the electron delocalisation.

substitution.

is
ts as a catalyst for the reaction of bromine with This intermediate then breaks down to form bromobenzene as two electrons

Y¥ retail ;
A- A
r bromine molecules until a positive Br+ ion is are returned from the C–H bond to the system and the stable, delocalised
**I
+
.

Began
, ,

lectrophile.
Fz¥
ring is restored (Figure 18.1.19). At the same time, an H+ ion is released
t.ae#.l*F from the Brintermediate cation. This +
Br HBr ion immediately combines with the

t.rs
:
δ+ δ−
Br − ion released in stage 1 to form hydrogen bromide.
→ Br−Br........FeBr3 → Br+ + FeBr4 %
.

ectrophile, which is strongly attracted to the H

H Br
ne. As it approaches the benzene ring, the Br+A-
¥ ;
H+
retail
+
go.gg#.itn:fq.E*s.::kI*s.
+ + A .

H+ H Br
Br +
Br
Began
, ,

one of the carbon atoms using two electrons

Fz¥
OH

+2
1.18). This step produces an intermediate cation.
Br+Brions
FigureBr 18.1.18 ElectrophilicA.Figure Bruse
18.1.19 The intermediate cationI breaks down to form bromobenzene.

.tk#af+*r
A .

.
.

two of the delocalised electrons in benzene

to form an intermediate cation. Begins
A similar reaction occurs when benzene is warmed with chlorine in the
presence Brof iron, iron(iii) chloride or
Br aluminium chloride. The catalysts

are often referred to as halogen carriers.

-

e positive charge is delocalised over five carbons. The

ubstitution occurs, is attached to four atoms, so it is go.gg#.itn:fq.E*s.::kI*s.
¥
H H

OH

+2
of the electron delocalisation.
.tk#af+*r
A I
A.
18.1.6 Electrophilic sub
.

.
.

ond to the system and the stable, delocalisedBegins

s down to form bromobenzene as two electrons
Marginalizer Bilal Hameed
Br Br

.19). At the same time, an H+ ion is released

:
-

Arenes
. This H+ ion immediately combines with the ¥
469983_18.1_Chem_Y1-2_519-540.indd 527
Bilal Hameed
form hydrogen bromide.
 Nitration
The mixture of concentrated nitric and sulfuric acids which reacts with benzene
is called a nitrating mixture. At 55 °C, concentrated nitric acid on its own reacts
very slowly with benzene, and concentrated sulfuric acid by itself has practically
17 reacts with nitric acid
no effect. However, in a mixture of the two, sulfuric acid
to produce nitronium
25 ions, NO +
, which7are very reactive electrophiles: Arenes and phenols
2

HNO3 + H2SO4 → NO2+ + HSO4− + H2O

The nitronium ions are formed by removal of OH Alkenes− ions
react byfrom nitricaddition.
electrophilic acid by
10. 19 Electrophilic Substitution: Step 1
Arenes react by electrophilic substitution.
sulfuric acid. In this reaction, HNO3 is acting as a base and H2SO4 is acting as
an acid. Bromination
The NO2+ ion is a reactive+ electrophile which is strongly attracted to bromine
the on warming in the presence of
The powerful electrophile (E ) becomes attractedBenzene towillthe !with
react bond of benzene.
non-aqueous

alt
delocalised electrons in benzene. As it approachesanhydrousthealuminium
benzene ring,orthe
chloride NO2+bromide, or iron(III) chloride, or even
aluminium
Ition
eventually breaks the ring of electrons and forms a "
metal. bond
In the to
latterone
case, of
an the
forms a covalent bond to one of the carbon atoms using two electrons reaction between iron and bromine
just iron initial

carbon atoms
from the of the(Figure
π system ring. 1.18).
The mechanism of electrophilic
provides the iron(III) bromide substitution
catalyst:

2Fe(s) + 3Br2(l) → 2FeBr3(s)

H H
Anhydrous aluminium The mechanism of electrophilic substitution
Figure 1.18
or iron(III) halides contain electron-defi ! They can
cient atoms.

The mechanism of electrophilic substitution

C
react with the bromine molecule by accepting one of
bromine:
C
Electrophilic
the lone pairs nitronium ions
attack the
of electrons on
H H H H delocalised electrons in benzene to form
ilic substitutions are the characteristic reactions ofCarenes, such C
as C Br C
1.7 The mechanism
in which the delocalised π electrons are attacked + of
by strong electrophiles. E+ electrophilic
NO 2
+
•
+substitutionE 2
NO
Br an intermediate cation.

Electrophilic substitutions
C are the characteristic reactions
C Br CBrof • arenes,
Al CBr such asBr Br Al Br (1a)
n benzene, in whichH theCdelocalised H π electrons are attacked H by
C Br H
strong electrophiles. Br
ure of concentrated nitric and sulfuric acids which reacts with benzene
Nitration nitric acidHon its own reacts
a nitrating mixture. At 55 °C, concentrated This causes strongH polarisation of the Br¬Br bond, weakening it, and eventually
leading to its heterolytic breaking:
ly with benzene, and concentrated Thesulfuric
mixture acid
of by itself has practically
concentrated nitric and sulfuric acids intermediate
which Br cation
reacts with benzene
The formation of a with
covalent bond in an intermediate cation disrupts the Br
However, in a mixture of the two,is sulfuric
called a acid reacts
nitrating mixture. nitric
At acid
55 °C, concentrated nitric acid on its own reacts
+
e nitronium ions, NO2 , which very delocalised
are very ring.
reactive A large input of energy is needed to do this and the reaction
with electrophiles:
•
slowly benzene, and concentrated sulfuric Br acid • Brby Al itselfBrhas practically Br + Br Al Br (1b)
has a fairly high activation energy.
− no effect. However, in a mixture of the two, sulfuric acid reacts with nitric acid
+ H2SO4 → NO2 + HSO4 + H2OThe unstable intermediate cation quickly breaks downBrproducing
+
Br
to produce− nitronium ions, NO2+, which are veryThe reactive electrophiles:
onium ions are formed by removalnitrobenzene.
of OH ions from This nitric
involvesacidthe byreturn of two the electrons fromthata isC−H
bromine cation formedbond to electrophile. It becomes attracted to
is a powerful
π bond of benzene. It eventually breaks the ring of electrons and forms a σ bond
the
HNO πaselectron
3a+base
H2SO 4 →
system. NOThe + stability−of the delocalised
+ HSO4 + H2O to one ring is restored and
10.
cid. In this reaction, HNO3 is acting
20
energy Electrophilic
and
is released
H2SO
Substitution: Intermediate
42is acting as
(Figure 1.19).
of the carbon atoms of the ring:
−
The nitronium ions are formed by removal of OH ions from nitric acid by H
O2+ ion is a reactive electrophile which is strongly attracted to the is acting as a base andBrH SO is acting asBr
Two of acid.
sulfuric
ed electrons in benzene. As it approaches thethe
six
In!this
electrons
benzene H ring,are
reaction,
theused
HNO
NO32+to form the (dative) H bond2 to the 4 Figure 1.19 !
(2)
an acid.
electrophile.
s a covalent bond to one of the carbon atomsTheusingother
two four ! electrons are spread
electrons over the remaining five The intermediate cation breaks down to
The NO2+Hion is aCreactiveHelectrophile which C six π electrons
H Twoisofstrongly
the
attracted
NO2are used totothe
form the (dative) bond to the bromine atom.
form nitrobenzene.
π system (Figure 1.18). carbon atoms of
delocalised electrons C thein ring,
C in a five-centre
benzene.
delocalised
As it approaches
The other four orbital.
C the benzene π electrons are spread over the
C ring, the NO + remaining five carbon atoms of the
(see2Figure 25.10).
+ H+
NO2 ring, in a five-centre delocalised orbital
+
H ion forms a covalent H bond to one of the carbon atoms
Figure 1.18 using two electrons
from the π system C
Figure 25.10CThe four π electrons are
(Figure 1.18). C ! C
H delocalised over five carbons
CH Electrophilic
H nitronium ions
C H attack the
H C H H C H delocalised electrons
5 in benzene
6 H
to form
C C C HC an intermediate H Figure 1.18 !
H cation.
+ NO2+
H NO
+ E 2 4
1
Electrophilic nitronium ions attack the
C C HC intermediate
CC cationH Hnitrobenzene
C H delocalised electrons in benzene to form
H C H H CC CH C
3 C
2 E+
Br
an intermediate cation.
+ NO
Halogenation + NO2 + 2

H CH is warmed
C with bromine in the presence
C C filings, the
When benzene
H H H distribution
of iron
C The C of the fourHπ electrons is not even. They are associated more with
intermediate
bromine
mation of a covalent bond in an intermediate
first reactscation
with the iron to form iron(carbon
cation disrupts the
III) bromide:
atoms 3 and 5 than with atoms 2, 4 and 6. The positive charge is therefore
distributed
25.10 JM/Chem.4over atoms 2, 4 and 6. This is best represented by the following classical
AS&A2
2Fe(s)to
ed ring. A large input of energy is needed + do
3Brthis H → 2FeBr
2(l) and 3(s)
the reaction mesomers: H
Barking Dog Art
ly high activation energy. H H H
TheThe iron(III) bromide
formation of producing then acts
a covalent bondasina catalyst for the reaction
an intermediate cation of bromine
disrupts thewith
nstable intermediate cation quickly breaks down δ+Br δ−
benzene
delocalised by polarising
ring.fromA large further
input bromine
of energy molecules as Br −Br (Figure
is needed to do this and the reaction 1.20).
Br Br Br
zene. This involves the return of two electrons a C−H bond to
hasdelocalised
ctron system. The stability of the a fairly high ring activation
is restoredenergy.and 3+ – δ+ δ– Figure 1.20 !
released (Figure 1.19). 10.The21 Electrophilic
unstable Br
intermediate Br +Substitution:
Fe (Br
cation )3
quickly breaksStep
Br down Br2..... Fe3+(Br– )3
producing Fe3+ ions in iron(III) bromide423 polarise 9
nitrobenzene. This involves the return of two electrons from a C−H bond to bromine molecules as Brδ+−Brδ−.
H Theπintermediate
the electron H system. carbocation
The stability thenofloses a proton,
theFigure 1.19 to
delocalised re-form
!ring the sextet
is restored and of !
energy is
electrons. released (Figure 1.19).
181333_25_A_Chem_BP_415-439.indd 423
The intermediate cation breaks down to 10/10/14 8:32 PM

H C H H C NO2 form nitrobenzene.

C C C C H H Figure 1.19 !
NO2 +
+ + H
The intermediate cation breaks down to
H
C C
H H
C H C C
H C
H H C E 2
NO form nitrobenzene.
C C C C C
+ E 2
NO + H+
H H
C C C C
intermediate cation H
nitrobenzene C H H C H

nation H H
intermediate
nzene is warmed with bromine in the presence of ironcation
intermediate cation
filings, the nitrobenzene
nitrobenzene
first reacts with the iron to form iron(III) bromide:
Halogenation
+ 3Br2(l) → 2FeBr3(s)
When benzene is warmed with bromine in the presence of iron filings, the
(III) bromide then acts as a catalyst for the
bromine reaction
first reacts of bromine
with with
the iron to form iron(III) bromide:
by polarising further bromine molecules as Brδ+−Brδ− (Figure 1.20).
2Fe(s) + 3Br2(l) → 2FeBr3(s)
δ+ δ– Figure 1.20 !
Br Br + Fe3+(Br– )3 The iron( Br ..... Fe3then
BrIII) bromide +
(Br–acts
)3 as a catalyst
Fe3+for thein reaction
ions of bromine
iron(III) bromide polarisewith 9
δ− Brδ+−Brδ−.
bromine as
benzene by polarising further bromine molecules Brδ+−Bras
molecules (Figure 1.20).
δ+ δ– Figure 1.20 !
Bilal Hameed Br Br + Fe3+(Br– )3 Br Br ..... Fe3+(Br– )3 Marginalizer
Fe3+ ions in iron(III) bromide polarise 9
bromine molecules as Brδ+−Brδ−.

Bilal Hameed Arenes

 ring at positions 2 or 4. These positions are ‘activat
Most reactions of benzene maintain the highly stable
384 by any electron-donating groups
The mechanism of bondedsubstitution
electrophilic directly t
delocalised ring of π bonding electrons intact. This occurs
benzene ring (see Table 25.4 on page 390). Other
by substituting an atom, or group of atoms, for one or more
examples of benzene compounds that are activated
hydrogen atoms1.7 attached
The tomechanism
the benzene ring. The initial
of electrophilic substitution
attack is usually 18
by an electrophile, which is attracted to the
these positions are phenol and phenylamine. So wh
Electrophilic substitutions are the characteristic reactions of arenes, such as
8 we react methylbenzene with chlorine gas, using a
high electronbenzene,
densityinaround
which the benzeneπring.
thedelocalised electrons are attacked by strong electrophiles.
anhydrous aluminium chloride catalyst, two produ
Nitration be made:
Electrophilic substitution with chlorine
The mixture of concentrated nitric and sulfuric acids which reacts with benzene
or bromine
is called a nitrating mixture. At 55 °C, concentrated nitric acid on its own reacts
10. 22 Bromination very slowly with benzene, and concentrated sulfuric acid by itself has practically CH3 CH3 CH3
Benzene willno
react with
effect. bromine
However, in the presence
in a mixture of the two,of an acid reacts with nitric acid
sulfuric
Electrophilic
Electrophilic
to produce
substitution
substitution
anhydrous iron(III) bromide catalyst. The
nitronium ions, NO + bybybromine
brominecan
catalyst can be
, which are very reactive
can occur AlCl
(Figure18.1.17)
electrophiles: occur (Figure
18.1.17)
Cl but,asas
but, 3

inin allallelectrophilic
electrophilic substitution reactions ofofbenzene,
benzene,the
thefirst
firststep
stepofofthe
the
2 + 2Cl2 +
Benzene willmade
react
in with non-aqueous
the reaction vessel by bromine
adding onsubstitution
+ iron warming
filings to thein the presence
reactions

