8 Arenes Notes

9
15 Arenes
Compounds containing only carbon and hydrogen are called hydrocarbons. This
class of compound can be subdivided into alkanes, alkenes and arenes.
15.4 Arenes
ARENES
CEDAR COLLEGE ARENES

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:
(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

11
STRUCTURE
25 Benzene consists of six carbon atoms arranged in a regular
Areneshexagon, each
Arenesjoined
and phenols to a
and phenols
hydrogen atom and to its neighbours by σ bonds.
There are six spare

The structure The structure
p orbitals,
of benzene oneof on
benzene
was described each was described
carbon
in detail in in detail
atom,
section 3.16. all in section
parallel
It consists 3.16.
to
of six It consists
each otherofand
six
carbon atoms arranged in a regular hexagon, each joined to a hydrogen atom and to
carbon atoms arranged in a regular hexagon, each joined to a hydrogen atom and to
perpendicular to theitsplane of the
neighbours byring.
σ bonds. There are six spare p orbitals, one on each carbon atom,
its neighbours by σ bonds. There are six spare p orbitals, one on each carbon atom,
Eachoverlaps
p orbital overlaps
all parallel
all parallel to each other
overlaps
to each othertoand
and perpendicular
equally with
equally withboth
both
theperpendicular
its
its neighbours,
neighbours,
to theEach
plane of the ring. plane
forming
forming a
of the ring. Each p orbital
p orbital
a delocalised
delocalised
equally with both its neighbours, forming a delocalised six-centre molecular six-centre six-centre
molecular
25
π πorbital (see π orbital
Figure 25.4). (see Figure 25.4).
Figure π25.4
4 The delocalised bondThe molecular
in delocalised bondπin orbital.
benzene
H H H H
H H H H
C C C C C C C C
H C H C C H = H CC H = H C C H C H
C C C C C C C C
H H H H H H H H
H H 1
H C H H C H All the bond angles in benzene are 120°. All the C¬C bonds haveFigure the same 25.4
length, The delocalised π bon
AllCthe bond C angles in benzene are 120°. All the C¬C bonds have the same length,
C C
0.13926_04
nm. This 0.139 nm.
is intermediate This is intermediate
between the
26_04 Cam/Chem between the length of
length of the C ¬C bond in an alkane
AS&A2 the C ¬C benzene
bond in an alkane
Cam/Chem AS&A2
C C C
(0.154 nm) Cand the C“C(0.154double
nm) and the in
bond C“C double(0.134
an alkene bond nm).
in an alkene (0.134 nm).
H C H Barking Dog Art
H C H Barking Dog Art The usual representation used for benzene
The usual representation used for benzene is either the symmetrical is either the symmetrical skeletal
skeletal
formula H (derived formula
from the (derived
Thiele from the
structure) or Thiele
the structure)
Kekulé or the
structure, Kekulé
either structure,
skeletal or either skeletal or
H
a b c
structural. Figure structural.
25.5 shows Figure
these 25.5 shows these
representations. The representations.
benzene Theisbenzene
structure normally structure is normally
b c
represented by the represented
skeletal by the
formula, as skeletal
in Figureformula,
25.5a. as in Figure
When we 25.5a.
want to Wheninwe want to show in
show
Figure 25.5 of
5 Three representations Three
the representations of the detail how
detail how the π electrons move π electrons
theduring move
reactions, during reactions,
however, however, we
we may sometimes use may
a sometimes use a
benzene
ecule: a the skeletal a the Thiele skeletal
Thielemolecule:
formula, b the Kekulé skeletal formula, c the Kekulé structure, as in Figure 25.5b or 25.5c. Figure
Kekulé structure, as in Figure 25.5b or 25.5c. Figure 25.6 shows models of the Kekulé 25.6 shows models of the Kekulé
he Kekulé skeletal formula, c the
em AS&A2 26_05 Cam/Chem
structural formulaAS&A2
for benzene and Thiele structures.
mula for benzene and Thiele structures.
Art Barking Dog Art
Figure 25.6
6 a Ball-and-stick and baelectron-
Ball-and-stick and b electron-
a a STRUCTURE
b b
density
cular models molecular models of benzene
of benzene
H
All carbon-carbon bonds are equal in length and strength, as are all carbon-hydrogen
bonds, and the C—C—C and H—C—C angles are all 120°. H C
C
The benzene structure is normally represented by the skeletal formula
C
H C
The six-centre In the

In the skeletaldelocalised
formula, skeletal
each formula,
πcorner
bond ofis each corner
theresponsible
hexagon of thethe
for
is assumed hexagon is assumed
to following
contain to contain
physical
a carbon andachemical
carbon
atom, toa which
atom, to which is attached is attached
hydrogen a hydrogen
atom, unless atom,
otherwise unless
stated. Forotherwise
example,stated. For example, H
properties of benzene.chlorobenzene
chlorobenzene can be can be written as follows:
written as follows: a b c
Cl Cl
• It causes all C—C bond lengths to be equal, creating a planar, regularFigure
hexagonal
25.5shape.
Three representations
benzene molecule: a the Thiele skel
• It prevents benzene undergoing any of the normal addition reactionsformula,
that alkenes
b theshow.
Kekulé skeletal formu
26_05 Cam/Chem
structural formulaAS&A2
for benzene
• The π bond also makes
The Kekulé structureThe
fitted
benzene
Kekulé structure
in with
more stable
with thethan
fitted inbonding
the chemical
expected.
chemical
ideas of thebonding ideas of the 1860s, but
1860s, but
was clearly incorrectwas clearly
in one incorrect
important in oneItimportant
respect. respect.
predicts that It predicts
benzene Barking
that benzene
is highly Dog Art
is highly
unsaturated – the formula suggestscontains
that thethree
molecule contains Figure 25.6 a Ball-and-stick and b
unsaturated – the formula suggests that the molecule double bonds.three double bonds.
It ought to undergo Itaddition
ought toreactions
undergoreadily,
addition reactions
just readily, In
2 an alkene.
like justfact,
likebenzene
an alkene. density molecular models of benzene
is In fact, benzene is
inert to most reagents that readily add on to
inert to most reagents that readily add on to alkenes (see Table 25.1). alkenes (see Table 25.1).
Table
A comparison of25.1
someAreactions
comparison of some reactions Reagent Benzene Benzene Cyclohexene Cyclohexene
of benzene and cyclohexene Reagent
nd cyclohexene
shaking with
shaking with KMnO4(aq) no KMnO 4(aq)
reaction no reactionimmediate decolorisation
immediate decolorisation
shaking with Br (aq) shaking with

2no Br 2(aq)
reaction no reactionimmediate decolorisationimmediate decolorisation
H (g) in the presence of nickel very
H2(g) in the presence of nickel very slow reaction at 100 °C
2 slow reaction °C and reaction at 20 °C and
rapid reaction at 20 °C rapid
at 100
and 100 atm and 100 atm1 atm 1 atm
417 417
stabilisation
by 149 kJ mol–1
25 Arenes and phenols

