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Learning objectives
Reactions of alkenes
The C=C contains four electrons and is thus a region of very high
electron density. Electrophiles will be attracted to the electron density in
the double bond.
H
C
+ H
Br
heat
Br
bromoethane
HBr is polar, with the H+ and the Br. The H is thus attracted to the
high electron density in the C=C.
The mechanism is shown in Figure G1.
H
C
Br
C+
H
H
:Br
Br
In the first stage, a pair of electrons is donated from the C=C to form
a bond between C1 and the H of the HBr. At the same time the HBr
bond breaks the pair of electrons from the bond goes to the Br. This is
shown in terms of electrons in Figure G2.
C1
C2
H Br
electron from H
H
H C1 H
Br
H C2+
electron from C2
H
HL
H
HC H
H C Br
H
Figure G3 Electrons in the nal compound,
bromoethane.
pair of electrons
from HBr bond
goes to Br
Br
H
H
H
H
Br
Br
C
H
minor product
1-bromopropane
Br
major product
2-bromopropane
H
H3C
H
H
H
H
Cl
H3C
Cl
C
H
The two possible carbocations that can be formed when propene reacts
with HBr are:
H
C+
C+
primary
carbocation
secondary
carbocation
CH3
CH3
CH3
C+
C+
C+
primary carbocation
CH3
H3C
secondary carbocation
CH3
tertiary carbocation
Extension
The electron-releasing effect of the
alkyl group comes from the donation
of electron density from a CH or a
CC bond into the vacant p orbital
on the carbocation. This is called
-conjugation or hyperconjugation.
Examiners tip
When asked to explain which
is the major product when
HX adds to an alkene, always
explain it in terms of the
stability of the intermediate
carbocation it is never
enough to just say due to
Markovnikovs rule.
H
H
H
C
2
H
Cl+
Cl
Br
Br
major product
1-bromo-2-chloropropane
Br
Cl
minor product
2-bromo-1-chloropropane
Examiners tip
You only need to learn one of
these mechanisms.
H
H
+ Br2
non-polar
solvent
H
C
Br
Br
C+
H
Br
:Br
Br
Br
H
C
C
H
Br
H
Br
H
Br+
:Br
Br
Br
bromonium ion
Test yourself
1 State the names of the major products formed
when the following alkenes react with HCl:
a but-1-ene
b 3-methylbut-1-ene
c 2,4-dimethylpent-2-ene
Learning objectives
Like alkenes, aldehydes and ketones also contain a double bond and
undergo addition reactions. This time, however, the type of addition is
nucleophilic addition.
O
C
+ HCN
HCN(aq) + alkali
N
2-hydroxypropanenitrile
C
H
O
C
H
C
H + HCN
HCN(aq) + alkali
N
2-hydroxy-2-methylpropanenitrile
Mechanism
The C=O is polar with C+ and therefore attracts nucleophiles. The
reaction mixture will contain CN, either from the dissociation of HCN
or from the KCN. The CN ion has a lone pair of electrons on the C
(Figure G10) and this attacks the C+ of the carbonyl (C=O) group.
The mechanism for the nucleophilic addition of HCN to ethanal is
shown in Figure G11.
As the CN attacks, the second () component of the C=O bond
breaks and the pair of electrons goes to the O. This makes the O
CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011
[C
N [
C +
H
H
H+
H
H
Figure G11 The mechanism for the nucleophilic addition of HCN to ethanol.
negatively charged (it has one extra electron). The O then attracts H+
from the dissociation of HCN (or the acid that has been added).
The second step may also be shown as in Figure G12, where the H+ is
removed from the undissociated HCN.
H
H + CN
N + H2O + H3O+
H2O / H+ reflux
hydrolysis
O
CH3
+ NH4+
C
O
The same reaction occurs when the cyanohydrins formed above are
heated with acid:
H
H
H + H2O + H3O+
H
heat under reflux
H
H
H
O
H + NH4+
O
N
2-hydroxypropanoic acid
OH
H3C
C
CN
H + H2O + NaOH
H2O / OH reflux
hydrolysis
H3C
H + NH3
COONa+
Test yourself
3 Draw the structural formulae of the products
formed when the following carbonyl compounds
react with HCN:
a butanal
b 4-methylpentan-2-one
Examiners tip
Notes on drawing mechanisms:
1 Curly arrows show the movement of an electron pair and
not of anything else.
2 Be clear where the electron pair is moving from and where
it is going to. For instance, if OH is attacking, the curly
arrow should start from a lone pair on the O and not from
the H.
3 In most mechanisms the movement of electron pairs is such
that a bonding pair of electrons becomes a lone pair of
electrons or a lone pair of electrons becomes a bonding pair.