alt
HNO 3 + H2SO4 → NO2 + HSO4 + H2O
−
reaction involves use of a catalyst to produce a stronger electrophile.
of anhydrous iron(III)
benzene andbromide
bromine.
The toThe
nitroniumform
reaction bromobenzene.
involves
substitution
ions are use of
reaction
formed by a catalyst to produce a stronger
removalis:of OH− ions from nitric acid by electrophile.
Cl
sulfuric acid. In this reaction, HNO3 is acting as a base and H2SO4 is acting as
Br
an acid. HH
anhydrous The mechanism of electrophilic substitutionBrBr 2-chloromethyl- 4-chlorom
The NO2+ ion is a reactive electrophile which is strongly attracted to the benzene benzen
Electrophilic substitution 3 catalyst
FeBrby bromine can occur (Figure 18.1.17) but, as +
delocalised
+ Br electrons in benzene. As+ it approaches
HBr the benzene ring,
Key the NO
terms
formsHa covalent
in all electrophilic Hsubstitution
2 C toofone
reactions
C H
Hbenzene, the first step of the excess H 2
C C is bubbled H H through, we can
1.7 The mechanism ofionelectrophilic
reaction involves
from
use of a catalyst
the π C
system
bond
substitution
C (Figure
to produce
C1.18).
of the carbon atoms using If
C a stronger electrophile.
Hchlorine
two electrons
ElectrophilicC C
gas
substitution C C
reactions
Electrophilic substitutions are the characteristic reactions of arenes, such as warm form
with 1-methyl-2,4-dichlorobenzene, 1-methyl-2,6-
+ Br2 warm with HBr
+ + HBr
Br Br2on
the+attack
benzene, in which theAt delocalised π in arenes involve the replacement of a
H electrons
first sight are attacked by
the electrophile strong
that electrophiles.
starts dichlorobenzene and 1-methyl-2,4,6-trichlorobenz
H H Figure 1.18
FeFeor or FeBr3hydrogen atom following attack by an!
C C C
C H is created FeBr C C
Nitration benzene isC not obvious. The electrophile when 3
electrophile. C
(Remember that the C 6 nitronium
2 and
Electrophilic positions inattack
ions substitute
the
H HH H HH H HH H H in benzene to form
H H C H
C C CCC H C C
Cuse
delocalised electrons
an iron(III)
The mixture of concentrated bromide
nitric and sulfuric molecule
+ acids warmpolarises
which
Br2 C reacts aCbromine
C with benzene
with
C
+ C
HBr are
C equivalent.)
Chemists sometimes the term
an intermediate cation.
is called a nitrating mixture. At 55 °C, concentrated nitric acid on its
+ own +
reacts
NO NO2 carrier to describe substances
The carbon–halogen
halogen bond in halogenoarenes is
molecule.
C TheC Br2 molecule formsFe or
HC3ahas
FeBr
dativeC (co-ordinate)
C +
H Hand aluminium
2
very slowly with benzene,Hand concentrated
C H sulfuric acid
C by H itself Hpractically
C H C C such as iron(iii) bromide
no effect. However, inbond withof iron(III)
a mixture bromide
the two, sulfuric by
C donating
H acid reacts withHnitrica acid
lone pair of
H C stronger
H
chloridethan the equivalent
which catalyse bond in a halogenoalk
bromobenzene of
the reaction
to produce nitronium electrons H
ions, NO2+, from
which one bromine
are very reactiveatom into an empty
electrophiles: H
3d orbital because withbromobenzene
benzeneone of the orlone
chlorine pairs on the halogen atom
bromine.
Figure
Figure 18.1.17
H
18.1.17 TheThe reaction
reaction of benzene H with bromine.
other of benzene with bromine.slightly with the π bonding system in the
bromobenzene
HNO3 + H2SO4 →in NOthe+
2 +iron.
Figure
HSOThis−
+H
4 The
18.1.17 draws
2O
reaction ofelectrons
benzene withfrom the
bromine. bromine overlaps
atom in the
The nitronium ions are formed by removalBr
The2 molecule
formation − making
of a it
covalent partially
bond
of OH ions from nitric acid by in positive,
an intermediate cation ring. This
disrupts thegives the carbon–halogen bond a partial
sulfuric acid. In this reaction, delocalised as ring.
baseAand
large
H2input isofacting
energyasis needed to do thisbond and the reaction
WhenHNO
creating is acting
the 3electrophile.
benzene is warmed a with bromine SO
When benzene is warmed with bromine in the presence of iron filings, the
in4 the presence of iron filings, the character.
bromine first reactsWhen
has a fairly high benzene is warmed
bromide. with bromine in the presence of iron filings, the
an acid. activation energy.
with the iron to form iron(iii)
Thewhich
unstable intermediate cation quickly breaks down to
romine can occur (Figure 18.1.17)
The NO2+ ion is a reactive electrophile
but, asdelocalised electrons in benzene.
2Fe(s) +As3Br
bromine
bromineis strongly
(l) → 2FeBrthe
nitrobenzene.
it 2approaches This
first
involves
3(s) benzene
reacts
attracted
first reacts to the
thethe
ring,
withthe
with
return
theironirontoproducing
formiron(iii)
form iron(iii)bromide.
NO2of+ two electrons from a C−H bond to
bromide.
Key terms
ion forms a covalent bond to one of the π electron
carbon system.
atoms using The
two stability
electrons of the delocalised ring is restored and
eactions of benzene, the first step
10. 23 Bromination: Electrophilic Substitution
of thefrom the π system (FigureThe iron(iii) bromide then
benzene
energy is released
1.18). by polarising
2Fe(s)
2Fe(s)
acts as+ a+3Br 3Br
catalyst
(Figure 2(l)
2(l)
for
1.19).
further bromine molecules
→→
the 2FeBr
2FeBr
reaction 3(s)+ with
3(s)
of bromine
until a positive Br ion is
o produce a stronger electrophile. Electrophilic substitution
formed. This ionreactions
acts The
H iron(iii)
as the electrophile. bromide then actsH as!a catalyst for the reaction
The iron(iii) bromide then acts as a catalyst for the reaction of bromine with
H Figure 1.18 of bromine with
Figure 1.19 !
Electrophilic nitronium ions attack the The intermediate cation breaks down to
in arenes involve Hthe replacement of a δ+Cbyby
benzene polarising further ++
Cbromine moleculesuntil until a positiveBrBr ionis is
δ−
Br H C
Br−Br
benzene
+
H
H
FeBr → Br−Br
polarising
H
........FeBr →
further
Br + +HFeBr bromine
delocalised Brmolecules
NO
electrons in a positive
2 benzene to form form nitrobenzene.
ion
hydrogen
C atom C following attackformed. by anC
3C
formed. This This
C
ion ion 3
acts as the C4electrophile.
an intermediateC cation.
Br
+ + NO
The Br
++
+
ion2 is a reactive electrophile, Br 2 acts
NO
which
as the electrophile.+ H+
is strongly attracted to the
H C H electrophile.
C Cdelocalised electrons in benzene.
C
C As itCapproaches the benzene C ring, the CBr+
H
H C H HH C H H C δ+ δ−δ−
δ+ H + + Br
C C ion forms a covalent bond to one of the carbon atoms using two electrons Br
m with Chemists Hsometimes from the πuse the(Figure
term18.1.18).HThis step ........
3→ 3→
Br−Br
produces+ an FeBr + + FeBr
HBr H Br−Br FeBr BrBr
+ system intermediate cation. ........
3→ →
Br−Br + FeBr Br−Br Figure FeBr
18.1.18
+Br+ FeBr
+ ions use 4 4
3Electrophilic
FeBr3 C C halogen carrier to describe substances intermediate cation nitrobenzene two of the delocalised electrons in benzene
H C H The
suchbromine
The formation of a
as Airon( cation
covalent bond
bromide
)Tip is attracted
in an intermediate
and The The toBr
aluminium theBrdelocalised
+ +
cation
ion disrupts the ! bondelectrophile,
ionis isa areactive
reactive ofelectrophile,
benzene. Itto form which
which is isstrongly
an intermediate strongly
cation. attractedtotothe
attracted the
delocalised ring. largeiiiinput of energy is needed to do this and the reaction
has a eventually
chloride
fairly breaks
which
high activation theintermediate
catalyse
Inenergy.
these ring
theof electrons
Halogenation delocalised
delocalised
reaction
cations, and
theofpositive forms
electrons
electrons
charge a in
" in
is delocalisedbond fiveto
benzene.
benzene.
over oneAs
carbons. of
Asitthe
The itapproaches
approachesthe thebenzene
benzenering, ring,the ++
theBrBr
carbon,When
the one benzene is warmed withisbromine infour
theatoms,
presence of iron filings, the
H carbon
benzene
nitrobenzene.
atoms
The unstable intermediate
Thiswith
ofsaturated
the
chlorine
involves
ring.
othercation quickly
orbromine
the return
and
atbreaks
ion
bromine.
of two
therefore
ionforms
which
first
down
forms
reacts
electrons
not part
producing
a acovalent
substitution
with
from
of the
covalent
occurs,
athe
C−H
electron iron
attached
bond
bondtoIIIto
to
bond
to form
to iron(
delocalisation. )one
oneofofthe
so it is
bromide:
thecarbon
carbonatoms atomsusing usingtwo twoelectrons
electrons
The other four !1.19). electrons are
from
spread
the πis2FeBr
πover system
the
(Figure
remaining
18.1.18).
five
This step produces anan intermediate cation.
as twocarbon
electrons atoms of
bromobenzene the π electron system. The stability of the from 3Brthe
delocalised
2Fe(s)
then+
ring
2(l) → system
restored
3(s)
(Figure
and 18.1.18). This step produces intermediate cation.
energy is released (FigureThis intermediate breaks down to form bromobenzene
with bromine.
In a Friedel–Crafts acylationIn athe ring, in a five-centre
Friedel–Crafts
reaction, an acylation
acyl
are returned delocalised
from
The the reaction,
chloride,
iron( C–H orbital.
RCOCl,
bond
III) bromide tothen an The
the acylasintermediate
reacts
system
acts chloride,
a and the stable,
catalyst carbocation
RCOCl,
for thedelocalised reacts
reaction of bromine with
then loses
H ring is restored
a proton,
(Figure
benzene
tointermediate
re-form
18.1.19).
by polarising
the
H
ansextet
Atfurther
the same time,molecules
bromine an HFigure Tip
+ ion is released
Brδ+−Br
as 1.19 ! δ− (Figure 1.20). Tip
with aluminium chloridewith to fromaluminium
an acylium chlorideion to from
(Figure 18.1.27). Hof
acylium ! immediately
This
Tip electrons.
ionion(Figure The 18.1.27). This iondown to Figure 1.20 !
Tip
from the cation. This + ion intermediate
combines with thecation breaks
H C Br−Hion released in H 1 toCform NO2 formδ+ δ–
nitrobenzene.
omine in the presence
acts as of
theiron actstheas two-step
filings, thein
electrophile theC electrophile
Celectrophilic in the two-step
stage
substitution
C electrophilic
BrC hydrogen
Br + Fe bromide.
reaction 3+
(Br– )3 substitution
Acylium
Br ions Fereaction
Br .....are
3+
(Br– )3
formed Acylium
in massFe3+ ionsions are
in iron( formed
III) bromide in mass
polarise
NO2 In these intermediate + H+ cations, the positive charge is delocalised bromineover five as
molecules Brδ+−Brδ−The
carbons. .
to form iron(iii) (Figure 18.1.28).
bromide. (Figure 18.1.28).
+
C C H
In these intermediate
C Br
C
cations,spectrometers
the positive charge is delocalised
as fragment of over five carbons.
spectrometers
ions as fragmentThe ions o
H C +H Br H other
other carbon,
Ccarbon,+H the
H
the one
+ one at at which
which substitution
substitution occurs,
occurs, is is attached
attached
compounds such as ketones orcompounds to
acid to four
four atoms,
atoms, soso
it it is or a
is
such as ketones
saturated
saturated andand therefore
therefore notnot part
part of of
thethe electron
electron delocalisation.
delocalisation.
derivatives (Chapter 19). derivatives (Chapter 19).
+ H +H –
CI + AICI3 CI + Figure –18.1.19 The intermediate
+ cation + breaks
of bromine withR RC intermediate AICI R nitrobenzene
C cation AICI
down to form bromobenzene.
a catalyst for the Rreaction
C C AICI 34 4
+
mine molecules untilOa positive Br ion isHalogenation
O O
10. 24 Bromination: Electrophilic Substitution
A similar reaction This This
occurs
presence of iron, iron(iii)
intermediate
intermediate
when then
benzene is warmedthenbreaks
breaks
with down
down
chlorine totoform
in the
Ochloride or aluminium chloride. The catalysts
formbromobenzene
bromobenzeneasastwo
twoelectrons
electrons
are are returned
returned from
from thetheC–HC–H bond
bond to to the
the system
system and
and the
the stable,
stable, delocalised
delocalised
ophile. When benzene is warmedarewith
often referredinto
an asacylium
halogen carriers.
presenceion
Benzene
bromine first reactswill
an acylium ion
withreact
bromine
with
the iron non-aqueous
the
to form
ring
ring
iron(III) bromide:
bromine(Figure
restored on
of iron filings, the
is isrestored warming
(Figure in theAtpresence
18.1.19).
18.1.19). Atthe
thesame
sametime, + +ion
time,ananHH ionis isreleased
released
Figure
Figure 18.1.27 Formation of an 18.1.27
acylium ion. Formation
of anhydrous iron(III) bromideof an acylium
from ion.
to form thebromobenzene.
intermediate cation. This H
+ + ion immediately combines with the
δ− 2Fe(s) + 3Br2(l) → 2FeBr3(s) from the intermediate cation. This H ion immediately combines with the
18.1.6 Electrophilic substitution reactions of benzene 527
− − ion
Br released ininstage
stage 1 to form hydrogen bromide.
−Br........FeBr3 → Br+ + FeBr4 for theion
The iron(III) bromide then acts as a catalystBr released
reaction of bromine with 1 to form hydrogen bromide.
benzene by polarising further bromine molecules as Brδ+R −Brδ− (Figure 1.20). R
phile, which is strongly attracted to the HBr 3+
Br + Fe (Br )3 –
469983_18.1_Chem_Y1-2_519-540.indd 527
δ+
BrH
Br
δ–
HH
C..... Fe3+(Br– )3
Figure 1.20 !
Ciron(
BrIII) bromide polarise 13/04/19 10:00 PM
Fe3+ ions inBr 9
As it approaches the benzene+ ring, the Br+ + bromine molecules as Brδ+−Br + δ−.
+ C +
RR + ++ C Br
BrBrOR + H+ + + +H+HH+
O
of the carbon atoms using CtwoRelectrons Br
This step produces an intermediate
O cation. O + ions use O
Figure 18.1.18 Electrophilic BrFigure
Figure 18.1.19
18.1.19 TheThe intermediate
intermediate cation
cation breaks
breaks down
down to to form
form bromobenzene.
bromobenzene.
Figure 18.1.28
Figure 18.1.28 Electrophilic substitution Electrophilic
mechanism for substitution
Friedel–Crafts mechanism
acylation of for Friedel–Crafts acylation of
two of the delocalised electrons in benzene
benzene. to form an intermediate cation.A Asimilar
benzene. similarreaction
reactionoccurs
occurswhen
whenbenzene
benzeneis iswarmed
warmedwith withchlorine
chlorineininthe
the
presenceofofiron,
presence iron,iron(iii)
iron(iii)chloride
chlorideororaluminium
aluminiumchloride.
chloride.The
Thecatalysts
catalysts
ive charge is delocalised over five carbons. The are often referred to as halogen carriers.
are often referred to as halogen carriers.
Tip Tip
tion occurs, is attached to four atoms, so it is
In Friedel–Crafts alkylation, theIninitial
electron delocalisation. Friedel–Crafts alkylation,
product contains anthe initial
alkyl groupproduct contains
attached to a an alkyl group attached to a
benzene ring. Alkyl groups arebenzene
electronring. Alkyl groups
releasing, are electron
so the electron releasing,
density on thesoringtheis electron density on the ring is 18.1.6
18.1.6 Electrophilic
Electrophilic su
wn to form bromobenzene as on
greater than two electrons
benzene, greater
which makesthan on benzene,
further which
substitution makes further substitution likely.
likely.
to the system and the stable, delocalised
In Friedel–Crafts
At the same time, an H+ ion isacylation,
releasedtheIninitial
Friedel–Crafts acylation,
product contains the initialgroup
a carbonyl product contains
attached to a carbonyl group attached to a
benzene ring. The carbonyl benzene
group ring.
withdraws The carbonyl
electron group
density withdraws
from the electron
benzene ring,density
so from the benzene ring, so
s H+ ion immediately combines with the 469983_18.1_Chem_Y1-2_519-540.indd527527
further substitution is unlikely.further substitution is unlikely.
469983_18.1_Chem_Y1-2_519-540.indd
hydrogen bromide. Marginalizer Bilal Hameed

r Test yourself
Arenes Test yourself Bilal Hameed
+ +
H
22 This question is about22theThis question is reaction
Friedel–Crafts about thebetween
Friedel–Crafts
benzenereaction between benzene
and ethanoyl chloride, CHand
3 ethanoyl
COCl, in the chloride,
presence CH
of3 COCl, in
aluminium the presence of aluminium
 In a Friedel–Crafts acylation reaction, an acyl chloride, RCOCl, reacts
19
with aluminium chloride to from an acylium ion (Figure 18.1.27). This ion Tip
9
acts as the electrophile in the two-step electrophilic substitution reaction Acylium ions are formed in mass
(Figure 18.1.28). spectrometers as fragment ions of
and phenol
compounds such as ketones or acid
10. 25 Bromination:
+ Formation
– of the Electrophile derivatives (Chapter 19).
R C CI + AICI3 R C + AICI4
The NOAnhydrous
+
iron(III)
2 then attacks one bromide
of the contain
carbon electron-deficient
atoms of the ring,atoms. They
forming can to it
a bond

alt
O react with
and disrupting thethe bromine O molecule
delocalised π-electron
by accepting
system: one of the lone pairs of
electrons on bromine.
an acylium ion
NO2
Figure 18.1.27 Formation of an acylium ion.
This causes strong polarisation of the Br—Br bond, weakening it, and
eventually leading toNO
its2heterolytic breaking.
+
+ H
R