4
d
Arenes and phenols
–205
igure 25.7 actual
Enthalpy changes of
ydrogenation of benzene and the
yclohexenes 25ORGANIC
25.7 Enthalpy changes of CHEMISTRY
cyclohexane
stabilisation
AROMATIC COMPOUNDSstabilisation
Arenes and phenols
Arenes and phenols
nation of benzene and the
ORGANIC CHEMISTRY by 149 kJ mol–1 by 149 kJ mol –1
energy/kJ mol–1
enes
Compounds that contain rings of delocalised electrons are called aromatic compounds.
−1 stabilisation
ene’ by 354 − 205 = 14925.7
Figure kJ mol (seechanges of
Enthalpy
–354 Or the two rings could–354sharebytwo
149 kJ mol–1 atoms in common (with their π electrons),
carbon
energy/kJ mol–1
5.7 Enthalpy changes Theof name
hydrogenation ofwas
predicted originally
benzene and the applied to certain natural products that
predicted had strong, pleasant
as inrings
naphthalene:
could share two carbon atoms in common (with their π electrons),
ation of benzene
variously the and
as–232 the
cyclohexenes
stabilisation energy, 25 Or the two 25
–232
nes aromas, such as vanilla-bean
–205 oil, clove oil, almond
as in naphthalene: oil, –354
thyme oil and oil of wintergreen.
–205
stabilisation
e energy. actual predicted actual
118 stabilisation
–118 by 149 kJ mol–1
energy/kJ mol–1
–1
All of these oils contained compounds whose structures were found
–232 by 149 kJ mol
–205to include a benzene
energy/kJ mol–1
cyclohexane cyclohexane
Figure 25.7 Enthalpy Figureof25.7 Enthalpy changes
changes actual
of
ring. –118 –354
electrons are called aromatic hydrogenation of benzenehydrogenation
and the –354 of benzene and thepredicted
cyclohexenes cyclohexenes
predicted cyclohexane
ed to certain natural products that had
The
Or term
the two ‘aromatic’
rings couldeventually
share two became
carbon associated
atoms
−1 in common with the–232
(with presence
their π of the ring itself, –205
electrons), −1 anthracene and pyrene:stabi
oil, clove
more oil,than
stable almond oil, thyme oilby 354 −So
‘cyclohexatriene’ = 149 kJismol
benzene
205 more More
–232stablerings
(see thancan fuse together,–205
‘cyclohexatriene’ giving
by − 205compounds
354 such = 149 kJ molas (see
actual by 14
energy/kJ mol–1
energy/kJ mol–1
as in naphthalene: –118
ained compounds whether or not the
whose structures werecompound
Figure –118
had
25.7). a pleasant aroma. actual
More rings can fuse together, giving such compounds as anthracene and pyrene:
m AS&A2
romatic’
ation of 149 kJ mol−1 became
eventually is known associated
variously
Soas 26_07
the The
benzene Cam/Chem AS&A2
isstabilisation
stabilisation
more stable ofthan
energy, kJ mol−1 is knownby
149 ‘cyclohexatriene’ 354 − 205
variously = 149
as the kJ mol−1 (seeenergy,
stabilisation cyclohexane
cyclohexane –354
or not the compound had a
ation energy or the resonance energy.pleasant the delocalisation
FigureBarking
25.7). Dog Art energy or the resonance energy. predicted
26_07
TheCam/Chem
stabilisation of 149 kJ mol−1 is known variously as the stabilisation energy,
AS&A2
–232 –232 –2
enes the delocalisation
Barking Dog Art energy
So benzene Other arenes
or the resonance
is more stableenergy.
than ‘cyclohexatriene’ by 354 − 205 =–118 149 kJ mol−1 (see ac
So benzene is more stable than ‘cyclohexatriene’ by 354 − 205 are
= 149 kJ mol (see –118 −1
naphthalene
hat contain rings of delocalised electrons areCompounds
called that
aromatic anthracene
contain
Figure rings anthracene
25.7). of delocalised electrons pyrene
called aromatic
pyrene
The name was originally
More ringsappliedcantofuse
Other
Figure
certain 25.7). arenes
compounds.
natural
together, products
giving such
The 26_07
name
Thehad
that
compounds
Cam/Chem
was
stabilisation
−1
AS&A2
3 originally of 149
as anthracene
applied molto
kJand −1
certain
is known
pyrene:
natural products
variously as the that had
stabilisation energy,
26_07
TheCam/Chem AS&A2
stabilisation of 149 kJ mol anthracene
is known variously as the pyrene
stabilisation energy,
nt aromas, such as vanilla-bean oil, clove oil,strong,
Compounds almond pleasant
that oil, thyme
contain the Notice
aromas, suchthat
delocalisation
oil
rings of aswith
delocalised each
vanilla-bean
energy successive
electrons or oil,the clove
are ring
resonance
called fused
oil, almondtogether,
energy.
aromatic oil, the hydrogen-to-carbon
thyme oil ratio
CO2CH3 Barking Dog Art
tergreen. All of these oils contained Barking the delocalisation
compounds and
Dog oil of
whose
Art energy
wintergreen.
structures or were
the
decreases,
All resonance
of from
these 1 :
oils 1energy.
in benzene
contained to
compounds5 : 8 in pyrene.
whose Eventually,
structures as
were many more rings fu
compounds. The Notice name was that originally
with eachapplied successive to certain
ring fused natural products
together, the that had
hydrogen-to-carbon ratio
de a benzene ring. The term ‘aromatic’ strong, found
eventually to
pleasant include
became
aromas, Other
a together,
benzene
associated
decreases, suchfrom arenes
a sheet
ring.
as vanilla-bean The of
1 : 1 in benzene the
term graphite
‘aromatic’
oil, clove oil, lattice
8 inalmond
toSo5 :benzene pyrene. (graphene)
eventually oil,
is more became
thyme
stable
Eventually, would
oil
So benzene
than result
associated (see
is more rings
‘cyclohexatriene’
as many Topic
stablefuse4).
than
by 354‘cyc−
OH
ylnce of the ring itself, whether
salicylate or not
CH2 CH CH2
Other
the
and with
compound
oil ofarenes
the presence
had
wintergreen. a of
pleasant
together,All of
aMany
the ring
these
sheet ofof the
itself,
oilsthe multiple-ring
whether
contained
graphite or
compoundsarenes,
not
Figure
lattice the such
compound
25.7).
(graphene)
Compounds that contain rings of delocalised electrons are called aromatic whose aswould
pyrene,
had
structures
Figurea are
result strongly
pleasant
were
25.7).
(see Topic carcinogenic
4).
gures 25.8 and 25.9).
wintergreen) found aroma
Compounds (see
that aFigures
contain (cancer
25.8
rings ofand producing).
25.9).
delocalised Even
electrons benzene
are asitself
called isAS&A2
a highly
aromatic 26_07 dangerous
kJ Cam/Chem
−1 substance,
AS&A2 causing −1
to include benzene
Many ofring.
compounds. the The termname
multiple-ring
The was26_07
‘aromatic’
arenes, The
such
originally Cam/Chem
eventually became
stabilisation
pyrene,
applied ofassociated
are
to 149 The
strongly
certain stabilisation
mol is products
known
carcinogenic
natural of variously
149
thatkJhad
molas is
th
compounds.
with the The
presence name
of the
(cancer was anaemia
ring originally
itself,
producing). and cancer
applied
whether or on
tonot prolonged
certain
the
the natural
compound exposure
delocalisation products
had to
a its
that vapour.
pleasant
the
energy had In
delocalisation
or theArt the past
resonance it
energy was used
or
energy. theas r
HO strong, pleasant Even aromas, benzene
suchBarking itself
as is a highly
vanilla-bean
Dog Art oil, dangerous
clove
Barking oil,substance,
almond
Dog causing
oil, thyme oil
strong,
anthracenearoma pleasant
(see aromas,
Figures 25.8
anaemia such
anda
pyrenelaboratory
as vanilla-bean
25.9).
andofcancer solvent, oil,
on prolonged butcloveits use
oil,
exposure is now
almond severely
oil, thyme
to its vapour. restricted,
oil
In the past although
it was it is still
used as were added t
OCH3
igure 25.8 Some pleasant-smelling naturally and oil wintergreen. All of these oils contained compounds whose structures
theirOther were arenes
ccurring aromatic compounds
Notice
eugenol
that
and oil of wintergreen.
with each
All
a laboratory
found
some
of these
to
brands
include
of
a
unleaded
oils contained
solvent, but its usecompounds
benzene Other
petrol
isring.
nowThe severely arenes
to increase
whose
term structures
restricted,
‘aromatic’
anti-knock
although
eventually
rating.
it is still added
became associatedto
(oil of cloves) foundsuccessive
to includering fused together,
a benzene ring. The theterm
hydrogen-to-carbon
‘aromatic’ eventually ratiobecame associated
25.8 Some pleasant-smelling
decreases, fromCO12with
naturally : 1CHO
CH
some
in benzene to 5 : 8 in pyrene. with Physical
brands the of unleaded
presence
Eventually,
3 the presence of the ring itself, whether or not the CO
properties
of petrol
the ring to
as many Compoundsmore
increase
itself,
2CH3
compound
of arenes
whether
rings
their anti-knock
or not
that contain
fuse the
had a pleasant
Compoundsrating.
compound
rings of delocalised had a
that contain pleasant
rings ofare
electrons de
aroma (see Figures 25.8 and 25.9). compounds. The name was origin
g aromatic compoundstogether, a sheet of the graphite lattice (graphene)
aroma (see Figures 25.8 Physical properties
25.9).would
AROMATIC COMPOUNDS
andBenzene and result (see Topic
most alkylbenzenes ofstrong,
arenes
compounds. The name was originally
4). are strongly oily-smelling colourless liquids,
pleasant aromas, strong,
such pleasant
as vanilla-bean
applied
aromas,oil,
to
such
certain
cloveas va
oil
CHO Many of the CHOmultiple-ring arenes, such as immiscible
OH pyrene, arewith, stronglyand carcinogenic
less
CO2CH denseOH than, water. They are non-polar, and the only
OH
Benzene
OH
and most alkylbenzenes and are
3
strongly
oil of oily-smelling
wintergreen. and
All colourless
oil
of of
these liquids,
wintergreen.
oils contained All of these
compou
(cancer producing).
methyl salicylateEven benzene itselfCH is2 a intermolecular
highly
CH CHdangerous bonding methyl
substance, salicylate
isthan,
due causing
to the They induced dipoles CH
of2 van CH der CHWaals’ forces. Their
Figure 25.8
O Some pleasant-smelling
Cl benzaldehyde naturally immiscible with,
2
and less dense water. are non-polar,
2
5.8 CHO
Some pleasant-smelling
CH(CH 3)2 occurring
anaemia(oil of wintergreen)
naturally
Cand (oil
aromatic cancer
compounds on prolonged exposure boiling CH(CH
to 3)2
its vapour. In the(oil of wintergreen)
past found
it was to
used include
as a foundring.
benzene to and
include
The thetermonly
a benzene
‘aromatic’ ring.
evenTh
of almonds) intermolecular bonding points areis similar
dueOHto to the those
induced of the equivalent
dipoles of van cycloalkanes
der Waals’ (see Table
forces. Their 25.3), an
aromatic compounds OCHa3 laboratory solvent, but its HO use isOH now severely restricted, although
methyl it is
salicylate withstill the
added presence HO ofas
tomass CH
with
the ring the presence
CH itself,
of the
CH2 whether or not the com
ring itself,
CHO increase
boiling points are similar steadily with
to relative molecular
those of the equivalent cycloalkanes CO CHexpected.
2
(see Table 25.8 25.3),and and25.9).
benzaldehyde (oil of wintergreen) 2 aroma
3 (see Figures
OH some brands of unleaded petrol toOCH
CHO increase
CH 33 CH(CHtheir3)2 anti-knock rating.CO2CH3aroma (see Figures 25.8 OCHand 3
25.9).
(oil of almonds) increase steadily with relative molecular mass as expected.
thymol vanillin Table 25.3 thymol
eugenol eugenol
OCH CHOBoiling points of some HO
l of thyme)
CHO
OH
3
(oil of vanilla bean) Physical properties of arenes
cyclohexanes and arenes CH3
(oil(oil
of of Compound
thyme)
cloves)
OH
Formula
OH
Boiling
point/°C OCH
OHCompound
(oil of cloves) Formula Boiling
CH2 point/°C
Table 25.3 Boiling points of some Figure 25.8 Some pleasant-smelling Some pleasant-smellingmethyl
Figure 25.8naturally salicylate
naturally
3 CH CH2
vanillin benzoyl and
Benzene chloride thymol
OH Compound Formula Boiling CompoundCH2 CH Formula
eugenol Boiling
cyclohexanes and arenes most alkylbenzenes
occurring are strongly
benzaldehyde
aromatic oily-smelling
occurring colourless
methyl salicylate
aromatic liquids,
compounds
CH(CH ) (oil of wintergreen) CH2
l of vanilla bean) (acidic and nauseating)
er) benzaldehyde (oil of
(oilthan,
of almonds)
CH(CH thyme) compounds
cyclohexane
(oil of wintergreen) C63H212point/°C 81 benzene C6H6point/°C 80 (oil of cloves)
immiscible
25_08 Cam/Chem AS&A2 with, and less dense 3)2They are non-polar, and the only
water.
(oil of almonds)
OCH3 methylcyclohexane CHO
C7H14 100 CHO HO C H
OCH3 intermolecular cyclohexane
bonding is due to the induced dipoles C6Hder
of van 12 benzene methylbenzene
Waals’81forces.HOTheir C6H6 7 8 80 111
CO2CH3
igure 25.9
Barking DogSome OH
Art not-so-pleasant-smelling CH 3 OCH3
can join together. O Cl O
ethylbenzeneCl C H 136
OH
Cam/Chem
romatic AS&A2 Two
compounds
rings
boiling
made in SH
couldare
points
vanillin
the
besimilar toCH
laboratory
those
3
NH2CHO
methylcyclohexane
of the C7H14 (see 100
equivalent cycloalkanes
thymol
CHO SH
methylbenzene
Table 25.3), and OCH3
C
C7H8 8 10111
eugenol
vanillin thymol C OH
(oil of vanilla
increase bean)
steadily with relative molecular (oil of thyme)
mass as expected. eugenol
ethylbenzene C
propylbenzeneH (oil
C 9H of cloves)
136 159
of vanilla OH 8 10 OH12
methyl salicylate
25.9
g Dog Artbean)
Some not-so-pleasant-smelling (oil of thyme) (oilOof cloves)
Cl
benzaldehyde benzaldehyde (oil ofCH(CH
wintergreen)
compounds made in the laboratory NH2 SH CCH(CH3)2 C9H12
propylbenzene 159 3)2
some (oil of almonds) (oil of almonds)
Compound
25_08 Cam/Chem AS&A2 Formula Boiling Compound Formula
OCH3
Boiling
OCH3
am/Chem AS&A2
niline)
Figure
Barking25.9
DogSome
cyclohexane
thiophenol C6H12
point/°C
Art not-so-pleasant-smelling
phenylamine
OH
81 vanillin
(aniline)
benzoyl benzene
chloride
OH
C6H6
thiophenol
vanillin
25.2 Isomerism and nomenclature
point/°C
80
CH3 CH3
benzoyl chloride thymol O Cl
5.9
ke)
Some
Dog Art not-so-pleasant-smelling
aromatic
(burntcompounds
rubber) made in the laboratory
compounds made in themethylcyclohexane
laboratory
(musty,
(acidic
C7H14NH2 100
tar-like)
(oil ofand nauseating)
vanilla bean) NH2(oil of(burnt
Aromatic vanillarubber)
compounds
methylbenzeneSH C7H8
bean)
with 25.2 Isomerism and nomenclature
more
111 than one
thymol
SH(oilOof(acidic
thyme)
Cland nauseating)
substituent
C on the (oil
benzene
C
of thyme)
ring can exist
419 asethylbenzene
positional
phenylamine (aniline) isomers.
thiophenol There areonethree dichlorobenzenes:
benzoylonchloride
Aromatic compounds withC8more
H10 than136 substituent the benzene ring can exist
(musty,
There
ways in which benzene rings can join together. tar-like)
are rings
Two two ways
could in which
be (burnt rubber)
benzene rings can join (acidic and
together. Two nauseating)
rings could be
as positional
25_08 Cam/Chem AS&A2 isomers.
25_08
4
propylbenzene
There
Cam/Chem are
C9H12
three
AS&A2 dichlorobenzenes:
159
ngle bond, as in biphenyl: joined by a single bond, Cl
as in biphenyl: Cl Cl
Figure
Barking 25.9
DogSome Figure
Barking 25.9
Dog Some
not-so-pleasant-smelling
Artwhich Art not-so-pleasant-smelling
There are two
10/10/14 25_09 ways in benzene
Cl
phenylamine rings
(aniline) Cl
can join Clthiophenol
together. Two rings could be Cl benzoyl chloride
hem AS&A2 aromaticCam/Chem AS&A2
8:32 PM
compounds madearomatic compounds made in the
in thiophenol
the laboratory laboratory
NH NH2
phenylamine
joined by a(aniline)
single bond, as in biphenyl:
(musty, tar-like) (burnt 2benzoyl chloride
rubber) (acidic SH
and nauseating)
Clrubber)
Art
25.2 Isomerism
(musty, Barking
25_09 Cam/Chem and AS&A2nomenclature
tar-like) Dog Art (burnt (acidic and nauseating)
Cl
There are two ways in which benzene rings can join together. Two rings could be
Aromatic compounds with
are more than in
one substituent onrings
the benzene ring can exist Cl
Barking
There Dog ways
two Art which
joinedbenzene can join
by a single bond, as intogether. Cl rings could be
Two
biphenyl:
as positional isomers. There are three dichlorobenzenes:
419
joined by a single bond, as in biphenyl: 419
CEDAR COLLEGE 25_09 1,2-dichlorobenzene
Cam/Chem AS&A2 phenylamine (aniline)
1,3-dichlorobenzene ARENES
Cl1,4-dichlorobenzene
phenylamine (aniline)
thiophenol t
25_09 Cam/Chem AS&A2 (musty, tar-like) (musty, tar-like)
(burnt rubber) (b
Cl Cl 1,2-dichlorobenzene
Cl 1,3-dichlorobenzene 419
1,4-dichlorobenzene
Barking Dog Art
The terms ortho-, meta- and para- are sometimes used as prefixes to represent the
Cl
Barking Dog Art
Molecules with delocalised electrons, in which the charge is spread over a
larger region than usual, are more stable than might otherwise be expected. In
benzene, this accounts for the compound being 152 kJ mol–1 more stable than
expected for the Kekulé 13 structure. This way of showing the structure explains
the shape and stability of benzene.
The development of ideas concerning the structure of benzene illustrates
thefuse
More rings can waytogether,
in which theories
giving suchdevelop and as
compounds getanthracene
modified as new
and knowledge
pyrene:
becomes available.
NAMING ARENES
1.4 Naming arenes
Arenes are hydrocarbons, such as benzene, methylbenzene and naphthalene. They are
The name ‘benzene’ comes from gum benzoin, a natural product containing
ring compounds in which there
benzene are delocalised
derivatives. electrons.ofThe
These derivatives simplest
benzene areneeither
are named is benzene.
as substituted
products
anthracene of benzene or as compounds
pyrene containing the phenyl group, C6H5−.
The
The names and structures ofnames
some and structuresofofbenzene
derivatives some derivatives
are shownof benzene
below. are shown in
Notice that with each successive ring fused together, the hydrogen-to-carbon ratio
Table 1.1.
decreases, from 1 : 1 in benzene to 5 : 8 in pyrene. Eventually, as many more rings fuse
together, a sheet of the graphite
Systematic name lattice (graphene)
Substituent groupwould result (see Topic 4).
Structure Table 1.1 !
Many of the multiple-ring arenes, such as pyrene, are strongly carcinogenic The names
chlorobenzene chloro, −Cl C6H5−Cl
(cancer producing). Even benzene itself is a highly dangerous substance, causing derivatives o
nitrobenzene
anaemia and cancer on prolongednitro, −NO2 to its vapour.
exposure C6H5−In
NOthe
2 past it was used as
a laboratory solvent, but its use is now severely restricted, although it is still added to
methylbenzene methyl, −CH3 C6H5−CH3
some brands of unleaded petrol to increase their anti-knock rating.
phenol hydroxy, −OH C6H5−OH
Physical properties of arenes
phenylamine
Benzene and most alkylbenzenesamine, −NH2 oily-smelling
are strongly C6H5−NHcolourless
2 liquids,
immiscible with, and less dense than, water. They are non-polar, and the only
intermolecular bonding is due to the induced dipoles of van der Waals’ forces. Their
5
boiling points are similar to those of the equivalent cycloalkanes (see Table 25.3), and
increase steadily with relative molecular mass as expected.
.3 Boiling points of some