C +
H
X
O
C
O
C
X
G3 Elimination reactions
Learning objectives
Cl
CH3 H
H
C
H
C
H3C
+H
Cl
2-methylprop-1-ene
conc. H2SO4
H
C
heat
+ H2O
H
H
H
CH3 H
conc. H3PO4
heat
H
C
CH3 H
H + H2O
3-methylbut-1-ene
H
H
CH3 H
conc. H3PO4
heat
CH3 H
H + H2O
2-methylbut-2-ene
H
H
H
H+
O
C
H
H
H
C
O+
C
H
H
C
H
H
H+H
H
O
H
H
C
C
+ H+
H +
H reformed
H
Test yourself
6 Name the organic products formed when the following alcohols
undergo dehydration:
a butan-1-ol
b butan-2-ol
c 3-methypentan-1-ol.
G4 Additionelimination reactions
Learning objectives
N
N
NO2
Hydrazine is N2H4.
Phenylhydrazine is a molecule
of hydrazine where one H has
been replaced by a phenyl (C6H5,
benzene ring) group.
NO2
Figure G14 The structure of 2,4-DNPH.
H
C
H
H
H
H
N
N
N
N
NO2
+
C
C
H
NO2
H
+
H
NO2
NO2
propanone 2,4-dinitrophenylhydrazone
The structure of the product of the reaction can be worked out most
easily by putting the C=O group of the aldehyde/ketone next to the
NH2 group of the 2,4-DNPH. Water is then removed and the C=O
becomes C=N (Figure G16).
H
C
H
H
N
H
H
H
C
O
C
H
H
H
NO2
C
N
Water is eliminated.
C
H
NO2
Figure G16 Predicting the product of the reaction between 2,4-DNPH and propanone.
H
H
H
H
C
H
N
N
NO2
NO2
butanal 2,4-dinitrophenylhydrazone
Test yourself
7 Draw the structures of the organic products formed
when the following carbonyl compounds react with
2,4-dinitrophenylhydrazine:
a pentan-3-one
b 3-methylbutanal
Learning objectives
G5 Arenes
10
H
H
C
H
H
C
C
The ring of electrons is formed when p orbitals overlap side-on to form a HL Figure G20 Benzene ring showing all atoms.
delocalised system (Figure G21).
Compound
C=C
ethene
0.133
CC
ethane
0.154
CC
benzene
0.139
Bond length / nm
11
H = 120 kJ mol1
+ H2
cyclohexene
cyclohexane (C6H12)
H = 360 kJ mol1
+ 3H2
cyclohexa-1,3,5-triene
cyclohexane (C6H12)
H = 205 kJ mol1
+ 3H2
benzene
cyclohexane (C6H12)
Enthalpy
155 kJ mol1
H = 360 kJ mol1
H = 205 kJ mol1
cyclohexane
12
+ 2H2
cyclohexa-1,3-diene
cyclohexane (C6H12)
Cl
Kekul benzene
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Reactions of benzene
Cyclohexa-1,3,5-triene (Kekul benzene) would be expected to undergo
addition reactions (like all other alkenes) and to decolorise bromine water.
Benzene does not, however, react like alkenes, i.e. it does not undergo
addition reactions under normal conditions and will not decolorise
bromine water.
The extra stability associated with the ring of delocalised electrons
means that it is regenerated in reactions, therefore benzene undergoes
substitution reactions.
For example, benzene reacts with chlorine in the presence of a catalyst
such as aluminium chloride to form chlorobenzene, C6H5Cl:
Cl
+ Cl2
AlCl3
+ HCl
Examiners tip
The evidence for the structure
of benzene can be classified
as either chemical (enthalpy
changes of hydrogenation
and substitution reactions) or
physical (CC bond lengths,
number of isomers).
13
OH
NO2
OH
C
Cl
methylbenzene
phenol
nitrobenzene
chlorobenzene
OH H
NaOH(aq)
H + OH
heat
H + Cl
+ NaOH
H
C
H
Cl
NaOH(aq)
H
C
+ OH
heat
OH
+ Cl
H
Worked example
What is the organic product formed when the compound shown is
heated with excess aqueous sodium hydroxide solution?
H
Cl
Cl
Cl
14
Two of the chlorine atoms are attached directly to the benzene ring and will therefore not be substituted but the
third chlorine, which is in the side-chain, will be substituted by an OH.
H
Cl
H
attached directly
to benzene ring
NOT substituted
H
Cl
Cl
OH
OH
H + Cl
will be substituted
Cl
Cl
The reason that halogen atoms attached directly to the benzene ring are
not easily substituted is due to overlap of a lone pair of electrons on the
halogen atom with the delocalised system of the benzene ring.
HL
lone pair on CI
OH
nucleophile must
attack this C
Extension
Halogens atoms attached directly to a benzene ring can be substituted.