H
The formation of this intermediate C
requires the input of considerable energy
+ break the delocalised π-electron system. Because of this, the reaction has a
to +
C Rhigh activation energy, C R O + H+
fairly which is why it needs heating.
O
Finally, the intermediate cationO breaks down, either reforming benzene or
producing
Figure 18.1.28 nitrobenzene. As
Electrophilic substitution
In a Friedel–Crafts this happens,
mechanism
acylation reaction, anfor the delocalised
Friedel–Crafts
acyl chloride, π systemreacts
acylation
RCOCl, ofre-forms,
with releasing energy:
aluminium chloride to from an acylium ion (Figure 18.1.27). This ion Tip
benzene.
national A Level Chemistry
NO2
acts as the electrophile in the two-step electrophilic substitution reaction Acylium ions are formed in mass
+
(Figure 18.1.28).H + NO2
− NO2 − spectrometers as fragment ions of
Tip 10. 26 Bromination: Catalyst
+
Regneration
H + H+compounds such as ketones or acid
We can think+of the electrophile
– as a Br+ cation: derivatives (Chapter 19).
R C
In Friedel–Crafts CI + AICIthe
alkylation, 3 initial Rproduct + AICI4 an alkyl group attached to a
C contains
Notice that the first twoδ+stages ofδ–this mechanism, up to the formation of the
lectrons arebenzene
involved ring.O Alkyl
in the groupscation,
π bonding
intermediate are electron releasing,
areBrsimilarO to theso
Br FeBr the electron
stages density
Br
in addition onalkene
+ to an
+ [FeBrthe] –ringdouble
is
3 4
benzene greater thanbond.
molecule?
ourings contain on benzene, which makes
The difference is thatfurther
an acylium substitution
ion
with aromatic likely.
compounds, the intermediate cation
+
rom aromatic
type Figure
of atomic orbital 18.1.27
doloses
the its charge
electrons by The
Formation of anBr
loss of Hcation
+ ion.
acylium and
, thus the ‘electron-rich’
regaining benzene
delocalisation ring are
energy. With alkenes
me from? In Friedel–Crafts
are rigorously
there acylation,
is no the attracted
initial energy
delocalisation product
to eachcontains
to other,
be as
lost athe
or carbonyl group
mechanism
gained, so attached
below
the shows.to acation
intermediate
they can be used
benzene ring. The carbonyl
combines The final stage regenerates the catalyst, by the reaction between the proton
with group withdraws
Remember
an anion thatelectron
to form curlydensity
theaddition
an arrows from
showthe
product. the benzene
movement
R ring,
of aso
mean by the term ‘delocalised
benzene? further substitution (H
+) formed with the [FeBr4]−.
is unlikely. pair of electrons.
H C
difference between the π bonding +in

.6
BrO
d the π bonding in hex-3-ene? C R H + FeBr4
+ + C — H
R —> HBr + FeBr
Br 3+ H+
Important electrophilic substitution
Heading
Test yourself
played or skeletal formula of:
O A stage
O 1
Br ⎯⎯⎯→ +
+
stage 2
⎯⎯⎯→ + HBr
bromobenzene reactions of benzene [FeBr ] acylation of
Figure 18.1.28 Electrophilic substitution mechanism for Friedel–Crafts
–
(+FeBr )
4 3

22 This
oro-5-nitrobenzene. question
benzene. is about the Friedel–Crafts reaction between benzene
olecules below: and ethanoyl chloride,ACHsimilar reaction happens when chlorine gas is bubbled
3COCl, in the presence of aluminium
u will learn to: Nitration through benzene at room temperature in the presence
ii Br
Tip AlCl3, as catalyst.
chloride,
electrophilic The detailed mechanism of a catalyst
of thissuch as iron(III)
reaction chloridebeen
has already or aluminium
considered in the
CH3 of
ions Cl
a) Write an equation to show how AlCl molecules react with tofrom
last section. alkylation,
In Friedel–Crafts chloride.
It is usedthe The
industrially products
initial product of
to contains this
manufacture
3 electrophilic
an alkylnitrobenzene, substitution
group attached a which
polarised
phenylamine CH COCl are
(aniline), chlorobenzene
molecules
C H NH to
, is and
producehydrogen
produced chloride.
reactive
by The
acylium
reduction. catalysts
ions.
Phenylamine is in is
benzene
10.
ring.
27
Alkyl groups
Chlorination
are electron releasing, so the electron density on the ring
Cl 3 6 5 2
hilic used to
greater than manufacture
on benzene, for thesedyes
which reactions,
(see
makes i.e.
Chapter FeBr ,
27).
further substitution AlCl and
likely. FeCl 3 benzeneas
, are known
lorobenzene
b) Write an equation the electrophilic 3 substitution
3 of
‘halogen carriers’.
by A similar
Halogenation
acylium
In Friedel–Craftsions electrophilic
to
acylation, produce
the initialwesubstitution
phenylethanone.
product contains reaction
a carbonyl occurs
group when chlorine gas is
known When halogenate methylbenzene or attached
other to a
bubbled through benzene at room temperature in the presence of a catalyst
f arenes
action and give benzene
c) Write ring.
Benzene
further
The
an equation carbonyl
does not react
such
substitution asis
group
alkylarenes,
to
iron(III)
unlikely.
show withdraws
withhow
chloride or
electron
the halogen
molecules
chlorine,
aluminium
density
atom of
bromine from
substitutes
orthe
chloride.
the benzene
into
aluminium
iodine on their ring,
the benzeneso
own in the
n it is used dark. This
chloride is because ring theat non-polar
positions 2 or 4. Thesemolecule
halogen positionshas are no‘activated’
centre of positive
zene maintain the highly stablecatalyst are regenerated.
charge to initiate electrophilic
by any attack on the
electron-donating benzene
groups bonded ring. However,
directly to thein the
bonding electrons
23 a)intact.
Why This
must
presence
The
occurs
the catalysts
of a reaction
catalyst
insuch
these
mixture
as
reactions,
iron be i.e. FeBr
completely
filings, iron( 3, AlCl
) dry3 and
bromide
FeCl
during or 3, are known as
aluminium
benzene ring (see Table 25.4 on page 390). Other
III
aTest
m, or group of atoms, for one orhalogen
yourself
more
Friedel–Crafts
chloride, benzene carriers.
reaction?
is substituted by chlorine or bromine:
examples of benzene compounds that are activated in
hed to the benzene ring. The initial
b) Draw
22 the
This structures
question is these
aboutof positions
the
the are phenol
products
Friedel–Crafts of aand phenylamine.
Friedel–Crafts
reaction between
− Cl So when
reaction
benzene
n electrophile, which is attracted to the anhydrous
and ethanoyl we react
chloride, CH
+ Cl methylbenzene
COCl, in the with
presencechlorine of gas,
aluminiumusing + anHCl
around the benzeneof benzene with:
ring. 32
chloride, AlCl3, asanhydrouscatalyst. aluminium AlClchloride
3 catalyst, two products can
ubstitution with i) 2-iodo-2-methylpropane
chlorine be made:
a) Write an equation to show how AlCl molecules 3 react with
chlorobenzene
ii) When
propanoyl
polarisedchloride.
CH3act
iron filings COCl
as molecules to they
the catalyst, produce
first reactive acylium
react with ions. forming
the halogen,
CH3 CH3 CH3
th bromine in the iron(
c) presence III)chloride
b) of
Suggest an
a reason
Write orfor
iron(
an equation III)the
using
for bromide.
an iodoalkane
electrophilic instead
substitution of benzene
Cl of
AlCl3
bromide catalyst. The catalyst
by can
a chloroalkane be
acylium ions to produce
in a Friedel–Crafts
The catalyst (called a ‘halogen phenylethanone.
reaction.
carrier’)
+ 2Cl accepts a lone pair
+ from one+ of
2HClthe
2
vessel by adding iron filings
halogento the
c) Write atoms. This induces
an equation to show polarisation in theofhalogen
how molecules molecule:
the aluminium
e. The substitution reaction is: Cl − Cl: → AlCl
chloride catalyst are regenerated. 3 Cl
δ+ be
Br 23 a) Why must the reaction mixture δ– completely
2-chloromethyl-dry during
4-chloromethyl-
anhydrous benzene 18.1.6 Electrophilic substitution reactions of benzene
benzene 531
a Friedel–Crafts reaction?
FeBr3 catalyst
r2 + HBr
b) Draw the structures ofchlorine
the products of a Friedel–Crafts
Bilal Hameed If excess gas is bubbled through, we reaction
can Marginalizer
of benzene with:
form 1-methyl-2,4-dichlorobenzene, 1-methyl-2,6-
rophile that starts the attacki)on2-iodo-2-methylpropane
dichlorobenzene and 1-methyl-2,4,6-trichlorobenzene.
Bilal Hameed Arenes
us. The electrophile is createdii)when
983_18.1_Chem_Y1-2_519-540.indd (Remember that the 2 and 6 positions in substituted arenes
propanoyl chloride.
531 13/04/19 10:
molecule polarises a bromine are equivalent.)
c) Suggest a reason for using an iodoalkane instead of
a chloroalkane inThe
olecule forms a dative (co-ordinate) carbon–halogen
a Friedel–Crafts bond in halogenoarenes is
reaction.
 CH3 methylbenzene
AlCl catalyst
+ CH3Cl Figure3 18.1.24 Friedel–Crafts alkylation
+ HCl of benzene with chloromethane forming
heat
methylbenzene.
20 methylbenzene
A similar reaction
Figure 18.1.24 Friedel–Crafts alkylation 10benzene
occurs when benzeneCH3 is refluxed with the acyl chloride,
ethanoyl AlClof
3 catalyst
chloride, plus
with chloromethane
aluminium chloride
forming
methylbenzene. + CH3Cl + asHCla catalyst. This time, the product
is phenylethanone, heat also known as methylphenylketone (Figure 18.1.25).

A similar reaction occurs when benzene ismethylbenzene refluxed with the acyl chloride,
10.ethanoyl
28 Alkylation
chloride, plus aluminium
Figure 18.1.24 Friedel–Craftschloride
alkylationasofa benzene
catalyst.with
This time, the product
chloromethane CH3
forming
is phenylethanone, also known as methylphenylketone (Figure 18.1.25).
methylbenzene.
O
When benzene is heated under reflux with a chloroalkane in the presence ofC

alt
AlCl3 catalyst O
aluminium chloride,
A similar thereaction
alkyl group+
occurs attaches
CH C
when
3 to the benzene
benzene isheat
refluxed
CH3 ring.with the acyl chloride, + HCl
ethanoyl chloride, plus aluminiumClchloride as a catalyst. This time, the product
This reactionisisphenylethanone,
an important
O method for substituting
also known an C alkyl group
as methylphenylketone for
(Figure a 18.1.25).
phenylethanone
hydrogen atom
+
in an arene.
Figure AlCl3 catalyst
18.1.25 Friedel–Crafts acylation of
O
benzene with
+ ethanoyl chloride forming
CH3C HCl
phenylethanone.
heat CH3
Cl CH3
AlCl3 catalyst
phenylethanone
+ CH3In Cl Friedel–Crafts
O reactions, the aluminium +C HClchloride plays the important
heat AlCl catalyst O
Figure 18.1.25 Friedel–Crafts
catalytic
+ CH3C role
acylation in
of creating
benzene
3 the
with electrophiles
ethanoyl chloride which
forming attack
+ benzene. So, when
HCl
phenylethanone. chloromethane is mixed heat with aluminium chloride, AlCl 3 molecules remove
Cl methylbenzene
Cl− ions from polar δ+CH3 –Clδ− molecules, allowing reactive carbocations,
phenylethanone
In Figure 18.1.24 Friedel–Crafts
Friedel–Crafts +
CH3 ions,
reactions, thealkylation
toaluminium of benzene
chloridewith
act as electrophiles. chloromethane
plays the important forming
Figure
methylbenzene.
catalytic role in18.1.25
creatingFriedel–Crafts
δ+the
acylation which
of benzene with+ethanoyl chloride forming
phenylethanone. CHelectrophiles
δ−
3 –Cl + AlCl 3 → CH3
attack benzene.
+ AlClSo, 4
− when
chloromethane is mixed with aluminium chloride, AlCl3 molecules remove
electrophile
Cl−Aions from polar δ+CH –Clδ− molecules, allowing reactive carbocations,
similar reaction
In toFriedel–Crafts occurs
3 when
reactions,
These reactive CH
benzene
the+ aluminium is refluxed
chloride with
playsthethe
the acyl chloride,
important
CH3+ ions, act as electrophiles. 3 electrophiles then attack delocalised system of
ethanoyl chloride,
catalytic plus
rolebenzene
in aluminium
creating chloride
form anas
the electrophiles
molecules to a catalyst.
which attack This
intermediate benzene.time,
cation, So,the product
when
which breaks down
isδ+phenylethanone,
–Clδ− + AlCl
CH3chloromethane is→
3 also
producing mixedCH
known + + AlCl −
3 as
with methylphenylketone
aluminium
methylbenzene 4and chloride, AlCl3(Figure
H+ ions (Figure 18.1.26).18.1.25).
molecules remove
10. 29 Alkylation
− electrophile
δ+ δ−
Cl ions from polar CH3 –Cl molecules, allowing reactive carbocations,
CH3+ CH
These reactive ions,+toelectrophiles
act as electrophiles. CH3
then attack the delocalised system of
3 CH3 CH3
benzene molecules
3
to δ−form
δ+CH –Cl an
+ 3 intermediate
+ AlCl +
CH→ CH3+ cation,
+ AlCl
+ 4
which
− H breaks down
+ H+
+ 3
producing methylbenzene and H ions (Figure 18.1.26).
electrophile
O C
+ AlCl3 catalyst O
These reactive
+ CH3C
CH 3 electrophiles thenintermediate
attack the delocalised methylbenzene
system
+ HCl
of
CH3 cation
benzene molecules to form heat an intermediate cation, CH3which breaks down
Figure 18.1.26 +
+
+producing
CH
Cl + The
methylbenzene reaction
and of CH(Figure
HH+ ions 3 electrophiles with benzene
18.1.26). + H+
in the Friedel–Crafts
3
alkylation reaction to produce methylbenzene.
phenylethanone
CH
Figure 18.1.25 Friedel–Crafts
Finally, acylation
intermediate
thecation
aluminiumof chloride
benzene
3
with ethanoyl
methylbenzene
catalyst chloride
CH3 asforming
is regenerated H+ ions released in
+ H
phenylethanone. + the
CHelectrophilic
3 + substitution
+ −
react with AlCl4 ions. + H+
Figure 18.1.26 The reaction of CH3 electrophiles with benzene in the Friedel–Crafts
+ AlCl4 → HCl + AlCl3
H+methylbenzene.
alkylation reaction to produce
In Friedel–Crafts reactions, the aluminium chloride
intermediate
cation
plays the important
methylbenzene

catalytic
Finally, the role
aluminiumin creating
chloride the electrophiles which + attack benzene.
in So, when
Figure 18.1.26 The reactioncatalyst
of CH3+ iselectrophiles
regenerated
CH withasbenzene
H ions in released
the Friedel–Crafts
thechloromethane
electrophilic is mixed
substitution with
react
AlCl3tocatalyst
alkylation reaction withaluminium
AlCl
produce methylbenzene. 4
3 chloride,
− ions. AlCl 3 molecules remove
Cl − +ionsCH 3Cl
from polar δ+CH –Clδ− molecules, + HCl
allowing reactive carbocations,
H+ + +AlCl4 → HCl +heat AlCl3 3
ions, totheact
CH3 Finally, as electrophiles.
aluminium chloride catalyst is regenerated as H+ ions released in
methylbenzene −
the electrophilic
δ+CH δ− + AlCl substitution react with
+ +AlCl 4 ions.
10. 3018.1.24
Acylation 3 →
−
530 Figure
18.1 Arenes – benzene3 –Cl
Friedel–Crafts
compounds alkylation CH3with
of benzene AlCl
chloromethane
4 forming
methylbenzene. H + AlCl4 → HCl +electrophile
+ AlCl3
A similar reaction occurs when + benzene is refluxed with the acyl chloride,
Thesereaction
reactive 3 electrophiles
CHwhen then attack the acyl
delocalised
chloride, system of
ethanoyl
A similar chloride, plus aluminium
occurs chloride as
benzene a catalyst.
is refluxed with the
ethanoyl chloride, plus aluminium chloride as a catalyst. This time, the productbreaks down
469983_18.1_Chem_Y1-2_519-540.indd 530 benzene molecules to form an intermediate cation, which 13/04/19 10:00 PM
530 + ions (Figure 18.1.26).
18.1 Arenes – benzene compounds This time, the product
producing
is phenylethanone, is phenylethanone,
methylbenzene
also and Halso known as(Figure 18.1.25).
known as methylphenylketone
methylphenylketone.
CH3 CH3
530 18.1 Arenes – benzene compounds CH3
+ H
469983_18.1_Chem_Y1-2_519-540.indd 530
+ + +
13/04/19 10:00 PM
CH
O3 + C H
AlCl3 catalyst O
+ CH3C + HCl
heat
469983_18.1_Chem_Y1-2_519-540.indd 530 Cl intermediate methylbenzene 13/04/19 10:00 PM
cation phenylethanone
+
FigureFigure 18.1.26
18.1.25 The reaction
Friedel–Crafts ofofCHbenzene
acylation 3 electrophiles with
with ethanoyl benzene
chloride in the Friedel–Crafts
forming
alkylation
phenylethanone. reaction to produce methylbenzene.