Compound Formula Boiling Compound Formula Boiling
nes and arenes
point/°C point/°C
cyclohexane C6H12 81 benzene C6H6 80
methylcyclohexane C7H14 100 methylbenzene C7H8 111
ethylbenzene C8H10 136
propylbenzene C9H12 159
NAMING ARENES
25.2 Isomerism and nomenclature
Aromatic compounds with more than one substituent on the benzene ring can exist as
Aromatic compounds
positional isomers. with more
There are three than one substituent on the benzene ring can exist
dichlorobenzenes:
as positional isomers. There are three dichlorobenzenes:
Cl Cl Cl
Cl
Cl
Cl
1,2-dichlorobenzene 1,3-dichlorobenzene 1,4-dichlorobenzene
The terms ortho-, meta- and para- are sometimes used as prefixes to represent the
relative orientations of the groups (see Table 25.4).
_415-439.indd 420 10/10/14 8:32 PM

14
NAMING ARENES
Arenes
The terms ortho-, meta- and para- are sometimes used as prefixes and phenols
to represent the relative
orientations of the groups.
ns of substituents on Orientation Prefix Abbreviation Example
1,2- ortho- o- CH3
NO2
1,3-
25
meta- m- Cl CO2H
Arenes
Table 25.4 Orientations of substituents on Orientation Prefix Abbreviation Example

1,4- the benzene p-
para- ring
1,2- ortho- o- CH3
CH3 NH2
Arenes
If the two substituents are different, one of them is andasphenols
defined the ‘root’ group, in the NO2
7
following order of precedence 1,3- meta- m- Cl CO2H
¬CO2H > ¬OH > ¬CH3 > ¬halogen > ¬NO2 (NO2 is called the nitro group)
substituents on Orientation Prefix Abbreviation Example
1,2- and theortho-
ring carbons
o- numbered from the
CH
carbon atom holding
1,4- that group.
para- For
p- example:
3
CH3 NH2
CH3
CO2H NO2acid
is 2-methylbenzoic If the two substituents are different, one of them is defined as the ‘root’
1,3- meta- m- Cl CO2H
following order of precedence
¬CO2H > ¬OH > ¬CH3 > ¬halogen > ¬NO2 (NO2 is called th
CH3 and the ring carbons numbered from the carbon atom holding that group
1,4- para- p- NAMING ARENES
CH3 NH2 CH3
is 3-bromomethylbenzene
CO‘root’
If the two substituents are different, one of them is defined as the 2H group, in the acid
is 2-methylbenzoic
If the two substituents are different, one of them is defined as the ‘root’ group, in the
following
following order of Br
order of precedence.
precedence
¬CO2NO
—CO H > 2¬OH > ¬CH3 > ¬halogen > ¬NO2 (NO2 is called CH
the nitro
3 2 group)
2H > —OH > —CH 3 > —halogen > —NO 2 (NO is called the nitro group)
and the ring carbons numbered from the carbon atom holding that group. For example: is 3-bromomethylbenzene
is 4-nitrochlorobenzene.
CH3
CO2H Br
is 2-methylbenzoic acid
Cl NO2
CH3 Worked example
Draw out allispossible positional isomers of C6H3Br2OH and name them.
3-bromomethylbenzene
Cl
Answer
Br
Worked example
There are six isomers. Their names and formulae are as follows:
NO2 OH OH OH
Draw out all possible positional isomers of C6H3Br2OH and name them.
Br Br
8 Br
is 4-nitrochlorobenzene. Answer
There are six isomers. Their names and formulae are as follows:
OH OH OH
Cl Br Br
Br Br B
Br
Worked example
2,3-dibromophenol 2,4-dibromophenol 2,5-dibromophenol
Br Br
OH OH OH Br
CEDAR COLLEGE
Answer ARENES
There areBr
six isomers. TheirBr
2,3-dibromophenol 2,4-dibromophenol 2,5-dibromophen
names and formulae are as follows:
OH OH OH OH OH OH
NO2
NO2
1,3- meta- m- Cl CO2H
When more than
1,3- one hydrogen
meta- m- atom is substituted, numbers are used to
15 Cl CO 2H
indicate the positions of substituents on the benzene ring (Figure 1.11). The
ring is usually numbered clockwise, and the numbers used are the lowest ones
Arenes – aromatic hydrocarbons
possible. In some cases the ring is numbered anticlockwise to get the lowest
1,4- para-
possible numbers. p-
1,4- para- p-than one hydrogen
When more
In phenyl compounds, such as phenol and CHphenylamine, the NH
3atom is substituted,
−OH2numbers
and are used to
NH2 ring (Figure 1.11). The
indicate NAMING ARENES
the positions of CH3
substituents
−NH2 groups are assumed to occupy the ‘1’ position. on the benzene
Note
ring is usually numbered clockwise, and the numbers used are the lowest ones
If the two substituents
possible. are different,
In some one
cases the of isthem
ring is defianticlockwise
numbered ned as the ‘root’
to get group, in the
the lowest
The names used for compounds with following
Cl
If the two order
substituents are different,Clone of them is defined Cl
of precedence as the ‘root’ group, in the
possible numbers.
a benzene ring can be confusing. The following order of Cl precedence
In phenyl compounds, such as phenol and phenylamine, the −OH and
phenyl group C6H5− is used to name ¬CO2H > −NH > ¬CH
¬OHgroups > ¬halogen > ¬NO (NO2 is called the nitro group)
are3 assumed to occupy the ‘1’
2 position.
many compounds in which one of the ¬CO2H > ¬OH 2
> ¬CH3 > ¬halogen > ¬NO2 (NO2 is called the nitro group)
hydrogen atomsNote
in benzene has been and the ring carbons numbered from the carbon CH3 atom Br
holding that group. For example:
replaced by another Cl Cl Cl
The atom
namesorused
group. and1,2-dichlorobenzene
for compoundsthewith
ring carbons numbered from the carbon atom
1-chloro-3-methylbenzene holding that group. For example:
1-bromo-3-chlorobenzene
The use of phenyl in this way dates
a benzene
back to the first studies
ring can be confusing.
of benzene.
CH3TheNH2 Cl
OH
phenyl group C6H5−At is used CHto name
3
this time, ‘phene’many suggested asin which one of theCO H
was compounds is 2-methylbenzoic acid
2 Cl
an alternative name In phenyl
for benzene
hydrogen atomsbased
compounds, such
in benzene has beenCO2H
asisphenol and phenylamine,
2-methylbenzoic acid the −OH
CH3
and −NH2 groups are Br
on a Greek wordreplaced
for ‘giving
by light’. The
another atom or group. the ‘1’ 1,2-dichlorobenzene
name ‘phene’ was
assumed to occupy position. 1-chloro-3-methylbenzene 1-bromo-3-chlorobenzene
Thesuggested
use of phenylbecause
in this way dates NO2
benzene had been back to the firstinstudies
discovered the of benzene. At NH2 OH
tar formed on heating coal‘phene’
this time, to produce CH3 as
was suggested Cl
gas for lighting. an alternative name for benzene CH3-nitrophenylamine
based
3 2,4-dichlorophenol Cl
on a Greek word for ‘giving light’. The is 3-bromomethylbenzene
name ‘phene’ was suggested Figure 1.11 !
because is 3-bromomethylbenzene
NO2
benzene had been discovered Naming
in thedisubstituted products of benzene and phenol.
tar formed on heating coal to produce Br Cl
gas for lighting. Br Test yourself
3-nitrophenylamine 2,4-dichlorophenol
NO2
NO
5 How
2 does the model
Figure of benzene
1.11 !
9
molecules with delocalised π electrons account
for the following?
Naming disubstituted products of benzene and phenol.
a) The benzene ring is 4-nitrochlorobenzene.
is a regular hexagon.
b) There are no isomers of 1,2-dichlorobenzene.Test yourself
c) Benzene is less reactive than cycloalkenes.
6 When chemists 5 thought
How does that benzene
the model ofhad alternate
benzene single and
molecules double
with bonds,πitelectrons account
delocalised
Cl was sometimes fornamed cyclohexa-1,3,5-triene. Why is this now an unsatisfactory
the following?
Cl systematic namea)forThebenzene?
benzene ring is a regular hexagon.
7 Why is the top right compoundare noinisomers
Figure 1.11 named 1-bromo-3-chlorobenzene
Worked example b) There
and not 1-chloro-3-bromobenzene?
of 1,2-dichlorobenzene.
Worked example c) Benzene is less reactive than cycloalkenes.
6 When chemists thought that benzene had alternate single and double bonds, it
1.5 The
Draw out all
Answer
was
possible sometimesisomers
properties
positional named cyclohexa-1,3,5-triene.
and reactions
of C6H3Br2OH
systematic name for benzene? ofand Why isthem.
arenes
name this now an unsatisfactory
Answer ISOMERS
Arenes are non-polar
7 Whycompounds OF
with
is the top right Cintermolecular
weak
compound
There are six isomers. Their names and formulae 6inH 3 Br
Figure
are
OHbetween
2forces
1.11 named
as follows:
1-bromo-3-chlorobenzene
theirare
molecules. andboiling
The not 1-chloro-3-bromobenzene?
pointsand
of arenes depend
There OHsix isomers. Their names formulae areonas the size of the
follows:
Data molecules. The bigger the molecules, OH OH
the higher the boiling point. Benzene
OH OH while naphthaleneOH
and methylbenzene
1.5
Br are The
solid (Figure 1.12).
Br
liquids at room temperature,
properties and
Br
Br
reactions of isarenes a Br
Br
Arenes are non-polar compounds with weak intermolecular forces between
their molecules. The CHboiling
3
points of arenes depend on the size of the
Data Br
molecules. The bigger the molecules, the higherBrthe boiling point. Benzene
Br methylbenzene are liquids at room temperature,
and Br while naphthalene is a
Br
Note
solid (Figure 1.12). Br
2,3-dibromophenol 2,4-dibromophenol 2,5-dibromophenol
Benzene is toxic. It is also a 2,3-dibromophenol 2,4-dibromophenolCH3 2,5-dibromophenol
carcinogen. Because of this, benzene Figure 1.12
OH ! OH OH
is banned from teaching laboratories. Three arenes
OH – benzene, methylbenzene and
OH naphthalene OH
Arene reactions can be studied using Br Br
other compounds,Notesuch as BrArenes, like other
Br hydrocarbons, do not mix with water, but they do mix
methylbenzene or methoxybenzene. freely with non-polar solvents such as cyclohexane.
Benzene is toxic. It is also a
this carcinogen. Because of this, benzene Figure 1.12 ! Br Br
y this is banned from teaching laboratories. Three arenes – benzene, methylbenzene
Br
Br
and naphthalene
Br Br
y isomers are there
Areneofreactions can be studied using Br
yethylbenzene,
isomers are there
Cotherofcompounds,
6H2Cl 3(CH3)? such as
Arenes, like other hydrocarbons,
Br do not mix with water, but they do mix
ethylbenzene, C H Cl (CH
methylbenzene )?or methoxybenzene. freely with non-polar
2,6-dibromophenol solvents such as cyclohexane.
3,4-dibromophenol 3,5-dibromophenol
their names? 6
6 2 3 3
their names? 2,6-dibromophenol 3,4-dibromophenol 3,5-dibromophenol
10
421
421
5-439.indd 421 10/10/14 8:32 PM

5-439.indd 421 10/10/14 8:32 PM

16
ISTRY
NAMING
If the benzene ring is a ‘substituent’ on an alkyl or alkenyl chain, it is given the name
If the benzene ring is a ‘substituent’ on an alkyl or alkenyl chain, it is given the name
phenyl:
phenyl:
CH2CO2H
C
C
H Cl
phenylethanoic acid 2,2-diphenylchloroethene
25.3 Reactions of arenes

Combustion 11
Benzene and methylbenzene (whose old name, toluene, is still in use) are
components of many brands of unleaded petrol. In sufficient oxygen, they burn
completely to carbon dioxide and steam:
1
C6H6 + 7 2 O2 → 6CO2 + 3H2O
If liquid arenes are set alight in the laboratory, they burn with very smoky flames.
Much soot is produced because there is insufficient oxygen for complete combustion.
A smoky flame is anPROPERTIES
indication of a compound with a high C : H ratio.
1
Benzene and most H6 + 1 O2 →are
C6alkylbenzenes
2
(s) + 3H
6Cstrongly 2O
oily-smelling colourless liquids.
They do notJust
mix with water,
as with but they do mix
hydrogenation, with
the non-polar
enthalpy solvents suchofasbenzene
of combustion cyclohexane.
is less exothermic
than expected,
They are non-polar, because
and the only of the stability
intermolecular bondingdueis to the
due to six
thedelocalised πelectrons.
induced dipoles of
Electrophilic
van der Waals’ forces. substitution in benzene
Their boilingIn a similar
points way to
are similar to the
thoseπbond
of the in alkenes,cycloalkanes,
equivalent andπ
the delocalised bond in benzene is an
increase
steadily witharea of high
relative electron
molecular mass density, above and below the six-membered ring. Benzene
as expected.
therefore reacts with electrophiles. Because of the extra stability of the delocalised
Benzene and methylbenzene
electrons, however, are the
liquids at room
species thattemperature, while naphthalene
react with benzene have to beis a solid.more
much
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
electron-attracting tendency. The other major difference between benzene and
alkenes is what happens after the 12
electrophile has attacked the πbond. In alkenes, an
anion ‘adds on’ to the carbocation intermediate. In benzene, on the other hand, the
carbocation intermediate loses a proton, so as to re-form the ring of πelectrons. This
demonstrates how stable the delocalised system is.
• Br
•
•
CH 2 CH 2 Br • Br CH2 CH 2 Br Br CH2 CH2 Br
carbocation intermediate
17
REACTIVITY
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.
13
REACTIVITY
The electrophiles that react with benzene are all positively charged, with a strong electron-
attracting tendency.
The other major difference between benzene and alkenes is what happens after the
electrophile has attacked the π bond.
In alkenes, an anion ‘adds on’ to the carbocation intermediate.
In benzene, on the other hand, the carbocation intermediate loses a proton, so as to re-
form the ring of π electrons.
This demonstrates how stable the delocalised system is.
14

acids have no effect on benzene.
The electrophiles that react with benzene are all positively charged, with a strong
Y¥ **I
electron-attracting Brst 18
tendency. The other major
|• :t.ae#.l*F
difference between benzene and
t.rs
:
alkenes is what happens after the electrophile has attacked the πbond. In alkenes, an
anion ‘adds on’ to the carbocation intermediate. In benzene, on the other% hand, the
.
carbocation intermediate loses a proton, so as to re-form the ring of πelectrons. This

ELECTROPHILIC MECHANISMS
is
demonstrates how stable the delocalised system is.
retail ;
A- A
• Br
Y¥CH **I
+
.
Began
, ,
t.ae#.l*F
CH 2 CH 2 Br •
• Br CH Br
Fz¥ 2 2 Br CH2CH Br 2
t.rs
:
Br Br Br
carbocation intermediate
%
.
Alkenes react by electrophilic addition. Arenes react by electrophilic substitution.
is
H Br Br
retail ¥ ;
go.gg#.itn:fq.E*s.::kI*s.
A- A
Br
+
. •
H H
Began
, ,
•
Fz¥
OH
–H
+2 .tk#af+*r
A I
Br A. Br Br .
.
.
Begins carbocation
intermediate
Br Br
-
15
go.gg#.itn:fq.E*s.::kI*s.
¥
H H
OH
+2 .tk#af+*r
A I
A. .
.
.
Begins
10/10/14 8:32 PM
Br Br
:
-
¥
BROMINATION
Benzene will react with non-aqueous bromine on warming in the presence of anhydrous
aluminium chloride or aluminium bromide, or iron(III) chloride.
: atoms.
¥Anhydrous aluminium or iron(III) halides contain electron-deficient
They can react with the bromine molecule by accepting one of the lone pairs of electrons
on bromine.
16

bromine:
Br 19 Br
Br Br •• Al Br Br Br Al Br (1a)
Br Br Arenes and phenols

BROMINATION
This causes strong polarisation of the Br¬Br bond, weakening it, and eventually
This causes strong polarisation
leading of the Br—Br
to its heterolytic bond, weakening it, and eventually leading to
breaking:
Alkenes react by electrophilic addition.
its heterolytic breaking. Br
Br
Arenes react by electrophilic substitution.
•
Br • Br Al Br Br + Br Al Br (1b)
Bromination
Benzene will Br react with non-aqueous bromineBron warming in the presence of
anhydrous
The bromine aluminium
cation chloride
that is formed is or aluminium
a powerful bromide, or
electrophile. iron(III) chloride,
It becomes or even
attracted to
just iron metal. In the latter case, an initial reaction between iron
the πbond of benzene. It eventually breaks the ring of electrons and forms a σ bond and bromine
provides
to one the iron(III)
of the carbon atomsbromide catalyst:
of the ring:
2Fe(s) + 3Br2(l) → 2FeBr3(s) H
aluminium or iron(III) halidesBrcontain electron-deficient atoms. They
Anhydrous Br (2) can
react with the bromine molecule by accepting one of the lone pairs of electrons on
Two bromine:
of the six πelectrons are used to form the (dative) bond to the bromine atom.
17
The other four πelectrons are spread over the remaining five carbon atoms of the
Br Br
ring, in a five-centre delocalised orbital (see Figure 25.10).
Br Br •• Al Br Br Br Al Br (1a)
.10 The four πelectrons are
over five carbons
Br Br
5 6 H
This causes strong polarisation of the Br¬Br bond, weakening it, and eventually
1
4 leading to its heterolytic breaking:
Br Br
3 INTERMEDIATE
2 Br
•
• Br
The bromine cation that is formed
Br Al Br
is a powerful electrophile. It becomes attracted to the π
Br + Br Al Br (1b)
bond of benzene. It eventually breaks the ring of electrons and forms a σ Brbond to one of
The distribution of theBrfour πelectrons is not even. They are associated more with
the carbon atoms of the ring:
carbonTheatoms 3 andcation
bromine 5 thanthat
with atoms 2,is4 aand
is formed 6. The electrophile.
powerful positive charge is therefore
It becomes attracted to
distributed
25.10 JM/Chem.4 over atoms
AS&A2
the πbond 2, 4 and
of benzene. It 6. This is best
eventually represented
breaks the ring by
of the following
electrons and classical
forms a σ bond
mesomers:
to one of the carbon atoms of the ring:
Barking Dog Art
H H H
H
Br
Br Br Br Br Br (2)
Two of the six πelectrons are used to form the (dative) bond to the bromine atom.
423
The other four πelectrons are spread over the remaining five carbon atoms of the
e 25.10 The
15-439.indd 423 four πelectrons are 18 10/10/14 8:3
lised over five carbons
5 6 H
1
4
3 2 Br
Br Br
•
Br • Al
Br 20 Br Br + Br Al Br (1b)
Br Br
The bromine cation that is formed is a powerful electrophile. It becomes attracted to
the πbond of benzene. It eventually breaks the ring of electrons and forms a σ bond
INTERMEDIATE
to one of the carbon atoms of the ring:
H
Two of the six π electrons are used to form theBr(dative) bond to the bromine
Br atom. (2)
The other four π electrons are spread over the remaining five carbon atoms of the ring, in a
Two of the six πelectrons are used to form the (dative) bond to the bromine atom.
five-centre delocalised orbital. The other four πelectrons are spread over the remaining five carbon atoms of the
Figure 25.10 The four πelectrons are

delocalised over five carbons
5 6 H
1
4
3 2 Br
The distribution of the four πelectrons is not even. They are associated more with
carbon 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
19
mesomers:
Barking Dog Art
H H H
Br
Br Br Br
CHEMISTRY
NIC CHEMISTRY 423
We shall return to this feature of the intermediate carbocation when we look at 10/10/14 8:32 PM
181333_25_A_Chem_BP_415-439.indd 423
We shall return to this feature of the intermediate carbocation when we look at
orientation effects on page 427.
BROMINATION
orientation effects on page 427.
The intermediate carbocation then loses a proton, to re-form the sextet of
The intermediate carbocation then loses a proton, to re-form the sextet of
π electrons:
π electrons:
The intermediate carbocation then loses a proton, to re-form the sextet of π electrons:
H Br Br
H Br Br
•
•
•
•
H (3)
H (3)
The final stage regenerates the catalyst,

The final stage by the
regenerates thereaction
catalyst,between the proton
by the reaction (H+) formed
between in formed in
the proton
the above step withstep The
the(3) fi
with
[AlBr nal stage regenerates
− the catalyst,
4] .the [AlBr4] formed in step (1b):
− by the reaction between the proton formed in
−
step
+ (3) with − the [AlBr4] formed in step (1b):
H + Al Br4 → HBr + Al Br3
H+ + Al Br4− → HBr + Al Br3
Further substitution can occur with an excess of bromine, to form dibromobenzene,
Further
and even substitution canFor
tribromobenzene. occur with an excess
the reactions of bromine, see
of bromobenzene, to form dibromobenzene,
section 25.4.
and even tribromobenzene. For the reactions of bromobenzene, see section 25.4.
Chlorination 20
Chlorination
Just as with bromine, chlorine in the presence of an electron-acceptor such as
Just aschloride
aluminium with bromine, chlorineinto
will substitute in the presence of an electron-acceptor such as
benzene ring:
aluminium chloride will substitute into the benzene ring:
Cl
Cl
AlCl 3
CEDAR COLLEGE Cl 2 HCl ARENES
warm AlCl
3
Cl 2 warm HCl
step (3) with the [AlBr4] formed in step (1b):
H+ + Al Br4− → HBr + Al Br3
21
Further substitution can occur with an excess of bromine, to form dibromobenzene,
and even tribromobenzene. For the reactions of bromobenzene, see section 25.4.
Chlorination CHLORINATION
ANIC CHEMISTRY Just as with Just as with bromine,
in the chlorine
presencein
of the presence of an electron-acceptor
such as aluminium such as
IC CHEMISTRY bromine, chlorine an electron-acceptor
HEMISTRY
chloride willaluminium chloride
substitute into will substitute
the benzene ring. into the benzene ring:
e 25.11 Three powerful explosives that CH3 OH

5.11
y-nitroThree powerful explosives that
compounds Cl
CH3 OH
Three powerful explosives that O2N NO2 O2NCH3 NO2 O2NOH NO2
itro compounds
ompounds
O2N O2N NO2 NOO2 N O2N NO2 O2NO
N 2 O2N NO2 NO2
2
AlCl 3
Cl 2 warm HCl
NO2 NO2 NO2

trinitrobenzene (TNB) trinitromethylbenzene trinitrophenol
The properties
NO2 NO2and reactions (trinitrotoluene)
ofNOchlorobenzene
2 NO(TNT)
2 are discussed
NO2 in section
NO
(picric acid) 2
25.4.
trinitrobenzene (TNB)
trinitrobenzene (TNB) trinitromethylbenzene
trinitromethylbenzenetrinitrophenoltrinitrophenol
(trinitrotoluene) (TNT)
(trinitrotoluene) (TNT) (picric acid) (picric acid)
Now trysubsequent
Also, via this reduction, nitration is an important route to aromatic amines,
Also, viawhich
Also,
are used
subsequent to make nitration
reduction,
viaa subsequent
a variety isofan
reduction,
dyes (see Topic
important
nitration is of
27).
route to aromatic
anbenzene.
important route amines,
to aromatic amines,
which Suggest
are Cam/Chem
25_11
mechanism
used to make for the chlorination
a variety of dyes (see Topic 27).
AS&A2
which NO
are 2used to make NH
a variety
2 of dyes (see Topic 27).
21
25_11 Cam/Chem
NO Dog
Barking AS&A2
Art NH
25_11 Cam/Chem
2
NO AS&A2 2 NH 2
2
Barking Dog Art dyes
Nitration
Barking Dog Art
dyes
Benzene does not react with nitric acid, dyes
phenylamine even when the acid is concentrated.
But a mixture phenylamine
of concentrated nitric and concentrated sulfuric acids produces
Alkylation (thephenylamine
nitrobenzene: Friedel–Crafts reaction)
Alkylation
In 1877 the(the
FrenchFriedel–Crafts
chemist Charles Friedel reaction)
and his co-worker, American chemist
Alkylation (the Friedel–Crafts reaction) NOwith
In 1877 James Crafts,chemist
the French discovered thatFriedel
Charles when benzene is heated
and his co-worker, a chloroalkane
2American chemist in the
presence
James Crafts,
In 1877
of aluminium
discovered
the French ALKYLATION
chloride,
thatchemist
when benzene the alkyl group
CharlesisFriedel
heated andattaches
with his to the benzene
a chloroalkane
co-worker, in thering. chemist
American
presenceJames
of aluminium chloride, theconc.
alkylH2group
SO 4 attaches to the benzene ring.
Crafts, discovered
HNO that when benzene is heated with a chloroalkane in the
CH3 H2 Ochloride, the
when benzenepresence
is heatedofwith 3 T< 55
a chloroalkane in°Cthealkyl
presence
aluminium chloride, the groupofattaches
aluminium
to the benzene ring.
CH3
alkyl group attaches to the benzene ring.AlCl3 ! heat
! CH3 Cl ! HCl
CH
nitrobenzene
AlCl3 ! heat 3
! CH3 Cl ! HCl
Further nitration
The reaction goesto
viadinitrobenzene
AlCl3 ! heat
the formation (and
of an also some
intermediate oxidation) can occur unless the
carbocation.
! CH3 Cl ! HCl
temperature is controlled to be below about
The reaction goes via the formation of an intermediate
55 °C.
carbocation.
! " !
TheCH role
3
ofClthe concentrated
AlCl3 CHsulfuric
3 Cl acid in3 this CH
AlCl reaction
3 !
is to"4 produce the
AlCl
The reaction goes via the ! of "
formation an intermediate! carbocation.
powerful
CH Cl electrophile
AlCl3 needed
CH3 to
Cl nitrate
AlCl3the benzene
CH3 ! ring.AlCl4By analogy with
"
3
The carbocation is the electrophile.
bromination: ! " ! "
CHis
The carbocation 3 theCl AlCl3
electrophile. CH3 Cl AlCl3 CH3 ! AlCl4
H CH3 CH3
Br
!
H electrophile.
CH3 CH3
CHis3 the
The carbocation
! ! ! H!
CH3
Br ! H CH3 H! H!CH3
! 22
AcylationCH (Friedel–Crafts
3 acylation)
! ! H!
Acylation
If an acyl (Friedel–Crafts
chloride (see section 26.3,acylation)
page 442) is used instead of a chloroalkane in
the Friedel–Crafts reaction, a phenylketone is produced.
If an acyl chloride (see section 26.3, page 442) is used instead of a chloroalkane in
Acylation (Friedel–Crafts acylation)
the Friedel–Crafts reaction, a phenylketone is produced.
3 CH O
.indd 424 CHpage
If an acyl chloride (see section 26.3, 3 OC
442) is used instead of a chloroalkane in 1
CEDAR COLLEGE the Friedel–Crafts reaction, a phenylketone C is produced. ARENES
AlCl3 ! heat
! CH3 COCl ! HCl
AlCl3 ! heat CH3 O
! CH COCl ! HCl
The carbocation is the electrophile.
H 22CH3 CH3
!
CH3
! ! H!
Acylation (Friedel–Crafts
ACYLATION acylation)
If an acyl chloride (see section 26.3, page 442) is used instead of a chloroalkane in
If an acyl chloride isthe Friedel–Crafts
used instead reaction, a phenylketoneaisphenylketone
of a chloroalkane, produced. is produced.
CH3 O
C
Arenes and phenols
AlCl3 ! heat
! CH3 COCl ! HCl
O
The reaction between an acyl chloride and aluminium
!
chloride produces the acylium
"
! AlCl
ion.CThe intermediate is formed
3
from CH
the attack
3 C of O
the ! AlCl
acylium ion4on the benzene
CH3ring. Cl an acylium ion
426 O CH3 O
CH3
!
C H C
CH3 C O
_Chem_BP_415-439.indd 426 ! ! H! 10/10/14 8:32 PM
23
Worked example
Draw the structural formulae of the products you would expect from the reaction of
benzene and aluminium chloride with
a CH3CH2Cl
this b (CH3)2CH—COCl.
anochlorine compounds are
Answer
synthesise the following
ds from benzene? a O
H3)3 O
C
SKILL CHECK 1
b
O O
Draw the structural formulae of the products you would expect from the reaction of
C benzene and aluminium chloride with
(a) CH3CH2Cl
(b) (CH3)2CHCOCl.
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
NO2
NO 2
58% 4% 24
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
3-positions, but only one 4-position). This non-random attack is seen in other
reactions too (see Table 25.5).