In Friedel–Crafts reactions, the

Finally, the aluminium aluminium
chloride chloride
catalyst plays the important
is regenerated as H+ ions released in
catalytic
the electrophilic substitution react with AlCl − ions. So, when
role in creating the electrophiles which attack benzene.
chloromethane is mixed with aluminium chloride, AlCl4 3 molecules remove
polar4δ+CH
+ + AlCl
Cl− ionsHfrom → HCl δ−
3 –Cl + molecules,
AlCl3 allowing reactive carbocations,
+
CH3 ions, to act as electrophiles.
Marginalizer
δ+CH –Clδ− + AlCl → CH + + AlCl − Bilal Hameed
3 3 3 4
electrophile
Arenes These reactive CH3+ electrophiles then attack the delocalised systemBilal
of Hameed
benzene molecules to form an intermediate cation, which breaks down
producing methylbenzene and H+ ions (Figure 18.1.26).
 chloromethane is mixed with aluminium chloride, AlCl3 molecules remove
Cl− ions from polar δ+CH3 –Clδ− molecules, allowing reactive carbocations,
CH3+ ions, to act as electrophiles.
δ+CH δ− + AlCl → 21 CH3+ + AlCl4−
3 –Cl 3
11 electrophile
In a Friedel–Crafts acylation reaction, an acyl chloride, RCOCl, reacts
These toreactive
from an CH + Tip
with aluminium chloride 3 electrophiles
acylium then attack
ion (Figure 18.1.27). the delocalised
This ion system of
acts as the In a Friedel–Crafts
benzene
electrophile acylation
in themolecules
two-step toreaction,
form anan
electrophilic acyl chloride,
intermediate
substitution RCOCl,
cation,
reaction reacts
which
Acylium ions breaks
are formeddown
Tip in mass
with aluminium
(Figure 18.1.28). producingchloride to from anand
methylbenzene acylium ion (Figure
H+ ions (Figure18.1.27). This ion as fragment
spectrometers
18.1.26). ions of
10. 31 Acylation acts as the electrophile in the two-step electrophilic substitution
(Figure 18.1.28).
reactionsuch asAcylium
compounds
derivatives (Chapter
ketonesions
19).
are formed in mass
or acid
spectrometers as fragment ions of
+ –
R C CI + AICI3 R C + AICI4 CH3
CH3 compounds such as ketones or acid

alt
O +
O H derivatives (Chapter 19).
+ – +
R C + 3 CH3
CI + AICI + + 4 + H
an acylium ion R C AICI
Figure 18.1.27 Formation
O of an acylium ion. O
intermediate
an acylium ion methylbenzene
cation R
Figure 18.1.27 Formation of an acylium ion.
Figure 18.1.26 The H
reaction of CH3+ electrophiles
C
with benzene in the Friedel–Crafts
+ alkylation reaction
+
to produce methylbenzene. + R
C R C R O + H

O O H C
Finally,
+ the aluminium chloride catalyst is regeneratedOas H+ ions
+ for Friedel–Crafts
released in
Figure 18.1.28 ElectrophilicCsubstitution
R mechanism C R acylation of − + H+
the electrophilic substitution react with ions.
AlCl4
benzene.
O O
H+ + AlCl
Figure 18.1.28 Electrophilic
→ HCl + AlCl
4 substitution mechanism
3 for Friedel–Crafts acylation of
Tip benzene.
In Friedel–Crafts alkylation, the initial product contains an alkyl group attached to a
benzene ring. Alkyl groups are electron releasing, so the electron density on the ring is
Tip
greater than on benzene, which makes further substitution likely.
In Friedel–Crafts alkylation, the initial product contains an alkyl group attached to a
In Friedel–Crafts acylation, the initial product contains a carbonyl group attached to a
benzene ring. Alkyl groups are electron releasing, so the electron density on the ring is
benzene ring. The carbonyl group withdraws electron density from the benzene ring, so
10. 32 Skill Check
greater than on benzene, which makes further substitution likely.
further substitution is unlikely.
530 18.1 Arenes – benzene compounds
In Friedel–Crafts acylation, the initial product contains a carbonyl group attached to a
Draw
25 the structural
Test formulae
benzene
yourself ofcarbonyl
ring. The the products you would
group withdraws electronexpect fromthethe
density from benzene ring, so
Arenes and phenols
further substitution is unlikely.
reaction of benzene and aluminium chloride with
22 This question is about the Friedel–Crafts reaction between benzene
469983_18.1_Chem_Y1-2_519-540.indd 530 and ethanoyl chloride, CH3COCl, in the presence of aluminium 13/04/19 10:00 PM
(a) CH3CHchloride,
2Cl Test
AlCl3yourself
, as catalyst. O
!
(b) (CH3)2CHCOCl.
a) Write an equation to show how AlCl molecules react with
22 This question is about the3 Friedel–Crafts reaction between benzene "
C ! AlCl CH3 C O ! AlCl4
polarised CH COCl molecules to produce reactive acylium ions. 3
and 3ethanoyl chloride, CHCH3COCl,
3
in the
Clpresence of aluminium an acylium ion
b) Write an chloride,
equation AlCl
for the electrophilic substitution of benzene
3, as catalyst.
by acylium ions to produce phenylethanone.
a) Write an equation to show how AlCl molecules react with
3
c) Write an equation to show
polarised how molecules
CH3COCl moleculesoftothe aluminium
produce O ions.
reactive acylium CH3 O
chloride catalyst are regenerated. CH3
b) Write an equation for the electrophilic substitution of C
! benzene
H C
23 a) Why must the CH C dryOduring
byreaction
acyliummixture
ions to be completely
3
produce phenylethanone.
a Friedel–Crafts reaction?
c) Write an equation to show how molecules of the aluminium ! ! H!
b) Draw the structures of the products of a Friedel–Crafts reaction
chloride catalyst are regenerated.
of benzene with:
23 a) Why must the reaction mixture be completely dry during
i) 2-iodo-2-methylpropane
a Friedel–Crafts reaction?
Worked example
ii) propanoyl chloride.
b) Draw the structures of the products of a Friedel–Crafts reaction
Draw the structural
c) Suggest a reason for using an iodoalkane formulae
instead of of the products you would expect from the reaction of
of benzene with:benzene and aluminium chloride with
a chloroalkane in a Friedel–Crafts reaction.
10. 33 Skill Check i) 2-iodo-2-methylpropane
a CH CH Cl
Now try this ii) propanoyl chloride.
3 2
b (CH3)2CH—COCl.
What
What organochlorine c)compounds
organochlorine compounds are needed
are a reason
Suggest for usingtoan
synthesise
18.1.6the
iodoalkane following
instead of substitution reactions of benzene
Electrophilic 531
Answer
compounds from benzene?
needed to synthesise the following
a chloroalkane in a Friedel–Crafts reaction.
compounds from benzene? a O
1 C(CH3)3 O
469983_18.1_Chem_Y1-2_519-540.indd 531 13/04/19 10:00 PM
18.1.6 Electrophilic substitution reactions of benzene 531
C

b
2 O O
C(CH3)3 469983_18.1_Chem_Y1-2_519-540.indd 531 13/04/19 10:00 PM

Electrophilic substitution in substituted arenes –

the orientation of the incoming group
When methylbenzene is treated with nitric and sulfuric acids, the three possible
mono-nitro compounds are formed in the following ratios:

CH 3 CH 3 CH 3
NO2
Bilal Hameed Marginalizer
NO2
Bilal Hameed NO 2 Arenes
58% 4% 38%

If the NO2+ electrophile had attacked the ring in a purely random way, the
distribution should have been 40 : 40 : 20 (there being two 2-positions and two
 26.5 22
The mechanism of substitution reaction
Heading A
of
12
benzene

The substitution reactions of benzene involve electrophilic substitution. In this section you w
The high density of negative charge in the delocalised electron system of the • Describe the mechan
benzene10.
ring34 Nitration
tends to attract electrophiles. the electrophilic sub
ConsiderWhen
as anbenzene reactions of benzene
exampleis added to a mixture
the nitration of concentrated
of benzene. Benzene nitric and sulphuric
reacts with a

alt
mixtureacid
of concentrated
and heated under reflux to around 50 C nitrobenzene is formed. a
nitric acid and concentrated
o sulfuric acid (called
nitrating mixture) at 50 °C. The product is nitrobenzene:
KEY POINT
− NO2
conc. H2SO4 The nitration of benze
+ HNO3 + H2O nitrobenzene involves
50 °C
attack by NO2+.
Sulfuric acid is a stronger acid than nitric nitrobenzene
so initial protonation of nitric
(a yellow oil)
acid occurs.
This is a substitution
HNO3 + reaction.
H2SO4 →AHhydrogen + atom on the benzene ring has been Tip
2NO3 + HSO4
substituted by a nitro group, − NO2.
The protonated acid then loses water to form the nitronium ion. In this reaction, concentrated
The reaction of benzene with concentrated nitric acid alone is slow, whilst pure acts as a base and accepts a
3 →
+ +
sulfuric acidHat2NO
50 °C hasNO 2 + H 2O
practically no effect on benzene. This suggests that from the stronger acid, H2SO4
sulfuric acid must somehow
An overall equation is:react with nitric acid, producing a species that
then reacts with benzene. There is good evidence that this species is NO2+, the
nitronium HNO 3+H
ion, also called → NO
2 SO4the nitryl+
2 + HSO4This
cation. +H O
is2formed by the removal of
–
OH from 10. 35
HNO
The NO Nitration:
by sulfuric Mechanism
acid:
3 + ion is a reactive electrophile. It replaces a hydrogen in the benzene
Tip
2
ring in a two-step electrophilic substitution mechanism (Figure 18.1.23)
The mechanism of the
3 +electrophilic
→ substitution
NO2+ +is: – +
similar to thatHNO
which 2H2SOin
occurs 4 the bromination2HSO 4 + H3O
of benzene. Make sure that the correct bon
nitryl cation shown. It is the nitrogen atom
NO2stronger bonded to a carbon atom in th
In this reaction, nitric acid is acting as a base
H in the presence of the
++ not an oxygen atom, so the bo
sulfuric acid. The NONO2 ion
2
is a strong
+ electrophile
NO 2
and is attracted to the
+ H+ Q Ufrom
E S the
T I nitro
O N group must
negative π-electron system in benzene. First a loose association is ring
formed: start at N, not
5 The typical O. reaction
Figure 18.1.23 Electrophilic substitution mechanism for the nitration of benzene. are electrophilic sub
2 H2SO4 + HNO3 ⟶ 2 HSO4 + H3O+ + NO2+ Explain why they ar
+ NO2+
Test yourself NO2+
electrophile a electrophilic not n
17 Explain why dilute nitric acid does not react with benzene.
b substitution, not
18 Write an overall equation for the formation of the nitronium ion in
which the water produced is also protonated.
19 Three possible isomers of dinitrobenzene can be produced. One of
these isomers is called 1,2-dinitrobenzene.
a) Draw and name the structures of the other two dinitrobenzenes.
10. 36b) Nitration:
Why is there Mechanism
no isomer called 1,6-dinitrobenzene?
20 Why is TNT mixed with a compound containing a high proportion of
Formation of the electrophile occurs in 3 steps:
oxygen, such as potassium nitrate, when it is used as an explosive?
21 Write a) an overall equation and b) a mechanism for the formation of
HNO3 ⟶from
1-methyl-4-nitrobenzene 2
+
+ OH
NOmethylbenzene.
OH + H2SO4 ⟶ HSO4 + H2O
Alkylation
H2Oand
+ Hacylation
2SO4 ⟶ HSO(Friedel–Crafts
4 + H3O+
reactions)
The2 Friedel–Crafts
H2SO4 + HNO3reaction
⟶ 2 HSO + H3O method +
4
is an important
+
+ NO2 for substituting
an alkyl group or an acyl group for a hydrogen atom in an arene. This
Key term
reaction was discovered and developed jointly by the French organic chemist The Friedel–Crafts reaction is
Charles Friedel (1832–1899) and the American, James Crafts (1839–1917). electrophilic substitution wher
The reaction is used on both a laboratory and an industrial scale. hydrogen atom in an arene is r
In a Friedel–Crafts reaction, a halogenoalkane or an acyl chloride is refluxed by an alkyl or an acyl group fo
with an arene in the presence of aluminium chloride as catalyst. For example, attack by a carbocation or an
if benzene is refluxed with chloromethane and aluminium chloride, a ion electrophile.
substitution reaction occurs forming methylbenzene (Figure 18.1.24).

Marginalizer Bilal Hameed

Arenes Bilal Hameed

18.1.6 Electrophilic substitution reactions of benze
 18.1.7 Addition reaction of benzene
with hydrogen
13
23

The characteristic reactions of benzene involve substitution because this

type of reaction retains the delocalised π electron system with its associated
stability. However, addition reactions involving disruption of the π electron
10. 37 Hydrogenation
system do occur. Benzene, like alkenes, will undergo addition with hydrogen
Benzene
in thereacts with hydrogen
presence gas andcatalyst,
of a nickel nickel catalyst
butatat200 oC to form
considerably higher temperatures

alt
cyclohexane.
(Figure 18.1.29).
The addition of hydrogen nickel
Raney nickel
ing cyclohexane. + 3H2
200 °C

cyclohexane

A higher temperature is needed with benzene in order to break up the stable

electron system and allow addition to occur. A special finely divided form
of nickel, called Raney nickel, is also used because this has an extremely high
surface area. The addition of hydrogen to benzene is thought to occur in
three stages. First, the formation of cyclohexa-1,3-diene, then cyclohexene
and finally cyclohexane.
10.The
38 catalytic
Skill Check
hydrogenation of benzene is important industrially in the
manufacture
Give 7ofAconditions
the reagants and cyclohexane,
synthesis of for stepswhich
1, 2 and
1-phenylpropene is3.used
from benzeneto make c)nylon.
The benzene ring in L-dopa is more
is shown below. reactive with electrophiles than that in
benzene.
Tip COCH2CH3 CH(OH)CH2CH3 Explain why the benzene ring in L-dopa is
more susceptible to attack by electrophiles
step 1 step 2 than benzene itself. (2)
In the presence of ultraviolet light, chlorine will add to benzene
d) Ininthe
a human
free- body, an enzyme called
radical reaction to form a mixture of chlorinated cyclohexanes including
‘L-dopa decarboxylase’ eliminates the
carboxylic acid group from L-dopa to
1,2,3,4,5,6-hexachlorocyclohexane, shown below. There are several
step 3
produceisomers of amine, dopamine.
the primary
C6H6Cl6, one of which has been used asCH=CHCHcommercial
3 insecticide, but such use is by
i) State what is meant nowthe term
‘primary amine’. (1)
restricted because of concerns about its toxicity to humans. ii) Draw the structural formula of
dopamine. (1)
CI 9 The following data are provided to answer
Identify a reagent and a catalyst for
a) i)
this question.
step 1. CI (2)CI
ii) Write an equation for the reaction Mean bond energy of C=C = 612 kJ mol−1
+ 3CI2 between them to form an electrophile Mean bond energy of C–C = 347 kJ mol−1
and draw a mechanism for the reaction Mean bond energy of C–H = 413 kJ mol−1
of this electrophileCIwith benzene. (3)CI
10. 39 Methyl Benzene b) Identify a reagent for step 2. Name the Enthalpy change of atomisation of
type of mechanism involved. CI (2) H2(g) = 218 kJ mol−1 (Hint: per mol of atoms
c) Identify a reagent for step 3. Name the
Methylbenzene reacts in the same way as benzene, via an electrophilic- formed.)
type of reaction involved. (2)
substitution mechanism.d) Discuss the stereochemistry of the
Enthalpy change of atomisation of
C(s) = 715 kJ mol−1
Test yourself compounds formed in steps 2 and 3. (6)
The conditions for the reactions of methylbenzene are slightly milder than a) Use the data provided to calculate the
8 The drug L-dopa is used in the treatment of
those for the reactionsParkinson’s
of benzene as the
disease. methyl group isis:an activating enthalpy change of formation of gaseous
Its structural
24 a) Why is Raney nickel used informula
the manufacture of cyclohexane
Kekulé benzene. from (7)
group. b) The experimental value for the enthalpy
HO
benzene? CH2 COOH
change of formation of gaseous benzene is
CH
+82 kJ mol−1.
b) Write equations
HO
to show NH2 the three stages in the hydrogenation
Calculate the difference between this figure
of benzene via cyclohexa-1,3-diene and cyclohexene to you
and the value form calculated in part (a) and
a) Write the structural formulae of the sodium give a reason for the difference. (3)
cyclohexane.
salts formed when L-dopa reacts with: *
10 a) The pKa values for ethanol and phenol are
i) excess sodium hydroxide solution
c) Why do cyclohexa-1,3-diene (1)
and cyclohexene react
16.0 andmore readily
10.0, respectively.
ii) excess sodium carbonate solution. (1) Compare the acid strengths of the two
with hydrogen
b) Predict thethan benzene?
structural formula of the compounds and explain why there is
organic ion produced when L-dopa such a large difference. (6)
25 Explain whyreacts 1,2,3,4,5,6-hexachlorocyclohexane
with excess dilute hydrochloric shows geometric
b) Both ethanol and phenol react with
isomerism. acid. (1) ethanoyl chloride to form esters.
Draw and name the two esters. (2)