!
Thewefimight expectregenerates
nal stage 23 nitration
the electrophilethe
for catalyst,to by
be NO +
the2 :reaction between the proton formed
Worked example
step (3) with the [AlBr4]− formed NO 2in step (1b):
Draw the structural formulae of the products you would expect from
+ −
H + Al Br4 → HBr + Al Br3 and aluminium chloride with
benzene
NO 2SKILL CHECK 2 H
Further substitution can occur a CH 3CHan
with 2Cl excess of bromine, to form dibromobenzene
Now try this b (CH3)2CH—COCl.
What and evencompounds
tribromobenzene. For
to the reactions of bromobenzene,
compounds see fromsection 25.4.
Whatorganochlorine
organochlorine
and thiscompounds
indeed seems are
are needed
to be the case. synthesise the following
Overthe
thefollowing
Answer
years, various pieces of evidence have been collected to substantiate the
needed to synthesise
benzene?
+
claim of NO
compounds from benzene?2 (known as the nitryl O to be the electrophile.
a cation or nitronium ion)
Chlorination
salts containingOthe nitryl cation exist, for example nitryl chlorate(VII),
1 )3 ● Stable
C(CH3Just as 2with
NO +
Cl O4−bromine, chlorine
, and nitryl tetrafl in the presence
uoroborate(III), of anof electron-acceptor
NO2+BF4−. Each these, when such as
aluminium
dissolvedchloride C
in an inert will substitute
solvent, into the
nitrates benzene benzene
smoothly and inring:
high yield to
give nitrobenzene.
●The infrared spectrum of a compound
b tells us about the types of bonds in the
compound, and its shape. The infrared spectrum Cl of a solution of nitric acid in
2 O
O sulfuric acid shows a strong absorbance
C(CH3)3 at 2350 cm−1. This absorbance is also
present in the spectra of nitryl
AlCl 3 salts, but is not present in that of nitric acid in
C the absence of sulfuric acid.
Cl 2 HClabsorbance
It is almost identical to a similar
warm
in the spectrum of carbon dioxide. CO2 and NO2+ are isoelectronic linear
molecules (see section 3.13), and so would be expected to have similar
infrared spectra.
The properties
● Various and reactions
physico-chemical ofexample,
data (for chlorobenzene are ofdiscussed
the depression in section
freezing point) show 25.4.
that when one molecule of HNO253 is dissolved in concentrated sulfuric acid, four
Electrophilic substitution in substitute
particles are formed. (The freezing point of a liquid is lowered if substances are
Now try this the orientation of the incoming group
dissolved in it, and the amount of the depression depends upon the mole ratio of
solute to solvent.)
Suggest a mechanism for theWhen
chlorination of benzene.
methylbenzene is treated with nitric and sulfuric acids, th
These three pieces of evidence suggest that the following reaction occurs when the
mono-nitro compounds are formed in the following ratios:
two acids are mixed:
2H2SO4 + HNO3 → H3O+ + NO2+ CH

+ 2HSO
3 4
− CH 3 CH 3
Nitration NO2
The mechanism
Benzene does not react of the withnitration
nitric acid,of benzene
even when the acid is concentrated.
ButSulfuric
a mixture
acid is aof NITRATION
concentrated
stronger nitric
acid than nitric and
acid. It is concentrated sulfuric
so strong that it NO
donates
2
acids produces
a proton
to nitric acid. In this reaction, nitric acid is acting as a base!
nitrobenzene: NO 2
When benzene is treated with a mixture −of concentrated
+
nitric and sulphuric acid at around
H2SO4 + HNO3 → HSO4 + H2NO3
55oC nitrobenzene is formed. 58% 4% 38%
NO
The protonated nitric acid then loses a water +molecule, and2 this is then protonated
If the NO2 electrophile had attacked the ring in a purely rando
by another molecule of sulfuric acid:
distribution should have been 40 : 40 : 20 (there being two 2-pos
H2NO3+ → H2O + NO2+ conc. H2SO 4
HNO 3 −+ HT<O
H2SO4 + H2O → HSO
3-positions,
+ H2 O This non-random attack is
but only one 4-position).
4 3 55 °C
reactions too (see Table 25.5).
The nitronium ion then attacks the benzene ring in the usual way, forming the
carbocation intermediate, which subsequently losesnitrobenzene
a proton:
O
Further nitration to dinitrobenzene (and
O also some
O oxidation) can occur unless the
O O
N is controlled
temperature H to N 55 °C.
N beObelow about
The role of the concentrated sulfuric acid in this reaction is to produce the
powerful electrophile needed to nitrate the benzene H ring. By analogy with
bromination:
26
Br
The nitration of benzene and other arenes is an important reaction in the production
181333_25_AS_Chem_BP_415-439.indd 427
of explosives (see Figure 25.11)
Br H 425

m_BP_415-439.indd 425 27/10/14 9:24 AM
NO2
show. 1-m
The π bond also makes benzene+more 24 than expected. Not only is benzene are
HNOstable
3 ⎯→ + H2O
much less reactive than cyclohexene, it is also thermodynamically more stable. We met
can demonstrate this by comparing the actual and the ‘calculated’ enthalpy changes form
of hydrogenation. The hydrogenation
The mechanism of alkenes is ansubstitution
of the electrophilic exothermic process:
is:
NITRATION b Benzen
CH2“CH2 + H2 → CH3¬CH3 ∆H = −137 kJ mol−1
1
substitu
NO2
H NO 2
For many higher alkenes, the enthalpy changes of hydrogenation are very similar sulfuric
to each other, and average about 118 kJ mol−1. Furthermore, for dienes and trienes called s
+ stage 1 stage 2
(containing two and threeNO
double +
bonds, respectively), + H+ of
the enthalpy changes
2
hydrogenation are simple multiples of this value (see Table 25.2). So we might expect
SO3 m
benzene to follow the same trend. benzen
FormationIn
of stage 1 in the occurs
the electrophile mechanism, the
in 3 steps electrophile,
@ 55 oC NO2+, i Wh
Alkene is attractedFormula
to the high electron∆H 1density
hydrogenation
-1 +
of/ the π∆Hbonding
1
per C“C acce
kJ mol
HNO3 ⟶ NO 2 + OH  
system in benzene. A pair of electrons from the benzene mec
cis-but-2-ene CH 3¬CH“CH¬CH −119 HSO4 + H+2O  −119
OH + H2SO43 ⟶
ring is donated to the nitrogen atom in NO 2 , and
ii Wri
cyclohexeneforms a new2 covalent2 bond.
H O + H SO 4 ⟶At this point,
−118HSO 4 + benzene’s
H 3O −118
+
aif
delocalised ring
2 H2SO 4 of
+ electrons
HNO3 ⟶ is disrupted.
2 HSO4 Th
+ ere
H3Oare+ now
+ NO+2 form
four π bonding electrons and a positive charge spread
butadiene CH2“CH¬CH“CH2 27 −236 −118
over five carbon atoms.
cyclohexadieneHowever, the full delocalised ring is restored in
−232 stage 2
−116
when the C H bond breaks heterolytically. Both electrons Oxidation of th

in the C H covalent bond go into nitrobenzene’s π The presence of t
‘cyclohexatriene’ [−354] + [−118]
bonding system, and hydrogen leaves
(predicted)
as an H ion. There
(assumed)
methylbenzene, c
are now six electrons spread over the six carbon atoms so its alkyl side-chain
the chemical stability of the benzene ring is retained in oxidised by a chem
thisthe
substitution
HYDROGENATION manganate(VII).
If we measure experimentalreaction.
enthalpy change of hydrogenation of benzene,
we find that
Benzene it iswith
reacts far less exothermic
hydrogen than
gas and thatcatalyst
nickel predicted for o‘cyclohexatriene’
at 200 in
C to form cyclohexane.
Table 25.2:
378 24 Benzene and its compounds
–1
3H 2 (g) ∆H hydrogenation
1
= –205 kJ mol
10/10/14 8:32 PM
28

The same stabilisation is possible when substitution occurs at position 4.
tivating groups and those that cause substitution to occur more slowly
an with benzene are called deactivating groups (Table G5 ). 25
2,4-directing groups usually cause substitution faster than benzene

and 3-directing groups normally cause
Acyl electrophilic
halides substitution
react with benzene in the presence of a halogen carrier
to occur more slowly than benzene REACTIONS
(chlorine
catalyst. Consider as OFof ethanoyl
thea reaction
substituentMETHYL BENZENE
is an chloride with benzene:
exception to this – it is a 2,4-directing
CH3COCl group+ Cand
6H6
chlorobenzene
C6H5COCH3 + HCl
Methylbenzene
reacts more slowly than benzene). reacts in the same way as benzene, via an electrophilic- substitution
mechanism. If substitution were to occur at position 3, stabilisation of the positively
enzene ring here is named as
charged intermediate is not possible by donation of the lone pair on the
nyl substituent. O into the ring.
The conditions for the reactions of methylbenzene are slightly milder than those for the
he rate-determining reactions of reaction

step in the benzene is asthe
the attack
methylof group is an activating group.
the electrophile
the ring. When an activating
The methylgroup
groupisdonates
presentelectron
this step occursinto
density morethe benzene ring (positive inductive effect).
ickly as there is more electron density in the ring so that an electrophile
ThisWhen
attracted more strongly. increases
the the
ringamount of electron
is deactivated by density in the ring so that it is more attractive to
the withdrawal
electron density, theelectrophiles
electrophileand reacts more
is attracted less readily.
strongly and the
action occurs more slowly. This is a similar reaction to that already seen on pages 34–35 for the
Thus methylbenzene reacts more formation
readilyofthan
the electrophiles
benzene due forThe
chlorination
to the
methyl group and
hasalkylation.
an electron-releasing effect and this also stabilises
the intermediate when substitution occurs at positions 2 and 4.
ectron-releasing effect of the –CH 3 group (positive inductive
+ −
CH3COCl + AlCl 3 CH3CO + [AlCl
The 4]
electron-releasing effect of the methyl group comes from the
ect). The methyl group activates the ring towards electrophilic overlap of the electron density in the C–H bond with a p orbital on an
The mechanism is the same as foradjacent
alkylation.
atom (Figure G43).
bstitution by donating electron density into the ring. This makes 29 the
The stabilising effect of the methyl group on the intermediate can be
shown as:
Examiner’s tip
A summary of the explanations
is that an electron-releasing
group stabilises the
intermediate by electron
donation into the ring. This − +
Again, isthe
stabilisation only possiblestep could be shown with [AlCl4] removing the H
second
to reform
when the catalyst.
substitution occurs
at positions 2, 4 and 6. An As for phenol, this stabilisation is only possible when substitution
REACTIONS OF METHYL BENZENE
electron-withdrawing group occurs at positions 2 or 4.
destabilises the intermediate
Methylbenzene
by withdrawing electron reacts in the same way as benzene, via an electrophilic-
Methylbenzene reacts more readily than benzene due to the electron-releasing effect of
substitution
density from themechanism.
ring. This The conditions for the reactions of
the –CH3 group (positive
destabilisation is inductive
greatest
methylbenzene are slightly effect).The
milder thanmethyl
those group
for theactivates
reactions of thebenzene
ring towards
when substitution occurs at
as the methyl by
electrophilicpositions
substitution group is an activating
donating electrongroup.
density Theinto
methyl group donates
the ring.
2, 4 and 6, therefore
electron density
substitution at positioninto
3 isthe benzene ring (positive inductive effect). This
This makes the ring more
increases
preferred. negative,
the amount i.e. more
of electron attractive
density in thetowards
ring so thatelectrophiles
it is more and the
attractive
reaction occurs more to electrophiles
quickly andbenzene.
than with reacts more readily.
The methyl group is a 2,4-directing group and so the major products
of substitution
The methyl group are:
is a 2,4-directing group and so the major products of substitution are:
Some of the electrophilic substitution reactions of methylbenzene are

30
shown in Figure G39.