1 Arenes – benzene compounds

Bilal Hameed Marginalizer

Bilal Hameed Arenes

540
indd 532 18.1 Arenes – benzene compounds 13/04/19 10:00 PM
 than with benzene are called deactivating groups (Table G5).
Acyl halides react with benzene in the presence of a halogen carrier
2,4-directing groups usually cause substitution faster than benzene
catalyst. Consider the reaction of ethanoyl chloride with benzene:
and 3-directing groups normally cause electrophilic24 substitution
to occur more slowly thanCH benzene (chlorine as a C 14 is an
substituent
3COCl + C6H6 6H5COCH3 + HCl
exception to this – it is a 2,4-directing group and chlorobenzene
benzene ring here reacts moreasslowly than benzene).
is named If substitution were to occur at position 3, stabilisation of the positively
enyl substituent. 10. 40 Methyl Benzene: Reactivity
charged intermediate is not possible by donation of the lone pair on the
O into the ring.
The methyl group donates electron density into the benzene ring (positive

alt
The rate-determining step inductive effect). is the attack of the electrophile
in the reaction
on the ring. When an activating group is present this step occurs more
This increases
quickly as there is more electron density the amount
in the ringofsoelectron
that andensity in the ring so that it is more
electrophile
attractive to electrophiles and reacts more readily.
is attracted more strongly. When the ring is deactivated by the withdrawal
of electron density, the electrophile is attracted less strongly and the
reaction occurs more slowly.
Thus methylbenzene reacts more readily than benzene due The to the
methyl group has an electron-releasing effect and this also stabilises
This is a similar reaction to that already seen on
the intermediate whenpages occurs for
34–35
substitution the 2 and 4.
at positions
electron-releasing effect of the –CH3 group (positive inductive
effect). The methyl groupformation of ring
the electrophiles for chlorination and alkylation.
The electron-releasing eff ect of the methyl group comes from the
activates the towards electrophilic
overlap of the electron density in the C–H bond with a p orbital on an
substitution by donating electron density+into the ring. This adjacentthe
makes atom (Figure G43).
+
CH COCl 3 AlCl CH 3CO + [AlCl ]−
3 The stabilising
4 effect of the methyl group on the intermediate can be
shown as:
The mechanism is the same as for alkylation.
Examiner’s tip
A summary of the explanations
is that an electron-releasing

10. 41 Methyl Benzene: Reactivity

group stabilises the
intermediate by electron
donation into the ring. This
Methylbenzene
stabilisation reacts more readily than benzene due to the electron-
is only possible
releasing effect of the –CH3 group (positive inductive effect).
when substitution occurs
at positions 2, 4 and 6. An As for phenol, this stabilisation is only possible when substitution
electron-withdrawing group occurs at positions 2 or 4.
The methyl group
destabilises the activates
intermediatethe ring towards electrophilic substitution by
donatingby electron
withdrawing density
electron into the ring.
Again, thefrom
density second This could be shown with [AlCl ]− removing the H+
the ring.step
4
This makes the ring
destabilisation more negative, i.e. more attractive towards electrophiles
is greatest
to reformwhen the catalyst.
substitution occurs at
and thepositions
reaction 2, 4occurs more quickly than with benzene.
and 6, therefore
substitution at position 3 is
preferred.

Methylbenzene reacts in the same way as benzene, via an electrophilic-

substitution mechanism. The conditions for the reactions of
methylbenzene are slightly milder than those for the reactions of benzene
as the methyl group is an activating group. The methyl group donates
electron density into the benzene ring (positive inductive effect). This
increases the amount of electron density in the ring so that it is more
10. 42 Methyl Benzene: Reactivity
attractive to electrophiles and reacts more readily.
The
Themethyl group
methyl is a 2,4-directing
group group and
is a 2,4-directing so theand
group major
soproducts of products
the major
substitution are:
of substitution are:

Some of the electrophilic substitution reactions of methylbenzene are

shown in Figure G39.

Marginalizer Bilal Hameed

Arenes Bilal Hameed

 25
15

26.8 Other arenes

10. 43 Chlorination
ii The aromatic ring of Methyl Benzene
If chlorine is bubbled through methylbenzene in the absence of sunlight
and in the presence of a halogen carrier such as AlCl3, the ring is substituted
If methylbenzene
instead of is
thereacted withThis
chlorine
reactionin the presence of a halogen

alt
CH3 side group. proceeds by the electrophilic
ic hydrocarbons and phenol
carrier catalyst (AlCl ) at room temperature 2-chloromethylbenzene
substitution mechanism described in Section 26.6. A mixture of two isomers
is obtained: 3 and 4-
chloromethylbenzene are formed. CH3
Table 26.3 Some arenes other than benzene
POINT

−
− Cl
Systematic name Other name Molecular formula Structural formula
e are many arenes apart from
ene. methylbenzene toluene
CH3
C7H8 CH3
2-chloromethylbenzene −

−
e include: AlCl3
58%

nzene rings with alkyl side + Cl2 + HCl

1,4-dimethylbenzene para-xylene C8H10
−CH3
CH3
ups,

−
ed benzene rings H3C −

−
naphthalene — C10H8
Cl
STIONS 4-chloromethylbenzene Fig 26.8 Manufacturing high explosive shells
42% in 1940. TNT was an important explosive in
anthracene — C14H10 both world wars
rite the structure of two Virtually none of the other possible isomer, 3-chloromethylbenzene, is
her compounds that might produced. Furthermore, the reaction proceeds at a considerably higher rate
rm when the − CH3 group is than the corresponding reaction of chlorine with benzene. The − CH3 group
influences the aromatic ring, making it more susceptible to electrophilic
bstituted by chlorine. substitution and dictating the positions in which it is substituted. This effect is
Reactions of methylbenzene
discussed further in the next section.

10.
The44 Chlorination of
with Methyl Benzene
nder certain conditions An important substitution reaction of methylbenzene is nitration. When
lorine will substitute H atoms properties of aromatic
methylbenzene compounds
is heated aremixture
a nitrating very different fromnitric
of concentrated thoseacidof aliphatic
the ring of methylbenzene ones. Methylbenzene’s
and concentrated molecule
sulfuric acid,has
it is an aromatic
substituted portion
by one, two or (the benzene
three − NO2 ring)
stead of those in the − CH3 If and
methylbenzene
an aliphatic is reacted
groups, depending
portion on
(the with
the− CHchlorine
3 group).in
conditions. The main
the presence
products
These twoare: of UV
portions light
make then
different
contributions to the properties of methylbenzene and have a modifying effect
oup. What will these side-chain substitution
on each other.
CH3 occurs where a hydrogen
CH 3 atom in the methyl group
−

nditions be?
is substituted by a Cl atom.
NO2
− NO2 −
CH3 CH3
i The — CH3 group
−

O2N − NO2
− CH3 group shows some reactions we would expect of an alkyl group. For
−
This
Theinvolves a free radical substitution mechanism as for alkanes.
−

2-nitromethylbenzene NO2
POINT example, its H atoms can be substituted by chlorine when chlorine is bubbled
−

2,4-dinitromethylbenzene
ylbenzene has two different into boiling methylbenzene in sunlight:
NO2 NO2
Fig 26.9 One of the earliest high explosives
tution reactions with CH3 4-nitromethylbenzene CH 2Cl
2,4,6-trinitromethylbenzene was nitroglycerine. It is made by heating
−

glycerol with a nitrating mixture, but the

ine, depending on the Note the effect of the − CH3 group in determining that substitution in positions reaction must be watched carefully to make
sunlight sure it does not get out of control. In this
tions. 2, 4 and 6 rather than 3 or 5.
+ Cl2 + HCl print of early nitroglycerine manufacture, the
operator minding the reaction is sitting on a
hen chlorine is bubbled 2,4,6-Trinitromethylbenzene (trinitrotoluene or TNT) is an important high one-legged stool to prevent him nodding off
o boiling methylbenzene in explosive. It is fairly resistant to shock and so can be used in shells without risk to sleep
of explosion under the shock of firing a gun. When detonated it decomposes
nlight, the − CH3 side group is The reaction has a free-radical mechanism similar to the reaction of methane
forming large volumes of CO, H2O and N2 at high temperature. The sudden
stituted. with chlorine described
expansion of thesein Section
gases 14.6.
gives TNT its explosive force. TNT has the additional
advantage that it is a solid which melts below 100 °C, so it can be melted with
hen chlorine is bubbled into Oxidation steam
of the side
and poured group incontainer.
into its methylbenzene
See Section 12.9 for more about high
thylbenzene in the presence
The − CHexplosives such as TNT and nitroglycerine.
3 group in methylbenzene does not behave as a typical alkyl group in
AlCl3 as a catalyst, the ring is
all its reactions. The benzene ring with its regions of high electron density has a
stituted.
modifying effect on any group that is attached to it. 497

STION
10. 45 Methyl Benzene: Reactions
One example of the way in which the ring modifies the properties of the
− CH3 group in methylbenzene is the reaction with potassium manganate(VII).
Alkanes are inert to oxidation, but the alkyl group in methylbenzene can
arting with ethylbenzene,
be oxidised by alkaline manganate(VII) to give benzoic acid. The purple
w would you produce the
manganate(VII) is reduced to green manganate(VI).
lowing? Give the reagents
d conditions.
− CH3 − COOH
+ 2H2O + 6MnO4– + 6MnO42– + 6H+
CHBrCH3
−
manganate (VII) benzoic acid manganate (VI)

CH CH Note that the ring is not affected in the reaction, which is another indication of its
− 2 3
stability.
Br −

If methylbenzene is reacted with chlorine in the presence of a halogen

carrier catalyst (AlCl3) at room temperature 2-chloromethylbenzene and
4-chloromethylbenzene are formed. This is chlorination in the ring.

Bilal Hameed Marginalizer

Bilal Hameed Arenes

If methylbenzene is reacted with chlorine in the presence of UV

light then side-chain substitution occurs where a hydrogen atom in Examiner’s tip
 26
16 i Write an equation, showing all reagents and condi
from benzene.
ii Draw the mechanism for the reaction in part i.
b Explain why phenol reacts more rapidly with chlorin
10. 46 Skill Check c Nitrobenzene reacts with a mixture of concentrated s
a compound with the molecular formula C6H4N2O4
Compound X, shown below, can be formed from benzene in a two-step

alt
reaction sequence. Design a reaction pathway showing all reagents
d Compoundand X, shown below, can be formed from ben
Design a reaction pathway showing all reagents and c
conditions and the intermediate compound for the conversion of benzene to
for the conversion of benzene to X.
X.

ORGANIC CHEMISTRYORGANIC CHEMISTRY

ORGANIC
In ethylbenzene, CHEMISTRY
In ethylbenzene, the hydrogen atoms on the carbon atom adjacent to the benzene
the hydrogen atoms on the carbon atom adjacent to the benzene
ring are substituted much more readily than the three hydrogens on the other carbon,
ring are substituted much more readily than the three hydrogens on the other carbon,
so the following reaction gives a good yield of the product:
so the following reaction gives a good yield of the product:
CH 2 CH 3
CH 2 CH 3 CHClCH 3 In CHClCH 3
ethylbenzene, the hydrogen atoms on the carbon atom adjacent to the benzene
UV light ring are substituted much more readily than the three hydrogens on the other carbon,

10. 47 Cl
Oxidation of the Side Chain
UV light
Cl HCl gives a good yield of the product:
so the following reaction
or boilingHCl
2
2
or boiling

ORGANIC CHEMISTRY CH 2 CH 3
> 90% CHClCH 3
When alkylbenzenes are >treated 90%
with hot acidified potassium
Oxidation of the side chain
manganate(VII), oxidation of the whole side chain occurs,Cl
Oxidation of the side chain leaving the
UV light
When alkylbenzenes are treated with hot alkaline potassium manganate(VII),
2 HCl
carbon atomIn closest to the ring as a carboxylic acid
When alkylbenzenes are treated with hot alkaline potassium manganate(VII),
oxidation group: or boiling
ethylbenzene, the hydrogen atoms on the carbon atom adjacent totothe
of the whole side chain occurs, leaving the carbon atom closest thebenzene
ring
oxidation of the whole side chain occurs, leaving the carbon atom closest to the ring
as are
ring a carboxylate or carboxylic acid group:
substituted > 90%
as a carboxylate or carboxylic acid group: much more readily than the three hydrogens on the other carbon,
CH 2CH yield ofCO 2Kproduct: CO2H
CH 2CH 3 so the following
KMnO4
reaction
3 COgives Oxidation
K a good
acidified
KMnO
2
the
4KMnO
COof
4
H 1 the 21 H (aq) side chain
1 H1(aq)
CH CH 3 heat with OH– CHClCH
heat with OH– 2 heat When alkylbenzenes
3 are treated with hot alkaline potassium manganate(VII),
oxidation of the whole side chain occurs, leaving the carbon atom closest to the ring
UV light
Cl2 as a carboxylate or carboxylic
HCl acid group:
or boiling
CH 3 CH2K2CH 3
CO CO2H CO2K CO2H
CH 3
KMnO4 acidified
2K 4KMnO4
COKMnO
1 H1(aq) > 90%
CO21HH1(aq) KMnO4 1 H1(aq)
–
heat with OH–
heat
heat with OH
heat with OH–
CH 2CH 3 Oxidation of
CH 2CH 3 the side chainCO2K
CO2K CO2H
CO2H

When alkylbenzenes are treated with hot alkaline potassium manganate(VII),

Worked example oxidation Worked example
of the whole side chain occurs, leaving the carbon atom closest to the ring
Three hydrocarbons A, B and C with the formula CCH
9 H12 were oxidised by hot potassium CO2K CO2H
Three hydrocarbons A, as a carboxylate
B and or carboxylic
C with the formula acid
C9H12 were group:
oxidised by hot potassium
3
manganate(VII). KMnO4 1 H1(aq)
manganate(VII).
CH 2CH
Hydrocarbon A 3gave benzoic acid,
CO2K
Hydrocarbon heat with
C gave OH– CO2H
benzene-1,2,4-trioic
Hydrocarbon A gave benzoic acid, KMnO4
Hydrocarbon C gave benzene-1,2,4-trioic1 H1(aq)
C6H5CO2H. –
CH
acid: 2CH 3 CO2K CO2H
C6H5CO2H. acid:with OH
heat
Hydrocarbon B gave benzene-1,2-dioic CO2 H
Hydrocarbon B gave benzene-1,2-dioic CO2 H