26
CHLORINATION OF METHYL BENZENE

If methylbenzene is reacted with chlorine in the presence of a halogen
If methylbenzene is reacted with chlorine in the presence of a halogen carrier catalyst
carrier catalyst (AlCl3) at room temperature 2-chloromethylbenzene and
(AlCl3) at room temperature 2-chloromethylbenzene
4-chloromethylbenzene andis4-chloromethylbenzene
are formed. This chlorination in the ring. are
formed.
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
the methyl group is substituted by a Cl atom. This involves a free radical The mechanism he
substitution mechanism as for alkanes. alkanes (see Chapt
31 of the Coursebook
summarised as
UV
If methylbenzene is reacted with chlorine in the presence of a halogen Cl2
4-chloromethylbenzene are formed. This is chlorination in the ring. RCH3 R
RCH2 2 R
plus a termination
CHLORINATION OF METHYL BENZENE

If methylbenzene is reacted with chlorine in the presence of UV light then side-chain
If methylbenzene
substitution occurs where a hydrogen atom inisthe
reacted withgroup
methyl chlorine in the presence
is substituted byofa UV
Cl atom.
light then side-chain substitution occurs where a hydrogen atom in Examiner’s t
the methyl group
This involves a free radical substitution is substituted
mechanism by alkanes.
as for a Cl atom. This involves a free radical The mechanis
substitution mechanism as for alkanes. alkanes (see C
of the Courseb
summarised as
UV
Cl2
RCH3
RCH2 2
plus a termina
32

27
METHYL BENZENE
33
Y ORGANIC CHEMISTRY
In ethylbenzene, the hydrogen In atoms

ethylbenzene,
on the carbon
the hydrogen
atom adjacent
atomstoon
thethe
benzene
carbon atom adjacent to the benzene
ring are substituted much morering readily
are substituted
than the three
muchhydrogens
more readily
on the
than
other
thecarbon,
three hydrogens on the other carbon,
If methylbenzene is reacted with chlorine in the presence of a halogen
so the following reaction gives so a good
the following
yield of the
reaction
product:
gives a good yield of the product:
4-chloromethylbenzene
CH CH
2 3
are formed. This
CHisCH
2
chlorination in the ring.
CHClCH3 CHClCH
3 3
UV light UV light
Cl2 Cl2 HCl HCl
OXIDATION
or boiling OF THE
or boiling SIDE CHAIN
> 90% > 90%

When alkylbenzenes are treated with hot acidified potassium manganate(VII), oxidation of
Oxidation of the side
Oxidation
chain of the side chain
the whole side chain occurs, leaving the carbon atom closest to the ring as a carboxylic
When alkylbenzenes are treated When
with alkylbenzenes
hot alkaline potassium
are treated manganate(VII),
with hot alkaline potassium manganate(VII),
acid group:
oxidation of the whole side chain oxidation
occurs,ofleaving
the whole
the carbon
side chain atomoccurs,
closestleaving
to the the
ringcarbon atom closest to the ring
as a If methylbenzene
carboxylate is reacted acid
or carboxylic with
as chlorine in the
a group:
carboxylate presence ofacid
or carboxylic UV group:
light then side-chain substitution occurs where a hydrogen atom in
CHgroup
the methyl 2 CH 3 is substituted by a Cl atom.
CH 2 CH CO
This 2K
3 involves a KMnO
free radical COExaminer’s
CO 2K
2H
tip CO2 H
KMnO4 acidified
KMnO
1H 1
4(aq) 4 The mechanism
1 H1(aq) here is as for
substitution mechanism as for alkanes.
heat with OH– heat with OH– alkanes (see Chapter 10, page 434
heat
of the Coursebook) and can be
summarised as
UV
Cl2
CH 3 CH 3 CO2 K CO
CO2 K
2H CO2 H
KMnO4 acidified
KMnO
1HKMnO
1
4(aq)
4 1 H1(aq)
RCH3 RCH2
heat with OH– with OH–
heat heat
CH 2 CH 3 CH 2 CH
CO3 2K CO
CORCH
2K
2H 2 2 RCH2 CO2 H
Worked example Worked example plus a termination step.
Three hydrocarbons A, B and C with

Threethe formula C9HA,
hydrocarbons B and
12 were C with the
oxidised
34 by hot
formula
potassium
C9H12 were oxidised by hot potassium
manganate(VII). manganate(VII).
● Hydrocarbon A gave benzoic acid, gave benzoicCacid,
● Hydrocarbon●AHydrocarbon ● Hydrocarbon C gave benzene-1,2,4-trioic
gave benzene-1,2,4-trioic
C6H5CO2H. C6H5CO2H. acid: acid:
● Hydrocarbon B gave benzene-1,2-dioic
● Hydrocarbon B gave
CObenzene-1,2-dioic
2 H CO2 H
acid: acid: CO H CO H
2 2
CO2 H CO2 H

CO2 H CO2 H
CO2 H CO2 H
Suggest the structures of A, B and C.
oxidation of the whole side chain occurs, leaving the carbon atom closest to the ring
g are substituted much more theCH
so readily 2CH 3the
than
following three hydrogens
reaction gives
acid agroup:
good theCHClCH
on yieldother carbon,
of the
CH 3 product:
3
as a carboxylate or carboxylic
the following reaction gives a good yield of the product: CO2 K
UV light KMnO4 1 H1(aq)
CHCH2 CH
2CH
3 3 CO2 K 3
28CHClCH CO2 H
CH 2CH 3 Cl CHClCH
KMnO
23 4 HCl
1
–
1 H heat
(aq) with OH
or boiling
heat with OH–
UV light CH 2 CH 3 CO2 K
UV light Cl2 > 90% HCl
Cl2 or HCl
boiling
Worked example
Oxidation of the side chain
or boiling
> 90%
When alkylbenzenes
> 90%
SKILL CHECK 3
are treated withThree hydrocarbons
hot alkaline A, Bmanganate(VII),
potassium and C with the formula C9H12 were oxidised by hot pot
Oxidation
CH 3 of the side chain CO2 K
manganate(VII). CO2 H
xidation ofThree thehydrocarbons
side
oxidation chain
of the wholeKMnO side 4chain occurs, leaving the carbon
A, B and C with the formula C9H12 were 1 atom closest to the ring
1 Hoxidised
(aq) by hot potassium
asWhen alkylbenzenes
a carboxylate or heat are treated with
carboxylic ● hot
with OH–acid group:
alkaline potassium
Hydrocarbon manganate(VII),
A gave benzoic acid, ● Hydrocarbon C gave benzene-1
hen alkylbenzenesmanganate(VII).
are treated with hot
oxidation of alkaline
the wholepotassium
side manganate(VII),
chain occurs, leaving the carbon atom closest to the ring
CHCH2 CH CH
3 C 6 5 CO
H CO 2 2 K2 K
COH. CO
CO22HH acid:
dation of the whole side chain occurs, 2leaving
as a carboxylate
3 the carbon
or carboxylic atom closest
KMnO4 acid group:
to the ring
● Hydrocarbon B gave 1benzene-1,2-dioic
H (aq)
1
a carboxylate or carboxylic acid A

group: CO2 H
Hydrocarbon gave benzoic heatacid, C6–H5CO2H.
Worked exampleCH 2 CH 3
with OH acid: CO 2 K CO 2 H CO H
CH 2 CH 3 CO2 K KMnO4 COCO
2 H H1 H (aq)
1 2
Hydrocarbon
KMnO4
Three B gave benzene-1,2-dioic
hydrocarbons A, B and C with
1 H1
–
the
heat with OH
acid:
(aq) formula C H
9 12 were 2
oxidised by hot potassium
heat with OH–
manganate(VII).
● HydrocarbonCH A 3gave benzoic acid, CO2 K CO2 HC gave benzene-1,2,4-trioic
● Hydrocarbon CO2 H CO H
KMnO4 1 H 1
(aq) 2
C6H5CO2H. –
acid:
Suggest theCO structures of A, B and C.
● Hydrocarbon CH 2K CO2 H
heat with OH
B gave 3 benzene-1,2-dioic CO2 HK
CH 3 Now try this CH 2 CH CO
3 2 K KMnO4 CO CO
2 2 H 1 H1(aq) CO2 H
acid:4
KMnO
Hydrocarbon C gave benzene-1,2,4-trioic 1OH
heat with H1– (aq) Answer
acid: CO2 H
OH– CO H Since A gaveCO benzoic acid, all three ‘extra’ carbon atoms must be in the same side ch
Suggest WorkedCH
structures
heat with for the2 2CH 3
example aromatic 2K CO2 H
CH 2 CH 3carboxylic acids which will beCO K
produced
2 CO
CH2CH2CH 2 H CH(CH3 )2
3
when the Three hydrocarbons A, Bare and C with the formula C9H12 were oxidised by hot potassium
Worked example
following compounds
CO2 H
Worked example Suggest
oxidised bymanganate(VII).
the
hot structures of A, B and C.
potassium manganate(VII). CO2 H
(All these ●Three hydrocarbons
Hydrocarbon
compounds are A gave
isomers A,benzoic
Bwith
and Cacid,
with the formula C9H12 were oxidised
● Hydrocarbon C or by hot potassium
gave benzene-1,2,4-trioic
ee hydrocarbons A, B and Suggest thethe
structures
Cmanganate(VII).
with formula C of9HA, B and C.
12 were oxidised by hot 35 potassium
C H5CO2H.C11H14.) acid:
nganate(VII). the molecular6formula
Answer HydrocarbonB Agave
●●Hydrocarbon gave benzoic acid, Compound
benzene-1,2-dioic ● Hydrocarbon
BCOmust
2H
containC gave twobenzene-1,2,4-trioic
side chains, since two carboxylic acid groups are
● Hydrocarbon C gave benzene-1,2,4-trioic
e aromatic A gave
Hydrocarbon
1
benzoic
Since A acid,
gave
C
acid:H
6 5 benzoic
CO 2H. acid, all three ‘extra’ carbon atoms
oxidation. must
acid:
What be
is in
more,
CO2 H
the same
the side
chains chain.be
must SoonA is:
adjacent carbons in the ring, as a
H5CO
Cll6be 2H.
produced ● Hydrocarbon B acid:benzene-1,2-dioic
gave 1,2-dicarboxylic acid is formed. So B is:
CH2CH2CH3 CO2 H CH(CH3 )2 CO2 H
pounds are B gave benzene-1,2-dioic
Hydrocarbon acid: CO2 H
CH3 CO2 H
acid:
m manganate(VII). CO2 H CO2 H
CO2 H or CH CH
isomers withCO2 2H CO2 H 2 3
1H14.)
Suggest the structures CO2 Hof A, B and C. CH3after
CO2 H Compound B must contain two side chains, since two carboxylic CO2 H acid groups are left
Answer
oxidation. CO H
What is more, the2chains must be on adjacent carbons in the ring, as a
CH3
or thethe
ggest A, BSince
structures of 1,2-dicarboxylic
aromatic and C. A gave acidbenzoic acid, all three
is formed. ‘extra’Bycarbon
So B is: similaratoms must beCinmust
reasoning, be: side chain. So A is:
the same
ch will be produced 3 AnswerCH3 CH2CH2CH3
ANSWER CH(CH3 )2
swer
compounds
for are
the aromatic Since A gave benzoic acid, all three ‘extra’ carbon atoms must be in the same side chain. So A is:
ce Awill
gave CH2CH must be in the same side chain. So A is:
assium
hich bebenzoic
producedacid, all three ‘extra’ carbon
manganate(VII). CH2CH
atoms
CH 3
CH(CH3 )2 CH3
2 3 or
are CH
gdscompounds CH2CH
isomers
2 with
are3
CH(CH3 )2
ula C11Hmanganate(VII). CH3
tassium 14.)
or
B must contain two side chains,CH
nds are isomers with or ACompound is: since two carboxylic acid groups are left after
430 By similar What isCmore,
reasoning,
oxidation. must the
3
be: chains must be on adjacent carbons in the ring, as a
mula C11H14.)
1,2-dicarboxylic
Compound B must acid contain
is formed. B is:
twoSoside chains, since two carboxylic acid groups are left after
mpound B must contain twooxidation. side chains, since is two carboxylic acid groups are left after
CHWhat
3
more, the chains must be on adjacent carbons in the ring, as a
dation. What is more, the chains must be on adjacent
1,2-dicarboxylic acid is formed. So BCH carbons in the
is:3 ring, as a
-dicarboxylic acid is formed. So B is: 430 CH2CH3
181333_25_A_Chem_BP_415-439.indd
CH3
CH3 B is:
CH2CH3 CH3
CH2CH3
CH3
By similar reasoning, C must be: CH3
CH3
CH3
CH3 C must be:
By similar reasoning,
similar reasoning, C must be: CH3 10/10/14 8:33 PM
C is:
CH3
CH3
36
430 10/10/14 8:33 PM
430 10/10/14 8:33 PM

10/10/14 8:33 PM

CO2 H
29 CO2 H
CO2 H
Now try this Answer
SKILL CHECK
Suggest structures for the aromatic
4 acid, all three ‘extra’ carbon atoms must be in the
Since A gave benzoic
carboxylic acids which will be produced CH CH CH
2 2 3
CH(CH3 )2
Suggest structures
when the following for the aromatic
compounds are carboxylic acids which will be produced when the
oxidised by
following hot potassium
compounds aremanganate(VII).
oxidised by hot potassium manganate(VII). (All these compounds
or
(All these compounds are isomers with
are isomers with the molecular formula C11H14.)
the molecular formula C11H14.)
Compound B must contain two side chains, since two carboxylic acid
1 oxidation. What is more, the chains must be on adjacent carbons in t
1,2-dicarboxylic acid is formed. So B is:
CH3
CH2CH3
2
CH3
CH3
By similar reasoning, C must be:
3
CH3
37
430
181333_25_A_Chem_BP_415-439.indd 430
REACTIONS OF SUBSTITUTED BENZENE RINGS

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.
Substituents on a benzene ring may be divided into two groups: those 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 orientation of the incoming group (NO2 or Br) depends on the substituent already in
the ring, and not on the electrophile.
38

30
If substitution were to occur at position 3, stabilisation of the positiv

charged intermediate is not possible by donation of the lone pair on th
O into the ring.
2,4-DIRECTING
If we look closely at the types of substituents that are 2,4-directing, we find that either
• they are capable of donating electrons to the ring by the inductive effect, or
ring more negative,
the reaction occurs m
• they have a lone pair of electrons on the atom joined to the ring. This lone pair can be
27 Amines, amides and amino acids
incorporated into the π system by sideways overlap of p orbitals.
Those amines that are soluble in water form weakly alkaline solutions, just as At first sight we migh
ammonia does, due to partial reaction with the solvent, producing OH− ions:
withdrawing due to t
CH3CH2NH2 + H2O CH3CH2NH3+ + OH− group also possesses a
The methyl group has an electron-releasing effect and this also stabilise
Table 27.3 lists some amines, with values of their dissociation equilibrium constants, pair into the ring a
Table 27.3 The basicity of some amines
theequilibrium:
Kb, for the following intermediate when substitution occurs at positions 2 and 4.
effect of the methyl group This π donation
from the in
Amine Formula Kb ORGANIC CHEMISTRY
/mol dm−3 R3N + H2O The R3NHelectron-releasing
+
+ OH− comes
+
[R NHoverlap
−
][OH ] of the electron density in the C–H bond with a p orbital on
effect (due to the elec
Kb = 3
phenylamine NH2 4.2 × 10−10 N]
[R 3adjacent atom (Figure G43).
Table 25.5 Orientation in some electrophilic donation of electro
Reaction Pe
substitution reactions
methylbenzene phenol
The larger Kb is, the stronger is the base. Ammonia is included for comparison. attract electrophile
ortho
ammonia NH3 1.8 × 10−5 The stabilising effect of the methyl group on the intermediate can b
From Table 27.3 we can see that electron-donating alkyl groups attached to the (1,2)
ethylamine CH3CH2NH2 5.1 × 10−4 shown
39
nitrogen atom increase the as:
basicity of amines. This is expected, since the basicity CH 3 CH 3 33
diethylamine (CH3CH2)2NH 1.0 × 10−3 depends on the availability of the lone pair of electrons on nitrogen to form a dative
+ Br Br
Examiner’s tip bond with a proton (see Figure 27.6). Electron donation from an alkyl group will
One2 particularly goo
encourage dative bond formation.
A summary of the explanations OH
reaction with OH
chlorin
50
is that
Figure 27.6 anWhen electron-releasing
an amine acts as a base, R R
Phenol reacts
+ HNO NO with
the nitrogen lone pair forms a dative bond with Phenol +is also made more reactive 3 2
group stabilises the

a proton. R N H R N + H 2,4,6-trichloropheno
in water since it is acidic and NO 2 NO
2 6
intermediate by electron R R
produces the phenoxide ion
donation into the ring. This −
+ HNO 3 NO 2
C 6H 5O . The negative charge

stabilisation is only possible The most dramatic difference in basicities to be seen in Table 27.3 is between that of CO H 2 CO H
2 19
phenylamine (Kb ≈ 10−10)on andthe O means
the alkyl amines (Kb withdrawal
≈ 10−3). Taking two compounds of
when substitution occurs about the same relative
AS&A2 molecular mass and shape, we see that phenylamine is about
27_06 Cam/Chem
2,4-DIRECTING isthan
reduced and donation is + HNO 3 NO 2
at positions
25
2, 4 and 6. An a million times less basic As for phenol, this
cyclohexylamine: stabilisation is only possible when substitution
Barking Dog Art
increased, therefore the Arenes ring and is phenols
electron-withdrawing group occurs at positions 2 or 4.
NH2 more attractive NHto electrophiles. The data in Table 25.5 can be interpreted
destabilises the intermediate 2
The orientation of the incoming group
25.4 Halogenoarenes
●
by withdrawing electron phenylamine cyclohexylamine

already in the ring, and not on the ele
We saw on pages 423–424 how bromobenzene and chlorobenzene can be made from H
●Some substituents favour both 2- and
density from the ring. ThisCl benzene.
–10 –4
K = 4.2 × 10
b K = 3.3 × 10b favour 3-substitution, at the expense o
The reactions of the ring in halogenobenzenes are similar to those of benzene. O
destabilisation is greatest Halogenoarenes undergo electrophilic substitution, and can be nitrated:

This is because in phenylamine, the lone pair of electrons on the nitrogen atom If is we look closely at the types of substi
when substitution occurs at up a planar Cl over the benzene ring. The bondsClaround the nitrogen atom can takeeither they
delocalised TheareNO capable group
2 of donatingis elec
el
arrangement, with the nitrogen’s lone pair in a p orbital, so that extrathey have a lone pair of electrons on th
positions 2, 4 and 6, thereforestability can be gained conc. HNO + conc. H SO
bond can
ring. With less electro
of be incorporated into the π system b
by overlapping this p orbital
25.12 with of the lone π
the delocalised
3 2 4
Figure 25.13 Delocalisation of the lone pair Figure Delocalisation pair

chlorobenzene the benzene ring (see Figure 27.7). in phenol
2,4-directing substituents
Figure 25.12).
strongly, therefore nit
substitution
in chlorobenzene
at position 3 is On the other hand, all those substitue
preferred.25_13 Cam/Chem AS&A2

NO2
26_12 Cam/Chem AS&A2
electron-withdrawing
joined directly to the ring (see Table 25.6
Figure 27.7 Delocalisation of the nitrogen
2- andin the group and, unl
However, unlike halogenoalkanes, halogenoarenes cannot be hydrolysed, even
Barking Dog Art Table 25.6 Substituents and their effects on 4-directing substituents
lone pair in phenylamine by boiling in aqueous sodium hydroxide. Thethe Barking Dog Art
carbon–halogen
benzene ring bond is stronger
in halogenoarenes than it is in halogenoalkanes, H possibly due to an overlap of p CH 3
ofAr electrons on the N
electrons similar to that in phenol (see Figure 25.13, and compare it with – Figure 25.12).
+
NH etc.delocalisation of the
In addition to this, the carbon attachedNto theorhalogen is not accessible
2 to the usual NH 2
nucleophilic reagents that attack halogenoalkanes, since its δ+ charge is shielded by the
H
negative π cloud of the ring. This means that halogenoarenes are inert to all nucleophiles.
•
•
H O Ar
Certain halogenoarenes find important uses as insecticides and herbicides (see the
panel below).
phenyl amine The position of subst
•
•
This overlap, causing a drift of electron density from nitrogen to the ring, has twoH2 N the
Ar
intermediate. The
effects on the reactivity
40 of phenylamine.
Organochlorine insecticides and herbicides be formed.
27_07 Cam/Chem
●Insecticides
It causes the lone pairAS&A2to be much less basic (see above) and also much less
nucleophilic.
Chlorobenzene
Barking Dogused
Artto be made in large quantities as an intermediate in the
This is most usuall
It causes of
●production thethering to be more
insecticide DDT: electron rich, and so to undergo electrophilic
CCl3 The enhanced reactivity of
but to understand the
substitution reactionsCl much more readily than benzene.
phenylamine in this regard is similar to that of phenol (see Topic 25, page 434), an about resonance.
CH
Cl
AlCl
2
CCl CHO
AlCl
3
453
Two possible Lewi
3 3
C1 C1 double bonds betwee

CEDAR COLLEGE
4,4!-dichlorodiphenyltrichloroethane
428 (DDT) ARENES resonance structures. T
Figure 25.14 453
181333_27_A_Chem_BP_449-468.indd Malaria is caused by a
microscopic parasite that is spread by the bite
The use of chlorinated insecticides is now banned in many countries. These
compounds are quite inert to biodegradation, so they stay in the environment
resonance hybrid o
09/10/14 1:39 AM
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, somewhere in betwee
they are insoluble in water, but soluble in fats and oils. They tend428to concentrate
181333_25_A_Chem_BP_415-439.indd
tion in some electrophilic Reaction Percentage of product Ratio
s (ortho + para)
ortho meta para
meta
(1,2) 31 (1,3) (1,4)
CH 3 CH 3 33 1 66 99 : 1
+ Br2 Br
3-DIRECTING
OH OH 50 1 49 99 : 1
On the other hand, all those substituents that favour 3-substitution have a δ+ atom joined
directly to the+ring.
HNO NO 2
3
NO 2 NO2 6 93.5 0.5 1 : 14
+ HNO 3 NO2
CO 2 H CO 2 H 19 80 1 1:4
+ HNO 3 NO 2
The data in Table 25.5 can be interpreted as follows.

● The orientation of the incoming group (NO41 2
or Br) depends on the substituent
already in the ring, and not on the electrophile.
H
● Some substituents favour both 2- and 4-substitution, whereas other substituents
O favour 3-substitution, at the expense of both 2- and 4-substitution.
If we look closely at the types of substituents that are 2,4-directing, we find that
either they are capable of donating electrons to the ring by the inductive effect, or
they have a lone pair of electrons on the atom joined to the ring. This lone pair
can be incorporated into the π system by sideways overlap of p orbitals (see
calisation of the lone pair
Figure 25.12).
tituents
On the other hand, all those substituents that favour 3-substitution have a δ+ atom
DIRECTING GROUPS
joined directly to the ring (see Table 25.6).
m AS&A2
uents and their effects on 2- and 4-directing substituents 3-directing substituents
CH 3 Ar O
N Ar
−
O
δ–
O
•
•
H O Ar δ+
C Ar
H
δ– δ+
N C Ar
•
•
H2 N Ar
δ–
O
δ+
C Ar
R
42

32
DIRECTING GROUPS
One explanation is that an electron-releasing group stabilises the 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.
43
DIRECTING GROUPS
An alternative way of explaining the directing This can also be shown using resonan
effect of substituent groups (not for examinations)
An alternative way of explaining isthe
in directing
terms of theeffect
chargeofdistribution
substituent groups
in the initial(not for
compound.
examinations) is in terms of the charge An electron-releasing
distribution group
in the initial will
compound.
increase the electron density at positions 2, 4 and
An electron-releasing group will 6increase
and therefore the electrophile
the electron is more
density attracted 2, 4 and 
at positions
to these positions. An electron-withdrawing group
6 and therefore the electrophile is more attracted to these positions.
withdraws electron density from positions 2, 4 and
6 and, therefore, there is more electron density at
An electron-withdrawing group withdraws electron density from positions 2, 4 and 6 and,
positions 3 and 5 and an electrophile is attracted to
therefore, there is more electronthese
density at positions 3 and 5 and an electrophile is
positions.
attracted to these positions.
– – + +
– +
44
Steric effects can also influence the position of substitution in a benzene

ring. On a purely statistical basis, for a 2,4-directing group, substitution
at position 2 should be twice as likely as substitution at position 4 as
CEDAR COLLEGE there are two position 2s but only one position 4. For nitration of methyl ARENES
benzene there is indeed greater substitution at position 2, but when the
much bulkier –C(CH3)3 group is attached to the benzene ring, nitration
c Nitrobenzene reacts with
a compound with the mo
33
d Compound X, shown be
Design a reaction pathwa
for the conversion of ben
SKILL CHECK 5
Compound X, shown below, can be formed from benzene in a two-step
reaction sequence. Design a reaction pathway showing all reagents and
conditions and the intermediate compound for the conversion of benzene to X.
45
RATE
2,4-directing groups usually cause substitution faster than benzene and 3-directing group
normally cause electrophilic substitution to occur more slowly than benzene (chlorine as a
substituent is an exception to this – it is a 2,4-directing group and chlorobenzene reacts
more slowly than benzene).
Substituents that cause substitution faster than with benzene are called activating groups
(2,4-directing groups except for chlorobenzene) and those that cause substitution to occur
more slowly than with benzene are called deactivating group (3-directing group).
46

34
RATE OF ELECTROPHILIC SUBSTITUTION

The rate-determining step in the reaction is the attack of the electrophile on 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.
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.
47
ORGANIC CHEMISTRY
Table 25.5 Orientation in some electrophilic Reaction Percentage of product

substitution reactions
PHENOL FASTER THAN BENZENE ortho

(1,2)
meta
(1,3)
para
(1,4)
CH 3 CH 3 33 1 66
At first sight we might expect the –OH group to be electron-withdrawing due to the high
+ Br 2 Br
electronegativity of O. However, the –OH group also possesses a lone pair of electrons
OH OH 50 1 49
and overlap of this lone pair into the ring activates the benzene ring. + HNO 3 NO 2
NO 2 NO2 6 93.5 0.
This π donation into the ring is a bigger effect than the electron withdrawing effect (due to
+ HNO 3 NO2
the electronegativity of O). ring more negative, i.e. more attractive towards electrophiles and
the reaction occurs more quickly than with benzene.
CO H CO H 2 2 19 80 1
Therefore there is net donation of electron density into the ring and the ring will attract
+ HNO 3 NO 2
electrophiles more strongly. At first sight we might expect the –OH group toThebedataelectron- in Table 25.5 can be interpreted as follows.
withdrawing due to the high electronegativity of● The O. However, the –OH
orientation of the incoming group (NO2 or Br) depen
group also possesses a lone pair of electrons and overlap of ring,
already in the thisandlone
not on the electrophile.
● Some substituents favour both 2- and 4-substitution, where
pair into the ring activates the benzene Hring (Figure G40).
favour 3-substitution, at the expense of both 2- and 4-subs
O
This π donation into the ring is a bigger effectIf we than the -withdrawing
look closely at the types of substituents that are 2,4-d
effect (due to the electronegativity of O). Therefore either there
they areiscapable
net of donating electrons to the ring by
donation of electron density into the ring they and have a lone pair of electrons on the atom joined to th
the ring will
can be incorporated into the π system by sideways overlap
Figure 25.12 Delocalisation of the lone pair
attract
48
electrophiles more strongly.
in 2,4-directing substituents
Figure 25.12).
On the other hand, all those substituents that favour 3-sub
joined directly to the ring (see Table 25.6).
26_12 Cam/Chem AS&A2
Table 25.6 Substituents and their effects on 2- and 4-directing substituents 3-directing subst
Barking Dog Art
One particularly the
good example
benzene ring of the ease of reactivity
CH Ar
of phenol is in its O
3
reaction with chlorine. N Ar