10. 48 Skill CheckCO H Worked example

acid: CO H
acid: CO H 2
2
2
CO H 2 Three hydrocarbons A, B and C with the formula C9H12 were oxidised by hot potassium
CH 3 CO2K CO2H
Three hydrocarbons A, BCO and
H CKMnOwith the formula C 9H12 were oxidised by hot
manganate(VII).
CO H 2 1 H (aq)
CO HA gave
4
1
Hydrocarbon C gave benzene-1,2,4-trioic
potassium manganate(VII).
2 Hydrocarbon benzoic acid, 2
heatCO HOH–
with 2
Suggest the structures of A, B and C.
Suggest the structures of A, B andCH
C. 2CH 3 C H CO H. 6 5 CO
2
2K CO2Hacid:
Now try this Now try this Answer Hydrocarbon B gave benzene-1,2-dioic CO2 H
Answer HydrocarbonSince A gave benzoic
benzoic acid,acid, C‘extra’
6H5CO 2H.
acid:
Suggest structures for the aromatic
Suggest structures for the aromatic Worked example
A gave all three carbon atoms must be in the same side chain. So A is:
Since A gave benzoic acid, all three ‘extra’ carbon atoms must be in the same side chain. So A is: CO2 H
carboxylic acids which will be produced CH2CH2CH3 CH(CH3 )2 CO2 H
Hydrocarbon B hydrocarbons
gave benzene-1,2-dioic
A, B and C with theacid:
carboxylic acids which will be produced CH2CH2CH3 CH(CH3 )2
when the following compounds are Three formula C9H12 were oxidised by hot potassium
when the following compounds are
oxidised by hot potassium manganate(VII). manganate(VII).
oxidised by hot potassium manganate(VII). or CO2 H
(All these compounds are isomers with or
(All these compounds are isomers with Hydrocarbon A gave benzoic acid, Hydrocarbon C gave benzene-1,2,4-trioic CO2 H
the molecular formula C11H14.)
the molecular formula C11H14.) 6H5CO2H. B must contain two side chains,
CCompound acid:
since the
Suggest
Compound B must contain two side chains, since two carboxylic acid groups are left after
two A,groups
carboxylic acid
structures of B andareC.left after
B gave
Hydrocarbon C gave benzene-1,2,4-trioic acid:
1 Now try Hydrocarbon
this
oxidation. What benzene-1,2-dioic
is more, the chains must be on adjacent COcarbons
2H in the ring, as a
oxidation. What is more, the chains must be on adjacent carbons in the ring, as a
1 1,2-dicarboxylic acid is formed. So B is: Answer
acid:
1,2-dicarboxylic acid is formed. So B is: CO2 H
Suggest structures for CH3theCO aromatic Since A gave benzoic acid, all three ‘extra’ carbon atoms must be in the same side chain. So A is:
2H
Suggest the structures of
CH3
carboxylic acids which CHA,
will be B and C.
produced
2 CH3
CH2CH2CH3 CH(CH3 )2
2 CH2CH
when the
3 following compounds are
2
CO H
oxidised by hot potassium manganate(VII).
2 CH3
CH3 CO2 H or
(All these compounds are isomers with CH3
Suggest the structures of A, B and C.
CH
the molecular formula
By similar C11H14
reasoning, .)C3must be:
Now 3try this By similar reasoning, C must be:
Answer Compound B must contain two side chains, since two carboxylic acid groups are left after
3
Suggest structures for the aromatic 1 Since A gave benzoic acid, all three ‘extra’oxidation. What
carbon atoms is more,
must the same
be in the chainsside
must be So
chain. on A
adjacent
is: carbons in the ring, as a
CH
1,2-dicarboxylic
3 acid is formed. So B is:
carboxylic acids which will be produced CH3
CH2CH2CH3 CH(CH3 )2
when the following compounds are CH3
oxidised by hot potassium manganate(VII). CH2CH3
430 or
430 (All these compounds are isomers with 2
the molecular formula C11H14.) CH3
Compound B must contain two side chains, since two carboxylic acid groups are left after
Marginalizer Bilal
oxidation. What is more, the chains must be on adjacent carbons in the ring, as a
Hameed
CH3
1
181333_25_A_Chem_BP_415-439.indd
181333_25_A_Chem_BP_415-439.indd 430
430
By similar reasoning, C10/10/14
must 8:33
be:PM 10/10/14 8:33 PM
1,2-dicarboxylic acid is formed. So B is:
3
CH3
Arenes CH3
Bilal Hameed
CH2CH3
2
CH3
430 CH3
 9 12
C6H5CO2H.
manganate(VII). acid: the hydrogen atoms on the carbon atom adjacent to the benzene
In ethylbenzene,
manganate(VII).
Hydrocarbon
Hydrocarbon BAgave
gavebenzene-1,2-dioic
benzoic acid, CO2 H muchCmore
ring are substituted
Hydrocarbon gave readily than the three hydrogens on the other carbon,
benzene-1,2,4-trioic
Hydrocarbon A gave benzoic acid, Hydrocarbon C gave benzene-1,2,4-trioic
acid:
C6H5CO2H. so the following
acid: reaction
CO2 Hgives a good yield of the product:
C6H5CO2H. acid:
Hydrocarbon BCO 2 H benzene-1,2-dioic
gave CH 2 CHCO 2H
Hydrocarbon B gave benzene-1,2-dioic CO2 H 3 CHClCH 3
acid: acid:
CO2 H CO 27
H 2

CO2 H CO2 H 17 CO2 H Cl2

UV light
HCl
or boiling
Suggest the structures of A, B and C.
CO2 H
Now try this CO2 H
Answer CO2 H CO2 H > 90%

Suggest structures for thethe

Suggest Suggest
structures of A, BSince
aromatic and C. the structures
A gave benzoic acid, A,three
of all C.Oxidation
B and‘extra’ carbon atoms must ofbethe in theside chain
same side chain. So A is:
Now tryacids
carboxylic this which will be produced
Answer
when the following compounds are
10. 49 Answer
Answer CH 2
CH 2
CH 3 WhenCH(CH )
alkylbenzenes
3 2 are treated with hot alkaline potassium manganate(VII),
Since A gave benzoic acid, all three oxidation of the must
whole beside chain
sameoccurs, leaving
So Athe
is: carbon atom closest to the ring
Suggest structures
aromatic forAthe
Since
oxidised by hot potassium gavearomatic
benzoic acid, all three
manganate(VII). ‘extra’ carbon atoms must be in ‘extra’ carbon
the same side atoms
chain. So A is: in the side chain.
carboxylic acids which will be produced CH CH CH or as aCH(CH
carboxylate
) or carboxylic acid group:
l be produced

alt
(All these compounds are CH CH2CH
isomers
2 with CH(CH
2 2 ) 3 3 2

oundswhen the following compounds are 3 3 2

CH 2CH 3 CO2K CO2H
theare
A is:
molecular formula C11H14.)
oxidised by hot potassium manganate(VII). KMnO 1 H1(aq)
m manganate(VII). Compound B must contain or two side chains, since two carboxylic acid 4groups are left after
these compounds are isomers with or
(All with heat with OH–
isomers oxidation. What is more, the chains must be on adjacent carbons in the ring, as a
1the molecular formula C11H14.)
1H14.) 1,2-dicarboxylic acid is formed. So B is:
Compound B must contain twoCompound side chains, B since
must twocontain two side
carboxylic chains,
acid groupssince
aretwoleft carboxylic
after acid groups are left after
oxidation. CH3
1 oxidation. What is more, the chains must What
be onisadjacent
more, the chainsinmust
carbons be onasadjacent
the ring, a carbons in the ring, as a
1,2-dicarboxylic acid is formed.1,2-dicarboxylic
So B is: acid
CH is formed. So B is:
2 CH3 CH 3 CO2K CO2H
B is:
2 KMnO4
CH3 1 H1(aq)
CH3 CH3 heat with OH–
CH2CH3
2 CH2CH3 CH 2CH 3
CH CO2K CO2H
3
By similar reasoning, C must be: CH3
3 CH3 Worked example
CH CH3
3
C must be:
C is:
By similar reasoning,
By similar reasoning, C must be: Three hydrocarbons A, B and C with the formula C9H12 were oxidised by hot potassium
CH3
3 manganate(VII).
Hydrocarbon A gave benzoic acid, Hydrocarbon C gave benzene-1,2,4-trioic
CH3 CH
C6H3 CO H. acid:
430 5 2
Hydrocarbon B gave benzene-1,2-dioic CO2 H
acid: CO2 H
430 CO2 H
25_A_Chem_BP_415-439.indd 430 10/10/14 8:33 PM

CO2 H
CO2 H
_25_A_Chem_BP_415-439.indd 430
10. 50 Skill Check Suggest the structures of A, B and
10/10/14 C.
8:33 PM
10/10/14 8:33 PM

Now try this Answer

Suggest structures
Suggest structures for the aromatic
for the aromatic carboxylic
Since A gave benzoicacids
acid, all which willcarbon
three ‘extra’ be produced
atoms must be in the same side chain. So A is:

when thefollowing
following compounds are oxidised by hot potassium
carboxylic acids which will be produced CH CH CH 2 2 3
CH(CH ) 3 2
when the compounds are
manganate(VII). (Allmanganate(VII).
oxidised by hot potassium these compounds are isomersorwith the molecular
formula H14.) C11H14.)
C11formula
(All these compounds are isomers with
the molecular
Compound B must contain two side chains, since two carboxylic acid groups are left after
1 oxidation. What is more, the chains must be on adjacent carbons in the ring, as a
1,2-dicarboxylic acid is formed. So B is:
CH3
CH2CH3
2
CH3
CH3
By similar reasoning, C must be:
3

CH3

430

10. 51 Reactions of Substituted Benzene Rings

181333_25_A_Chem_BP_415-439.indd 430 10/10/14 8:33 PM

Substituted benzene rings undergo basically the same reactions as a

benzene ring, i.e. electrophilic substitution.

The nature of the substituent determines the position of further

substitution and the rate of the reaction relative to unsubstituted
benzene.

Bilal Hameed Marginalizer

Bilal Hameed Arenes

 28
18

10. 52 Reactions of Substituted Benzene Rings

Substituents on a benzene ring may be divided into two groups: those

alt
which cause substitution predominantly at positions 2 and 4 (and 6) (ortho
and para positions) and those that cause substitution at position 3 (and 5)
(the meta position).
The same stabilisation is possible when substitution occurs at position 4.
The orientation of the incoming group (NO2 or Br) depends on the
substituent already in the ring, and not on the electrophile.

If substitution were to occur at position 3, stabilisation of the positively

charged intermediate is not possible by donation of the lone pair on the
10. 53 2,4-Directing O into the ring.

27 Amines, amides and amino acids

If we look closely at the types of substituents that are 2,4-directing, we find
that either
Those amines that are soluble in water form weakly alkaline solutions, just as

•
ammonia does, due to partial reaction with the solvent, producing OH− ions: ring more negative, i.e. more attrac
they are capable of donating electrons
CH3CH2NH2 + H2O
to
CH3the ring
CH2NH + by the inductive effect, or
3 + OH
−
the reaction occurs more quickly than
• they have a lone pairTable
of electrons
Table 27.3 The basicity of some amines on the
27.3 lists some amines, withatom
values ofjoined to theequilibrium
their dissociation ring. This lone
constants,

pairFormula
can be incorporated into the ! system − by sideways overlap of p
K , for the following equilibrium:
b
Amine K +
ORGANIC CHEMISTRY
R3N + H2O
b
R3NH + OH
orbitals.
−3
/mol dm
+ − At first sight we might expect the –OH
[R NH ][OH ] 3
phenylamine NH2 4.2 × 10−10
Kb =
[R 3N] withdrawing due to the high electrone
Table 25.5 Orientation in some electrophilic Reaction
Percentage of product Ratio
The larger K b is, the stronger is the base. Ammonia is included
substitution reactions
The methyl group has an electron-releasing effect and this also
for comparison. group also ortho possesses
stabilises
metaa lone
para pair of elect
(ortho + para)
meta
ammonia NH3 1.8 × 10−5 (1,2) (1,3) (1,4)
From Table 27.3 we can see that electron-donating alkyl groups attached to the
the intermediate when substitution occurs pair
at positions into the ring activates the ben
ethylamine CH3CH2NH2 5.1 × 10−4 nitrogen atom increase the basicity of amines. This is expected, since the basicity CH CH 2 and334. 1 66 99 : 1

group This π donation

from the into the ring is a bi
3 3

diethylamine (CH3CH2)2NH 1.0 × 10−3 depends on the availability of the The

loneelectron-releasing effect
pair of electrons on nitrogen of the
to form methyl
a dative comes
bond with a proton (see Figure 27.6). Electron donation from an alkyl group will
overlap of the electron density in the C–H
+ Br
bond effwith
ect (due
Br
a p to the on
orbital electronegativity
an
2
of O
encourage dative bond formation.
adjacent atom (Figure G43).
OH donation
OH of
50 electron
1 density
49 99 : 1 into t

methylbenzene phenol R attract electrophilescan be more strongly

Figure 27.6 When an amine acts as a base, R
the nitrogen lone pair forms a dative bond with The stabilising effect of the methyl group+ HNO on the intermediate
NO 3 2

+ N+
a proton. R N
shown
H
as: R H
NO 2 NO2 6 93.5 0.5 1 : 14
R R
Examiner’s tip One particularly good example of the
+ HNO 3 NO2

A summary of the explanations The most dramatic difference in basicities to be seen in Table 27.3 is between that of CO H 2 reaction
CO H with
2 19 chlorine. 80 1 1:4
−10 −3
phenylamine (Kb ≈ 10 ) and the alkyl amines (Kb ≈ 10 ). Taking two compounds of
is that an electron-releasing Phenol reacts with chlorine water –
10.25 54 2,4-Directing
about the same relative
27_06 Cam/Chem AS&A2 molecular mass Phenol is also made more reactive
and shape, we see that phenylamine is about + HNO 3 NO 2

group stabilises the a million times less basic than cyclohexylamine: 2,4,6-trichlorophenol (no halogen carr
Barking Dog Art in water since itArenes is acidic and
and phenols
intermediate by electron
produces the phenoxide ion The data in Table 25.5 can be interpreted as follows.
donation into the ring. This NH2 NH2
−
25.4 Halogenoarenes C H
6 5 O . The negative charge The orientation of the incoming group (NO2 or Br) depends on the substituen
stabilisation is only possible already in the ring, and not on the electrophile.
phenylamine on the10 O
cyclohexylamine means canwithdrawal Some substituents favour both 2- and 4-substitution, whereas other substituen
when substitution occurs We saw K on pages
= 4.2b× 10 423–424 how bromobenzene
–10
K = 3.3 ×andb
chlorobenzene
–4 be made from H
favour 3-substitution, at the expense of both 2- and 4-substitution.
Cl
issubstitution,
reducedandand donation Ois
benzene. The reactions of the ring in halogenobenzenes are similar to those of benzene.
at positions 2, 4 and 6.This An Halogenoarenes
is because inundergo Asthefor
electrophilic
phenylamine, lonephenol, this
can bestabilisation
pair of electrons nitrated:
on the nitrogen atom is onlyis we possible
If look closely when substitution
at the types of substituents that are 2,4-directing, we find th
Cl over the benzene ring. increased, The bondsClaround therefore theatomringcanistakeeither they are capable of donating electrons to the ring by the inductive effe
electron-withdrawing delocalised group occurs at positions the nitrogen
2 or 4.
up a planar arrangement, with the nitrogen’s more attractive
lone pair in to a p electrophiles.
orbital, so that extra they have a lone pair of electrons on the atom joined to the ring. This lone p
destabilises the intermediate conc. HNO + conc. H SO
bond canof be incorporated into the π system by sideways overlap of p orbitals (see
phenol
stability can be gained by overlapping this p orbital
25.12 with of the lone π
the delocalised
chlorobenzene
3 2 4

Figure 25.13 Delocalisation of the lone pair Figure Delocalisation pair

Figure 25.12).
by withdrawing
in chlorobenzene electronthe benzene ring (see Figure 27.7). in 2,4-directing substituents
On the other hand, all those substituents that favour 3-substitution have a δ+
NO2
density
25_13 Cam/Chem from
AS&A2 the ring. This 26_12 Cam/Chem AS&A2
joined directly to the ring (see Table 25.6).
Figure 27.7 Delocalisation of the nitrogen However, unlike halogenoalkanes, halogenoarenes cannot be hydrolysed, even
destabilisation
Barking Dog Art
lone pair in phenylamine is greatest by boiling in aqueous sodium hydroxide. Thethe
Table 25.6 Substituents and their effects on
Barking Dog Art
carbon–halogen
benzene ring bond is stronger
2- and 4-directing substituents 3-directing substituents

when substitution occurs in halogenoarenes than it is in halogenoalkanes,

at H possibly due to an overlap of p CH Ar 3 The NO2 groupO is electron-withdrawi
electrons similar to that in phenol (see Figure 25.13, and compare it with – Figure 25.12).
positions 2, 4 and 6, therefore NH
In addition to this, the carbon attachedNto theorhalogen is not accessible to the usual NH
2
+
2 etc. ring. With less electron O
−
N Ar
density in the r
substitution at positionnegative
nucleophilic reagents that attack halogenoalkanes, since its δ+ charge is shielded by the
H
3 is π cloud of the ring. This means that halogenoarenes are inert to all nucleophiles. H O Ar strongly, therefore δ–
O
nitrobenzene reacts m
•
•

preferred. Certain halogenoarenes find important uses as insecticides and herbicides (see the electron-withdrawing C because
δ+
Ar of the h
panel below).
in the group and,Hunlike the O in phen
phenyl amine δ– δ+

of electrons on the N N that

C Ar can be dona
•
•

This overlap, causing a drift of electron density from nitrogen to the ring, has twoH N 2Ar
effects on the reactivity of phenylamine.
Organochlorine insecticides and herbicides delocalisation of the δ–
O electrons from th
δ+
27_07 Cam/Chem
Insecticides
It causes the lone pairAS&A2to be much less basic (see above) and also much less C Ar
nucleophilic.
Chlorobenzene
Barking Dogused
Artto be made in large quantities as an intermediate in the R
It causes of
production thethering to be more
insecticide DDT: electron rich, and so to undergo electrophilic
substitution reactionsCl much more readily than benzene. CCl3 The enhanced reactivity of
phenylamine in this regard is similar to that of phenol (see Topic 25, page 434), an
The position of substitution is determi
CH
Cl2 CCl3CHO the intermediate. The more stable the i
AlCl3 AlCl3 453
C1 C1 be formed.
4,4!-dichlorodiphenyltrichloroethane
(DDT)
This is most usually explained using
428
Figure 25.14 453
181333_27_A_Chem_BP_449-468.indd Malaria is caused by a The use of chlorinated insecticides is now banned in many countries. These 09/10/14 1:39 AM but to understand the explanation we m
microscopic parasite that is spread by the bite compounds are quite inert to biodegradation, so they stay in the environment
Marginalizer
of the Anopheles mosquito. Malaria affects
over 300 million people worldwide and kills
for many years. What is more, being non-hydrogen-bonded covalent substances, Bilal Hameed about resonance.
around 3 million a year. DDT treatment of the
Anopheles mosquito saves millions of human
they are insoluble in water, but soluble in fats and oils. They tend428to concentrate
181333_25_A_Chem_BP_415-439.indd
in the fatty tissue of animals, especially those higher up the food chain. Birds of
Two possible Lewis structures may b
lives, so the environmental price is considered
worth paying.
prey were especially vulnerable. At one time, the shells of their eggs were so thin double bonds between different atoms
Bilalresonance
Hameed
that they cracked during attempted incubation, with disastrous consequences for
Arenes their populations. DDT may still be used in parts of Africa and Asia to control the structures. The actual structu
malaria mosquito, as the advantages to human health are considered to outweigh the
disadvantages to the environment.
resonance hybrid of these two struct
Herbicides somewhere in between.
The compounds 2,4-dichlorophenoxyethanoic acid (2,4-D) and
2,4,5-trichlorophenoxyethanoic acid (2,4,5-T) have been successfully used for many
 ituents
either they are capable The of donating
On the
able 25.5 Orientation in some electrophilic
data
Reaction
electrons
in other
Table hand, to
25.5 canallthe
be ring
those by theof as
substituents
interpreted
Percentage
inductive effect,
that favour
follows.
product Ratio
or
3-substitution have a δ+ atom
hand, all those substituents
bstitution reactions
they have a lone that favour
pair of electrons on 3-substitution
the atom joinedhave to a δ+
the atom
ring. This lone
(orthopair
+ para)
joined directly to the ring (see orthoTable meta
25.6). para meta
mocan
thebe
AS&A2ring (see Table 25.6).
incorporated into The
the πorientation
system byofsideways
the incoming(1,2) group
overlap (1,3) (NO
of (1,4)or Br) depends on the substituent
p orbitals
2 (see
uents and 25.12).
Figure their effects on alreadyCH in the ring, CH
2- and 4-directing and not 33on the electrophile.
substituents
3 1 366
29 99 : 1 substituents
3-directing
ng substituents 3-directing
Somesubstituents substituents
substituents favour 19
both3-substitution
2- and 4-substitution,
On the other hand, H all those
CH 3 Ar+ Br that favour
Br 2
have
O a δ+whereas
atom other substituents
joined directly O favour
O 3-substitution,
to the ring (see Table 25.6). at the expense of both 2- and 4-substitution.
OH OH 50 1 49 N 99 : 1 Ar
If we lookN closely
Ar at the types of substituents− that are 2,4-directing, we find that
10.
O 55they 3-Directing
−
2- and 4-directing substituents 3-directing substituents O
+ HNO
either are capable ofNOdonating 3
electrons to the ring by the inductive effect, or
2