−
Phenol reacts with chlorine water – Cl2(aq) – to form O
Phenol is also made more reactive
2,4,6-trichlorophenol (no halogen carrier required): δ–
O
•
•
in water since it is acidic and H O Ar δ+

C Ar
CEDAR COLLEGE
produces the phenoxide ion ARENES H
C6H5O−. The negative charge δ–

N
δ+
C Ar
•
•
H2 N Ar
on the O means withdrawal δ–
O
is reduced and donation is δ+
3
heat with
CH 3CO2H conc. H 2SO 4
H 2O
ester not formed
35
Phenol can, however, be esterified by adding an acyl chloride:
OH O CH3
! CH3COCl
1NaOH C ! HCl
or pyridine
RING REACTIONS WITHO PHENOLS phenyl ethanoate
See section 26.3 for a fuller description of the conditions used for this reaction.
Phenols are more susceptible to electrophilic attack than benzene, owing to the
Substitution
delocalisation reactions
of the lone pair of the
of electrons benzene ring
on oxygen.
As we mentioned on page 428, phenols are more susceptible to electrophilic attack
than benzene, owing to the delocalisation of the lone pair of electrons on oxygen.
This allows phenol to react with reagents that are more dilute, and also to undergo multiple
This allows phenol to react with reagents that are more dilute, and also to undergo
substitution withsubstitution
multiple ease. with ease.
Nitration
When treated with dilute aqueous nitric acid (no sulfuric acid is needed) phenol gives a
When treated with dilute aqueous nitric acid (no sulfuric acid is needed) phenol gives
mixture ofa 2- and of4-nitrophenols.
mixture 2- and 4-nitrophenols:
OH OH OH
NO2
dilute HNO 3at room temperature
50% NO 2
50%
49
_BP_415-439.indd 434 10/10/14 8:33 PM
25 BROMINATION Arenes and phenols

Phenol decolorises a dilute solution of bromine in water at room temperature, giving a
Bromination
white precipitate of 2,4,6-tribromophenol.
Phenol Noofaluminium
decolorises a dilute solution
Bromination bromide
bromine in water is needed.
at room temperature, giving aContrast this
white precipitate of 2,4,6-tribromophenol. No aluminium bromide is needed. Contrast
with the conditions needed forconditions
this with the the bromination
Phenol decolorises of benzene.
a dilute solution of bromine
needed for the bromination
in water at room temperature, giving a
of benzene on page 423.
white precipitate of 2,4,6-tribromophenol. No aluminium bromide is needed. Contrast
OH the conditions needed for the
this with OHbromination of benzene on page 423.
OH Br OH Br
3Br2 (aq) Br Br 3HBr
3Br2 (aq) 3HBr
Br
Br chlorine water on phenol, is used in dilute
A similar product, formed by the action of
solution
A similar product, formed by the action436).
as the antiseptic TCP (see page
A similar product is formed by the action of chlorine water on phenol. of chlorine water on phenol, is used in dilute
solution
OHas the antiseptic TCP (see page
OH436).
OH Cl OH Cl
3Cl2(aq) Cl Cl 3HCl
3Cl2(aq) 3HCl
Cl
Cl
2,4,6-trichlorophenol
(TCP)
2,4,6-trichlorophenol
50(TCP)
Coupling
Coupling
Phenols couple with diazonium salts (see section 27.3) to form azo dyes:
Phenols couple with diazonium salts (see section 27.3) to form azo dyes:
OH
N
N1 N N OH
OH
aqueous NaOH at 5 8C
N1 1 OH 1
N N
(2H
aqueous ) at 5 8C
NaOH
1 N
(2H1)
CEDAR COLLEGE phenyldiazonium ion an azo dye
ARENES
phenyldiazonium ion an azo dye
A specific test for phenols
A specifi
When c testof for
a dilute solution phenols
iron(III) chloride is added to a dilute solution of a phenol,
a coloured complex is formed. The colour depends on the substituents on the ring.
36
Arenes and phenols
25.4 Halogenoarenes
CHLOROBENZENE
We saw on pages 423–424 how bromobenzene and chlorobenzene can be made from
Halogenoarenes
Cl undergo
benzene. The reactions electrophilic substitution,areand
of the ring in halogenobenzenes can
similar of benzene.25
be nitrated:
to those
Halogenoarenes undergo electrophilic substitution, and can be nitrated:
Cl Cl 25.4 Halogenoarenes
We saw on pages 423–424 how bromobenzen
Cl benzene. The reactions of the ring in halogeno
conc. HNO3 + conc. H2 SO4 Halogenoarenes undergo electrophilic sub
13 Delocalisation of the lone pair Cl
zene
conc. HNO3 + conc. H2 SO4
Figure 25.13 Delocalisation of the lone pair
NO2 in chlorobenzene
Cam/Chem AS&A2
However, unlike halogenoalkanes, halogenoarenes cannot be hydrolysed, even 25_13 Cam/Chem AS&A2
g Dog Art However, by

unlike
boilinghalogenoalkanes, halogenoarenes
in aqueous sodium hydroxide. cannot
The carbon–halogen bondbe hydrolysed, even by boiling
is stronger Barking Dog Art
However, unlike halogenoalkanes, halogenoa
by boiling in aqueous sodium hydroxide. The
in halogenoarenes than it is in halogenoalkan
in halogenoarenes
in aqueous than it is in
sodium hydroxide. halogenoalkanes,
The possibly due
carbon–halogen bondto anisoverlap of p in halogenoarenes
stronger electrons similar to that in phenol (see Figure
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 th
nucleophilic reagents that attack halogenoalkan
than it is in halogenoalkanes, dueattached
In addition to this, the carbon to antooverlap of ispnot
the halogen electrons similar
accessible to to that in phenol.
the usual negative π cloud of the ring. This means that h
nucleophilic reagents that attack halogenoalkanes, since its δ+ charge is shielded by the Certain halogenoarenes find important use
panel below).
negative
The p orbitals π cloud
from theofCl
theatom
ring. This
tendmeans
tothat halogenoarenes
overlap with theare delocalised
inert to all nucleophiles.
p electrons in the
Certain halogenoarenes find important uses as insecticides and herbicides (see the
benzene ring. This causes the C—Cl bond to be stronger, and hydrolysis does not occur.
panel below). Organochlorine insecticides an
Insecticides
Chlorobenzene used to be made in large qua
production of the insecticide DDT:
Cl
51
Organochlorine insecticides and herbicides Cl2
AlCl3
CCl3 CHO
AlCl3
Insecticides
Chlorobenzene used to be made in large quantities as an intermediate in the
Figure 25.14 Malaria is caused by a The use of chlorinated insecticides is now ba
production of the insecticide DDT: microscopic parasite that is spread by the bite compounds are quite inert to biodegradation
of the Anopheles mosquito. Malaria affects
CCl3 over 300 million people worldwide and kills
for many years. What is more, being non-hy
Cl around 3 million a year. DDT treatment of the they are insoluble in water, but soluble in fa
in the fatty tissue of animals, especially those
Anopheles mosquito saves millions of human
CH lives, so the environmental price is considered
worth paying.
prey were especially vulnerable. At one time
that they cracked during attempted incubatio
Cl2 CCl3 CHO
their populations. DDT may still be used in p
AlCl3 AlCl3 malaria mosquito, as the advantages to huma
disadvantages to the environment.
C1 C1 Herbicides
4,4!-dichlorodiphenyltrichloroethane The compounds 2,4-dichlorophenoxyethano
(DDT) 2,4,5-trichlorophenoxyethanoic acid (2,4,5-T)
years as selective weedkillers for broad-leave
ELECTROPHILIC SUBSTITUTION ON CHLOROBENZENE
.14 Malaria is caused by a The use of chlorinated insecticides is now banned in many countries. These
ic parasite that is spread by the bite compounds are quite inert to biodegradation, so they stay in the environment
narrow-leaved plants such as grass and cerea
weedkillers. Their action mimics that of the n
opheles mosquito. Malaria affects

for many years. What is more, being non-hydrogen-bonded covalent substances,
million people worldwide and kills
Chlorobenzene reacts with electrophiles more slowly than benzene does.
million a year. DDT treatment of the they are insoluble in water, but soluble in fats and oils. They tend to concentrate
The chlorine is a
mosquito saves millions of human in the fatty tissue of animals, especially those higher up the food chain. Birds of
deactivating group.
e environmental price is considered prey were especially vulnerable. At one time, the shells of their eggs were so thin
ing. that they cracked during attempted incubation, with disastrous consequences for
Chlorine istheir
more electronegative
populations. DDT may stillthan carbon,
be used and
in parts of soand
Africa pulls
Asiathe electrons
to control the in the ring towards
181333_25_A_Chem_BP_415-439.indd 431
malaria mosquito, as the advantages to human health are considered to outweigh the
itself.
disadvantages to the environment.
Herbicides
That makes the electron density around the ring rather less in chlorobenzene.
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
It becomes less attractive for electrophiles, and so the reaction is slower.
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
Halogenobenzenes areaction
weedkillers. Their deactivating,
mimics that ofyet
theare 2,4-directors.
natural (The exception
plant growth hormone indole to the rule).
431
52
5-439.indd 431 10/10/14 8:33 PM

37
SKILL CHECK 6
8 Give
Give the structure of the structure of the organic
organic products formedproducts formed
when the when molecules
following the are
following molecules are heated
heated with excess aqueous sodium hydroxide:  with excess aqueous sodium
hydroxide:
a b
e the formation of Organometallic compounds are organic molecules which also contain a
d reagents metal atom. More precisely, they contain
53 a bond between a carbon atom
quations for reactions of and a metal atom. These are useful in organic synthesis.
d reagents The most commonly used organometallic reagents are Grignard
reagents. These may be formed when a halogenoalkane is reacted with
magnesium turnings using a dry ether (usually ethoxyethane, (C2H5)2O)
ium compounds are also as the solvent.
used.
s pronounced as
The solvent must be dry as Grignard reagents react vigorously with

water.
The general equation for the formation of a Grignard reagent is:

dry ethoxyethane
ard reagent cannot be RX + Mg RMgX
m solution.
For example:
dry ethoxyethane
C2H5Br + Mg C2H5MgBr
ethylmagnesium
bromide
The structure of the Grignard reagent is shown in Figure G24. There is a

covalent bond between the Mg and the C and between the Mg and the Br.
C is significantly more electronegative than Mg and the Grignard
reagent acts in reactions as R−, that is, a negatively charged alkyl group.
The alkyl group is a nucleophile and will attack positive regions in a
molecule.
1 Reaction of Grignard reagents with water
d, however, be rather a An alkane is formed, e.g.
Grignard reagent!
C H MgI + H O C H + Mg(OH)I

8 Arenes Notes

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9

CEDAR COLLEGE ARENES

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

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

CEDAR COLLEGE ARENES

There are six spare

The six-centre In the

shaking with Br (aq) shaking with

25 Arenes and phenols

.3 Boiling points of some

propylbenzene C9H12 159

_415-439.indd 420 10/10/14 8:32 PM

CEDAR COLLEGE ARENES

Table 25.4 Orientations of substituents on Orientation Prefix Abbreviation Example

5-439.indd 421 10/10/14 8:32 PM

CEDAR COLLEGE ARENES

phenylethanoic acid 2,2-diphenylchloroethene

25.3 Reactions of arenes

Benzene therefore reacts with electrophiles.

Bromine water and aqueous acids have no effect on benzene.

In alkenes, an anion ‘adds on’ to the carbocation intermediate.

This demonstrates how stable the delocalised system is.

CEDAR COLLEGE ARENES

carbocation intermediate loses a proton, so as to re-form the ring of πelectrons. This

Alkenes react by electrophilic addition. Arenes react by electrophilic substitution.

CEDAR COLLEGE ARENES

Br Br Arenes and phenols

Figure 25.10 The four πelectrons are

The final stage regenerates the catalyst,

e 25.11 Three powerful explosives that CH3 OH

NO2 NO2 NO2

_Chem_BP_415-439.indd 426 ! ! H! 10/10/14 8:32 PM

CEDAR COLLEGE ARENES

2H2SO4 + HNO3 → H3O+ + NO2+ CH

CEDAR COLLEGE ARENES

when the C H bond breaks heterolytically. Both electrons Oxidation of th

CEDAR COLLEGE ARENES

2,4-directing groups usually cause substitution faster than benzene

he rate-determining reactions of reaction

Some of the electrophilic substitution reactions of methylbenzene are

CEDAR COLLEGE ARENES

CHLORINATION OF METHYL BENZENE

If methylbenzene is reacted with chlorine in the presence of UV

CHLORINATION OF METHYL BENZENE

CEDAR COLLEGE ARENES

In ethylbenzene, the hydrogen In atoms

> 90% > 90%

Worked example Worked example plus a termination step.

Three hydrocarbons A, B and C with

CEDAR COLLEGE ARENES

a carboxylate or carboxylic acid A

430 10/10/14 8:33 PM

430 10/10/14 8:33 PM

CEDAR COLLEGE ARENES

REACTIONS OF SUBSTITUTED BENZENE RINGS

CEDAR COLLEGE ARENES

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

group stabilises the

C 6H 5O . The negative charge

by withdrawing electron phenylamine cyclohexylamine

destabilisation is greatest Halogenoarenes undergo electrophilic substitution, and can be nitrated:

Figure 25.13 Delocalisation of the lone pair Figure Delocalisation pair