δ–
CH 3 Ar theyδ –have
NO a lone pair NO
O of electrons on 93.5
the atom O 1 : 14 to the ring. This lone pair
0.5 joined

•
•
On
H the
O OotherAr hand, all those substituents
6
that favour 3-substitution have a

alt
2 2
δ+
can be incorporated into theAr
Nthe π system by sidewaysC overlap Ar of p orbitals (see
!+ atomCjoined directly to ring.
δ+
lisation of the lone pair
Figure 25.12). Ar O −
+ HNO NO 3 2

uents H
On HtheCO other
H hand, COallHthose19substituents
2 80 that
1 favour
2 1 : 4 3-substitution have a δ+ atom
δ– δ– δ+
joined directly to the O
ring (see Table 25.6). N C Ar
•
•

•
•

H O Ar δ– δ+
HN
2N C Ar
δ+
AS&A2 Ar
+ HNO NO 2
3
Ar C
nts and their effects on 2- and 4-directing substituents δ–
3-directing
O substituents
δ– H
O
The data in Table 25.5 can be interpreted as follows.
δ+
CH 3 Ar
δ+ δ– δ+ O C Ar
Ar of the
TheCorientation N incoming
C groupAr (NO2 or Br) depends on the substituent
•
•

H2 N Ar R
N Ar
already in the ring, and not on the electrophile.
RSome substituents favour both 2- and 4-substitution, whereas
−
other substituents
H δ– O
O favour 3-substitution, O
at the expense of both 2- and 4-substitution.
δ+
δ–
If we look closely at the types Ar
C of substituents O
that are 2,4-directing, we find that
•
•

H O they
either Ar are capable of donating electrons to the ring by theδ+inductive effect, or
they have a lone pair ofRelectrons on the atom joined to the ring. This Ar
C lone pair
can be incorporated into the π system by sideways overlap of p orbitals (see
gure 25.12 Delocalisation of the lone pair H
Figure 25.12).
2,4-directing substituents
On Aromatic
the other hydrocarbons
hand, all those substituents that favour 3-substitution have a δ+ atom
H10. 56Ar Directing Groups
and phenol δ– δ+
N C Ar
•
•

joined directly to the ring (see Table 25.6).

26_12 Cam/Chem AS&A2 2N

26.9
able 25.6 Substituents and their effects on 2- and 4-directing substituents 3-directing substituents
Barking Dog Art
e benzene ring
Theδ –position
O of substitution
CH 3 Ar O
Headingδ+ A
N inArbenzene
C derivatives
Ar
−
O
R
δ–
In this section you will learn to: O The methyl group in methylbenzene activates the ring towards electrophilic
•
•

428 H O Ar δ+ 10/10/14 8:33 PM

• Explain why substitution occurs substitution.
C Ar It also favours substitution in positions 2, 4 and 6 rather than 3 or
10/10/14 8:33 PM
at certain positions on the 5. In fact, any substituent group attached to a benzene ring affects the rate and the
H
c hydrocarbons and phenol Aromatic hydrocarbons
benzene ring and phenol position at which further substitution occurs. Table 26.4 shows the main products
δ– of mononitration
δ+
(i.e. substitution by one nitro group) of different benzene
Predict which isomers would be N
H2 N • Ar C Ar
•
•

derivatives, and whether they are nitrated faster or slower than benzene.
given as the main products from

26.9 Heading A
in benzene derivatives R
The
The position of substitution Table
C
26.9
26.4position
various substitution reactions δ – O
Heading
Ar
Compound

QUESTION
ofofsubstitution
Mononitration products 10/10/14
benzene 8:33 PM
derivatives
AMain products of mononitration
in benzene derivatives
δ+

methylbenzene
Rate of nitration relative
to benzene
Faster
CH3 CH3 CH3
CHmethyl CH3NO activates the ring towards electrophilic
CH3in methylbenzene
−
−

s section you will learn to: The methyl group14

In Look
this at Tableyou
section
in methylbenzene 26.4will
and answer
learn
activates to: ring towards
the The 3 group
electrophilic − 2
−
−

NO2
lain why substitution occurs substitution. It•alsothese questions:
favours
Explain why substitution
substitution occurs 2, 4substitution.
in positions and 6 ratherItthan also−3favours
or substitution in positions 2, 4 and 6 rather than 3 or
ertain positions on the 5. In fact, any substituent
a certain
at Which group attached
groups
positions onto
tend to
the benzene ring5.affects
adirect In fact,the
anyrate and thegroup attached to a benzene ring affects the rate and the
substituent
−

NO2 Table 26.4 shows the main products

−

zene ring position at whichbenzene

further substitution 2 or 4 Table 26.4position
ring to theoccurs.
substitution shows the at which further substitution
main products NO2
occurs.
of mononitration (i.e. substitution by one nitro group) of
position? of different
mononitration
benzene (i.e. substitution by one nitro group) of different benzene
dict which isomers would be • Predict which isomers would be phenol Faster
derivatives, and whether they are nitrated faster or slowerderivatives, OHand whetherOH
than benzene. OH faster or slower
they are nitrated than benzene.
10. 57 Directing Groups
n as the main products from b Which
given groups
as the maintend to direct
products from
−
−

OH OH NO2
OH
ous
28 substitution reactions substitution
various to
substitution the 3 position?
reactions − 10/10/14 8:33 PM
428
−
−

Table 26.4 Mononitration products of benzene derivatives Table 26.4 Mononitration products
NO of benzene derivatives
− 2
c Is there any correlation Compound Main products of mononitration Rate of nitration relative
−

Compound Main products of mononitration Rate of nitration relative

between the position to which NO2 to benzene
to benzene
−

a group directs substitution NO

TION methylbenzene Q U E S T I O N methylbenzene
Faster
nitrobenzene NO
2
NO2 Faster
Slower
Chem_BP_415-439.indd 428 CH3 and the CH rate
3 at which CHit3causes CH 2
3 CH 3 CH 3 PM
10/10/14 8:33
−−

CH3 14CHLook CH326.4 CH

NO32 CH3 NO2 CH3NO
−
−

3 the at Table and answer

−
−

ok at Table 26.4 and answer ring to − NO

substitute?
2 − 2
−
−

NO
−
−

NO
−

se questions: these
− 2questions: − 2 −
NO2
Which groups tend to direct a Which groups tend to direct −
−
−

NO2 NO2 NO2

−
−

ubstitution to the 2 or 4 substitutionNO2to the 2 or 4 NO2

osition? position? phenylamine NH2 NH2 NH2 Faster
− −
− −

− −

phenol OH OH OH phenol
Faster OH NH OH NH NO OH Faster
Which groups tend to direct b Which groups tend to direct NH2 2 − 22
NO
−
−

OH OH NO
OH 2 OH OH NO2 OH 2
−−
−−

−−

ubstitution to the 3 position? −

substitution to the 3 position? −NO −
−
−

NO2
− 2
c −Is there any correlation
− −

there any correlation NO 2

−

−−

etween the position to which NO2to which

between the position NO2 NO2
−

group directs substitution a group directs

NO2 substitution NO2
nitrobenzene NO2 NOwhich benzoic
Slower acid COOH
nitrobenzene NO2 COOH
NO2 Slower
nd the rate at which it causes and the rate at 2 it causes
−

−
−

−
−

NO2 NO2
COOH NO2
COOH
he ring to substitute? theNO
ring
2 to substitute?
−

−
−

− −−
NO2 NO
NO2 2
− −−
NO2 NO22
NO
phenylamine NH2 NH2 NH2 phenylamine
Faster NH2 NH2 NH2 Faster
−
−

NO2 benzene derivatives fall into two classes as far

−
−

NO You
NH2 NH2 POINT −
KEY NH2 2 NH2can see from
NHTable
2
26.4−NH
that
2
−
−

as further substitution
NO is concerned.
−
−

NO
− 2
A substituent that is already − 2
−
−

present on a benzene ring NO2directs • Those which substitute faster than benzene
NO2 and in which the new
−

further substituents to either:

−

NO2
substituent is directed to the
NO22 and 4 position, a mixture of the two isomers
• the 2 and 4 position, or being obtained. Functional groups causing this behaviour include:
benzoic acid COOH COOH benzoic
Slower acid COOH COOH Slower
− CH3 and all alkyl groups, − OH, − NH2, − OCH3.
−

• the 3COOH
position.
−

COOH COOH COOH

• Those which substitute more Marginalizer
−

Bilal Hameed
−

− −
slowly than benzene and in which the new
NO2 NO2
− substituent is directed−to the 3 position. Functional groups causing this
NO2 NO2
behaviour include:
Bilal Hameed − NO2, − COOH, − SO3H. Arenes
OINT You can see from
KEYTable
POINT26.4 that benzene derivatives fall Youinto
cantwo
see classes
from Table
as far26.4 that benzene derivatives fall into two classes as far
498
as further substitution is concerned. as further substitution is concerned.
tituent that is already A substituent that is already
nt on a benzene ring directs • Those whichpresent on afaster
substitute benzene
thanring directsand in which
benzene • Those
thewhich
new substitute faster than benzene and in which the new
r substituents to either: further
substituent is substituents
directed to either:
to the 2 and substituent
4 position, a mixture of the twois isomers
directed to the 2 and 4 position, a mixture of the two isomers
 30
20

10. 58 Directing Groups

One explanation is that an electron-releasing group stabilises the

alt
intermediate by electron donation into the ring.

This stabilisation is only possible when substitution occurs at positions 2, 4

and 6.

An electron-withdrawing group destabilises the intermediate by

withdrawing electron density from the ring.

This destabilisation is greatest when substitution occurs at positions 2, 4

and 6, therefore substitution at position 3 is preferred.

Arenes
Test yourself
3 a) Describe the mechanism for the reaction between bromine and
benzene in the presence of FeBr3(s).
b) Explain why FeBr3(s) can be regarded as a catalyst.
c) FeBr3(s) can be replaced by Fe(s).
d) Explain why Fe(s) is not regarded as a catalyst.

10. 59 Skill Check

4 Under certain conditions benzene can be nitrated to form a mixture of
isomers each with molecular formula C6H4N2O4. Draw and name the
isomers.
Write the reagants and conditions for the following reactions:
5 Write equations and state the conditions for each of the following
conversions.

(a)

(b)

(c)
CH3
requires two
separate reactions

NO2

Bromination of alkenes and arenes

Alkenes, such as cyclohexene, react readily with bromine, in the absence of
sunlight, and undergo electrophilic addition reactions. The reaction is rapid

10. 60 Rate of Electrophilic Substitution

and is initiated by the induced dipole in bromine. Alkenes like cyclohexene
are able to induce a dipole in bromine because of the high electron density
in the carbon-to-carbon double bond, C=C, which is sufficient to induce a
dipole in the Br–Br bond:
2,4-directing groups usually cause substitution faster than benzene and 3-
directing group normally Br Brcause electrophilic
Br Br substitution to occur more
slowlyThethan benzene
C=C double bond has (chlorine as a substituent is an exception to this – it is a

2,4-directing groupbond and chlorobenzene reacts more slowly than benzene).

high electron density which
polarises the Br-Br
The mechanism for the reaction between cyclohexene and bromine is
Substituents that cause substitution faster than with benzene are called
shown below:

activating groups (2,4-directing groups except for chlorobenzene) and

Br Br

those that cause substitution to occur more slowly than with benzene are
Br Br
+ :Br –
Br
called deactivating group (3-directing group).

153

Marginalizer Bilal Hameed

Arenes Bilal Hameed

 31
21

10. 61 Rate of Electrophilic Substitution

The rate-determining step in the reaction is the attack of the electrophile on

alt
the ring.

When an activating group is present this step occurs more quickly as there
is more electron density in the ring so that an electrophile is attracted more
strongly.

10. 62 Rate of Electrophilic Substitution

When the ring is deactivated by the withdrawal of electron density, the
electrophile is attracted less strongly and the reaction occurs more slowly.

Activating groups donate electron density into the ring. This makes the ring
more negative, i.e. more attractive towards electrophiles and the
reaction occurs more quickly than with benzene.

10. 63 Phenol Faster Than Benzene

At first sight we might expect the –OH group to be electron-withdrawing
due to the high electronegativity of O. ring more negative, i.e. more attractive towards electrophiles an
the reaction occurs more quickly than with benzene.
However, the –OH group also possesses a lone pair of electrons and overlap
of this lone pair into the ring activates the benzene ring.
At first sight we might expect the –OH group to be electron-
withdrawing due to the high electronegativity of O. However, the –O
group also possesses a lone pair of electrons and overlap of this lone
pair into the ring activates the benzene ring (Figure G40).
This π donation into the ring is a bigger effect than the -withdraw
effect (due to the electronegativity of O). Therefore there is net
donation of electron density into the ring and the ring will
attract electrophiles more strongly.

One particularly good example of the ease of reactivity of phenol is in

reaction with chlorine.
Phenol reacts with chlorine water – Cl2(aq) – to form
Phenol is also made more reactive
2,4,6-trichlorophenol (no halogen carrier required):
in water since it is acidic and
Bilal Hameed produces the phenoxide ion Marginalizer
C6H5O−. The negative charge
on the O means withdrawal
Bilal Hameed is reduced and donation is Arenes
increased, therefore the ring is
more attractive to electrophiles.
 Consequently, phenol not only reacts with sodium metal, giving off hydrogen gas:

OH O Na
+ Br2 Br

1–
Na H 2(g) OH OH 50 1 49
32
2

22
sodium phenoxide + HNO 3 NO 2
(a white solid)
but, unlike alcohols, it also dissolves in aqueous sodium hydroxide:
NO 2 NO2 6 93.5 0.5
OH O Na

10. 64 Phenols Faster Than Benzene + HNO 3 NO2

NaOH H2 O
This !Phenol
donation into the ring is a bigger effect than the electron CO H withdrawing CO 2 H 19 80 1

alt
2
is visibly acidic: the pH of a 0.1 mol dm−3 solution in water is 5.4, so it will
effectturn
(due to theindicator
universal electronegativity
solution yellow. of
An O).
old name for phenol is carbolic acid (see
+ HNO 3 NO 2
section 25.6).
Therefore
Esterifithere
cation is net donation of electron density into the ring and the ring
will attract electrophiles more
Because of the delocalisation overstrongly.
the ring of the lone pair on the oxygen atom,
The data in Table 25.5 can be interpreted as follows.
phenol is not nucleophilic enough to undergo esterification in the usual way, that is,
by heating with a carboxylic acid and a trace of concentrated sulfuric acidThe
(for orientation
the of the incoming group (NO2 or Br) depends o
mechanism of esterification, see section 18.3). already in the ring, and not on the electrophile.
OSome substituents favour both 2- and 4-substitution, whereas
H
favour 3-substitution, at the expense of both 2- and 4-substitu
O
OH O C CH 3
heat with If we look closely at the types of substituents that are 2,4-dire
CH 3CO2H conc. H SO HO
2 4 either26.11
they Substitution reactions
are2 capable of of electrons
donating the aromatic ringring
to the in phen
by th
ester they
not formed
have a lone pair of electrons on the atom joined to the r
Phenol can, however, be esterified by adding an acyl chloride: can be incorporated into the π system by sideways overlap o
Figure 25.12 Delocalisation of theOH
OH lone pair
Figure 25.12).

−
in 2,4-directing substituents
−

ClOH
− Cl O CH3 On the other hand, all those substituents that favour 3-substit
! CH3− C
1NaOH
COCl or pyridine ! HCldirectly to the ring (see Table 25.6).
joined
26_12 Cam/Chem AS&A2
− −
O
Table 25.6 SubstituentsCH CH3
and3 their effects on

−
10. 65 Ring Reactions With Phenols
2- and 4-directing substituents 3-directing substitue
−

Barking Dog Art phenyl ethanoate

the benzene ring
Cl Cl
CH 3
See section 26.3 for a fuller description of the conditions used for this reaction. Ar O
2,4,6-trichlorophenol: 4-chloro-3,5-dimethylphenol:
Phenols are more susceptible
effective a to electrophilic timesattack than
ringbenzene, owing to
N Ar
Substitution
23 times as reactions of the 280 benzene as effective −
O
the delocalisation of
germicide
As we mentioned the
onas lone
phenol
page pair ofare
428, in
phenols electrons on oxygen.
as phenol
more susceptible This allows
to electrophilic attack phenol
a given concentration
to react with reagents that are more dilute, and also to undergo Omultiple
than benzene, owing to the delocalisation of the lone pair of electrons on oxygen. δ–
O

•
•
This allows phenol to react with reagents that are more dilute, and also H to undergo Ar δ+
Fig 26.13 Derivatives of phenol used in antiseptics
substitution with ease.
C Ar
multiple substitution with ease.
Fig 26.12 TCP is a commonH household
Esterification antiseptic which contains phenol and phenol
Nitration of phenol
When treated with dilute aqueous nitric acid (no sulfuric acid is needed) derivatives δ–
N
δ+
C Ar
•
•
When treated with phenol
dilute aqueous
formsnitric acid However,
(no sulfuric acid is needed)
Hphenol gives
phenol gives a 2-
mixture of 2- andesters.
4-nitrophenols. 2 N phenol
Like aliphatic alcohols, unlike alcohols, Ar
a mixture of and 4-nitrophenols:
does not react directly with carboxylic acids. Phenyl esters are normally made by δ–
reacting phenol OHwith acyl halides (Section 19.5). ForOH example, phenylOH benzoate is QUESTION O
δ+

made by reacting phenol with benzoyl chloride in the presence C Ar

NO2 of aqueous alkali: 18 a How would you convert
dilute HNO 3 at room temperature
R
phenol to phenyl ethanoate?
OH
b Why do you think aqueous
−

− C − Cl 50% NO 2 alkali is added to the mixture

=

+ C−O − + HCl of phenol and acyl halide in

−
O 50%
=

the preparation of phenyl

O esters?
434 benzoyl chloride phenol phenyl benzoate

428
10. 66 Bromination of Phenols
26.11
181333_25_A_Chem_BP_415-439.indd 434 10/10/14 8:33 PM

Substitution reactions of the aromatic

Phenol decolorises a dilute solution ofring inin phenol
bromine water at room
temperature, giving a white precipitate of 2,4,6-tribromophenol. No
181333_25_A_Chem_BP_415-439.indd 428

aluminium bromide is needed.

When aqueous bromine is added to a solution of phenol, the bromine is In this section you will learn to:
immediately decolorised and a white precipitate is formed. This is a substitution
Contrast
reaction andthis
thewith the
white conditions
precipitate needed
is 2, for the bromination of benzene.
4, 6-tribromophenol.
• Describe the bromination of
phenol and explain why this
OH OH reaction and nitration occurs
more readily than with using
−
−

Br − − Br benzene
+ 3Br2 + 3HBr • Test for the presence of a phenol
compound
−

Br • Summarise the reactions of

2,4,6-tribromophenol phenol

Benzene does not react with bromine except in the presence of a halogen
carrier catalyst (Section 26.6). In general, phenol is more readily attacked
than benzene by electrophiles. This is because the lone pairs of electrons KEY POINT
on the oxygen of the —OH group in phenol become partially delocalised The aromatic ring in phenol is
around the ring. This increases the electron density on the ring and makes readily substituted by electrophiles.
it more attractive to electrophiles. The 2, 4 and 6 positions on the ring are The 2, 4 and 6 positions are
preferentially substituted (Section 26.9). preferentially substituted.
Phenol can also be nitrated far more readily than benzene. Dilute nitric
acid alone is sufficient, and the products are 2- and 4-nitrophenol. If
Marginalizer Bilal Hameed
you use a ‘nitrating mixture’ of concentrated nitric and sulfuric acids,
2,4,6-trinitrophenol, commonly known as picric acid, is formed. Picric acid,
Arenes like other highly nitrated molecules, is a high explosive. Bilal Hameed
50
 33
23
25 Arenes and phenols

25.4 Halogenoarenes
10. We
67saw onChlorobenzene
pages 423–424 how bromobenzene and chlorobenzene can be made from
Cl benzene. The reactions of the ring in halogenobenzenes are similar to those25of benzene.
Halogenoarenes
Halogenoarenes undergo electrophilic substitution, and can be nitrated:
Arenes and phenols

alt
undergo electrophilic substitution, and can be nitrated:
Cl Cl 25.4 Halogenoarenes
We saw on pages 423–424 how bromobenzene and chlorobenzene can be made from
conc. HNO3 + conc. H2 SO4 Cl benzene. The reactions of the ring in halogenobenzenes are similar to those of benzene.
Halogenoarenes undergo electrophilic substitution, and can be nitrated:
Figure 25.13 Delocalisation of the lone pair
Cl Cl
in chlorobenzene
conc. HNO3 + conc. H2 SO4
NO2 Figure 25.13 Delocalisation of the lone pair
25_13 Cam/Chem AS&A2 in chlorobenzene
However, unlike halogenoalkanes, halogenoarenes cannot be hydrolysed, even
However, unlike sodium hydroxide. Thehalogenoarenes
halogenoalkanes, cannot be
NO2
25_13 Cam/Chem AS&A2
Barking Dog Art
by boiling in aqueous carbon–halogen bond is stronger Barking Dog Art
However, unlike halogenoalkanes, halogenoarenes cannot be hydrolysed, even

hydrolysed,
by boiling in aqueous sodium hydroxide. The carbon–halogen bond is stronger

even by boiling in aqueous sodium hydroxide.

in halogenoarenes than it is in halogenoalkanes, possibly due to an overlap of p
electrons similar to that in phenol (see Figure 25.13, and compare it with Figure 25.12).
in halogenoarenes than it is in halogenoalkanes, possibly due to an overlap of p
electrons similar to that in phenol (see Figure 25.13, and compare it with Figure 25.12).
In addition to this, the carbon attached to the halogen is not accessible to the usual
In addition to this, the carbon attached to the halogen is not accessible to the usual nucleophilic reagents that attack halogenoalkanes, since its δ+ charge is shielded by the
negative π cloud of the ring. This means that halogenoarenes are inert to all nucleophiles.
nucleophilic reagents that attack halogenoalkanes, since its δ+ charge is shielded by the Certain halogenoarenes find important uses as insecticides and herbicides (see the
negative π cloud of the ring. This means that halogenoarenes are inert to all nucleophiles. panel below).

Certain halogenoarenes find important uses as insecticides and herbicides (see the
panel below). Organochlorine insecticides and herbicides
Insecticides
Chlorobenzene used to be made in large quantities as an intermediate in the
production of the insecticide DDT:
CCl3
Cl
Organochlorine insecticides and herbicides Cl2 CCl3CHO
CH

Insecticides AlCl3 AlCl3

C1 C1
Chlorobenzene used to be made in large quantities as an intermediate in the 4,4!-dichlorodiphenyltrichloroethane
(DDT)

production of the insecticide DDT: Figure 25.14 Malaria is caused by a The use of chlorinated insecticides is now banned in many countries. These

10. 68 Chlorobenzene
microscopic parasite that is spread by the bite compounds are quite inert to biodegradation, so they stay in the environment
CCl3 of the Anopheles mosquito. Malaria affects
Cl over 300 million people worldwide and kills
for many years. What is more, being non-hydrogen-bonded covalent substances,
they are insoluble in water, but soluble in fats and oils. They tend to concentrate
around 3 million a year. DDT treatment of the

CH Anopheles mosquito saves millions of human

lives, so the environmental price is considered
in the fatty tissue of animals, especially those higher up the food chain. Birds of
prey were especially vulnerable. At one time, the shells of their eggs were so thin
Cl2 CCl3CHO
The carbon–halogen bond isAlClstronger in halogenoarenes than it is in
worth paying. that they cracked during attempted incubation, with disastrous consequences for
AlCl 3 3
their populations. DDT may still be used in parts of Africa and Asia to control the
malaria mosquito, as the advantages to human health are considered to outweigh the

halogenoalkanes, due to an overlapC1of p electrons similar

C1
to that in phenol.
Herbicides
disadvantages to the environment.

4,4!-dichlorodiphenyltrichloroethane
(DDT) The compounds 2,4-dichlorophenoxyethanoic acid (2,4-D) and

The p orbitals from the Cl atom tend to overlap with the delocalised p
2,4,5-trichlorophenoxyethanoic acid (2,4,5-T) have been successfully used for many
Figure 25.14 Malaria is caused by a The use of chlorinated insecticides is now banned in many countries. These years as selective weedkillers for broad-leaved weeds. They have little effect on
narrow-leaved plants such as grass and cereals, and so can be used as lawn or field
microscopic parasite that is spread by the bite
electrons in the benzene ring. This causes the C—Cl bond to be stronger,
compounds are quite inert to biodegradation, so they stay in the environment weedkillers. Their action mimics that of the natural plant growth hormone indole
of the Anopheles mosquito. Malaria affects
for many years. What is more, being non-hydrogen-bonded covalent substances,
over 300 million people worldwide and kills
and hydrolysis does not occur.
around 3 million a year. DDT treatment of the they are insoluble in water, but soluble in fats and oils. They tend to concentrate
in the fatty tissue of animals, especially those higher up the food chain. Birds of
Anopheles mosquito saves millions of human
lives, so the environmental price is considered prey were especially vulnerable. At one time, the shells of their eggs were so thin 431
worth paying. that they cracked during attempted incubation, with disastrous consequences for
their populations. DDT may still be used in parts of Africa and Asia to control the 431
181333_25_A_Chem_BP_415-439.indd 10/10/14 8:33 PM

malaria mosquito, as the advantages to human health are considered to outweigh the
disadvantages to the environment.

Herbicides
The compounds 2,4-dichlorophenoxyethanoic acid (2,4-D) and
2,4,5-trichlorophenoxyethanoic acid (2,4,5-T) have been successfully used for many
years as selective weedkillers for broad-leaved weeds. They have little effect on
narrow-leaved plants such as grass and cereals, and so can be used as lawn or field
weedkillers. Their action mimics that of the natural plant growth hormone indole

10. 69 Electrophilic Substitution On Chlorobenzene

431

Chlorobenzene reacts with electrophiles more slowly than benzene does.

333_25_A_Chem_BP_415-439.indd 431 The chlorine is a deactivating group. 10/10/14 8:33 PM

Chlorine is more electronegative than carbon, and so pulls the electrons in

the ring towards itself.That makes the electron density around the ring rather
less in chlorobenzene.

It becomes less attractive for electrophiles, and so the reaction is slower.

Halogenobenzenes are deactivating, yet are 2,4-directors. (The exception

to the rule).

Bilal Hameed Marginalizer

Bilal Hameed Arenes

 34
24

10. 70 Skill Check

Give the structure of the organic products formed when the following

alt
8 Give the structure of the organic products formed when the
molecules are heated with excess aqueous sodium hydroxide:
following molecules are heated with excess aqueous sodium
hydroxide:
a b

Describe the formation of Organometallic compounds are organic molecules which also contain a
Grignard reagents metal atom. More precisely, they contain a bond between a carbon atom
Write equations for reactions of and a metal atom. These are useful in organic synthesis.
Grignard reagents The most commonly used organometallic reagents are Grignard
reagents. These may be formed when a halogenoalkane is reacted with
10. 71 asmagnesium
Skill Check
End of chapter questionsturnings using a dry ether (usually ethoxyethane, (C2H5)2O)

Organolithium compounds are also the solvent.

commonly used. 7 Predict the major products of the following reactions. 9 a Write structural formulae for all the compounds of
CH3
molecular formula C8H10 containing one benzene ring.
NO2
conc. H2SO4
−

H2/Ni
b For each of these compounds, write the formulae of
conc. HNO3
Grignard is pronounced as a d − 120 °C all the possible mononitration products (not just the
300 °C
grin-yard. NO2 ones you would expect as the major product).
c For one of the compounds, state which of the
OH
(mono- mononitration products you would expect to be
−

ClThe
2(aq) solvent must be dry as Grignard
CH3CHClCH reagents
3 substituted react vigorouslyproduced
with in the majority.
b e product
water. Al Cl3, warm
only) 10 Consider two possible reactions of chlorine with
benzene in the gas phase:
CH3
alkaline
−

KMnO 4(aq)
The general equation CH3COCl
for the A
formation of a Grignard reagent is: −Cl
c f (g) + 2Cl2(g) (g) + 2HCl(g)
warm Al Cl3, heat −
dry ethoxyethane Cl
−

The Grignard reagent cannot be CH3 RX + Mg RMgX

isolated from solution. Cl
For example: B −
(g) + Cl2(g) − (g)
8 Ethyl-1-methylethylbenzene, commonly called
dry ethoxyethane Cl
cumene, has
C2HtheBrstructure:
+ Mg C2H5MgBr
5
CH3− CH − CH3 ethylmagnesium
bromide Some relevant bond energies (in kJ mol–1) are: Cl − Cl
−

242; C − Cl (general value) 339; C − H (in benzene)

The structure of the Grignard reagent is shown in Figure G24. There is a
430; H − Cl 431.
covalent bond between the Mg and the C and between the Mg and the Br.
It is an important intermediate in a process used to
C is significantly more electronegative than Mg and the Grignard
a Which of the two reactions is addition and which is
manufacture phenol and propanone (acetone).
reagent acts in reactions as R−, that is, a negatively charged alkyl group.
substitution?
Ethyl-1-methylethylbenzene is manufactured
The alkyl group is a nucleophile by a positive regions in a
and will attack b Calculate the energy change in reaction A by the
Friedel–Crafts-type
molecule. reaction between propene and following stages.
benzene1inReaction
the presence of an reagents
of Grignard acid catalyst:
with water i How much energy is needed to split two moles of
This would, however, be rather a An alkane is formed, e.g. CH3− CH − CH3 chlorine molecules into atoms?
−

waste of a Grignard reagent! H+ ii How much energy is needed to break two moles
+ CCH 2H3− CH +
5MgI =HCH 2O2 C2H6 + Mg(OH)I of C − H bonds in benzene?
iii How much energy is released when two moles of
The reaction is believed to proceed via a carbocation new C − Cl bonds form?
intermediate. iv How much energy is released when two moles of
a Write the structures of the two possible carbocations HCl molecules are formed?
formed by the attack of H+ on the double bond of v What is the total energy change for reaction A?
propene. (Sections 15.4 and 15.5 may help you.) c Calculate the energy change in reaction B by the
b Which is the more stable of these two carbocations? following stages, assuming that the energy needed
c Show how the carbocation you identified in b can to break one C − C bond in benzene, i.e. convert
attack and substitute the benzene ring. Explain why −
ethyl-1-methylethylbenzene is virtually the only to − is 434 kJ mol–1
product of this reaction, hardly any propylbenzene
being produced. i How much energy is needed to split one mole of
chlorine molecules into atoms?
Treatment of the product with air followed by dilute
ii How much energy is released when two moles of
acid gives propanone and phenol:
C − Cl bonds form?
CH3− CH − CH3 OH iii What is the total energy change in reaction B?
−

Marginalizer Bilal Hameed

d Which reaction is more likely to occur between
+ O2 + CH3− C − CH3
chlorine and benzene, A or B? Give reasons for your
=

O answer.
Arenes d Suggest a reason why this is the most economic of
Bilal Hameed
the several methods available for manufacturing
phenol.