These reactions occur when there is another group (such as a nitro
group) also attached to the ring (at position 2 or 4) and strangely enough
the reaction occurs more quickly when it is a fluorine atom attached
to the ring rather than chlorine. This reaction occurs by a slightly
different mechanism than that discussed in Chapter 10, page 468 of the
Coursebook for nucleophilic substitution, and the rate-determining step
does not involve breaking the carbonhalogen bond. This suggests that
the explanation given here that it is the increased strength of the carbon
halogen bond that is responsible for the lack of substitution may not be
strictly accurate.
15
Test yourself
8 Give the structure of the organic products formed when the
following molecules are heated with excess aqueous sodium
hydroxide:
a
b ClH2C
CH2Cl
H H
C
Cl
Cl
Cl
G6 Organometallic chemistry
Learning objectives
Grignard is pronounced as
grin-yard.
ethoxyethane
For example:
dry ethoxyethane
C2H5Br + Mg C2H5MgBr
Mg
Br
16
dry ethoxyethane
RX + Mg RMgX
ethylmagnesium
bromide
C3H7MgBr + CO2
propylmagnesium
bromide
H+
C3H7MgBr
(i) CO2
(ii) H+ / H2O
O
C
O
Examiners tip
The mechanism is not required
for the examination.
C +
O
Mg
Br
O
C
C +
H
C2H5Mgl
(ii) H+ / H2O
H
H
H
H + Mg(OH)l
pentan-3-ol
17
Br
Mg H
H
C
H
(ii) H+ / H2O
+ Mg(OH)Br
butan-1-ol
Br
H
Mg H
H
H
H
(ii) H+ / H2O
H + Mg(OH)Br
H
3-methylhexan-3-ol
H H
H
Figure G25 The initial stage in the reaction of an ethyl Grignard with propanal. In
the reactions of Grignard reagents with CO2, aldehydes and ketones, the alkyl group
of the Grignard adds to the C of the C=O and the C=O is converted to an alcohol group.
tertiary alcohol
ketone
methanal
primary alcohol
Mg
halogenoalkane
Grignard reagent
ne
dr
tha
xye
o
h
t
ye
H2O
alkane
aldehyde
secondary alcohol
CO2
carboxylic acid
18
H
O
R2
R2
R1
R1
H
H
R2
R1
H
R1
C
C
R2
Br
(ii) H+/H2O
H
H
R2
Mg
dry ethoxyethane
R2
H
(ii) H+/H2O
(i)
H
H
H
R2
ketone
H
R1
O
H
R1 C
H aldehyde
H
H Mg
(ii) H /H2O
R2
R2
C
R2
R1 R2
H
secondary alcohol
R1 Br
R2
(ii) H+/H2O
H2O
C
H
H
R1 C
(i) CO2
H
C
methanal
R2
R1 Mg
primary alcohol
HBr
Markovnikovs rule
H
R1
Br
(i)
ne
electrophilic
addition
elimination mechanism
Mg
eth
oxy
eth
a
(i)
dry
H
R1 C
H tertiary alcohol
H
H
R1
elimination mechanism
elimination mechanism
H
H
H
H
R1
R2
Br
Figure G27 Reaction pathways for Grignard reagents and dehydration of alcohols.
Test yourself
9 Draw the structure of the final organic products
formed when CH3CH2CH2MgBr reacts with the
following compounds:
a CO2
b propanone
c CH3CH2CHO
19
G7 Reaction pathways
Learning objectives
Worked examples
Design a reaction pathway showing all reagents and conditions for the conversion of 1-bromobutane to
pentanoic acid.
The first thing we notice here is that the product has one more C atom than the starting material. This suggests
that a Grignard reagent must be used. The final product is also a carboxylic acid, therefore it can be formed by the
reaction between a Grignard reagent and carbon dioxide.
Br
H
H
Br
H + Mg
dry ethoxyethane
Mg
(i) CO2
(ii) H+ / H2O
O
C
+ Mg(OH)Br
O
H
HL
This synthesis could also have been brought about by reacting the halogenoalkane with CN (Chapter 10,
page 467 of the Coursebook) then hydrolysing the product by boiling with aqueous acid.
Design a reaction pathway showing all reagents and conditions for the conversion of molecule A to molecule B.
H
H
Br
H
C
A
20
H
H
H
H
The product of the reaction is a tertiary alcohol with more carbon atoms than the original starting material and is
therefore formed in the reaction between a Grignard reagent and a ketone.
If we highlight the carbon skeleton of the starting material in the final molecule we can see with which ketone we
need to react the Grignard reagent.
H
H
H
H
H
from ketone
from Grignard
reagent
Mg
H
H
+ Mg
(i)
dry ethoxyethane
H
H
H
H
(ii) H+ / H2O
+ Mg(OH)Br
Test yourself
11 Give reaction sequences for the following
transformations:
a chloroethane to propanoic acid
b ethanal to 2-hydroxypropanoic acid
c ethanal to butan-2-ol
Learning objectives
Acidity
O
R
C
O
H
+ H2O
C
O
+ H3O
carboxylate ion
21
Acid
change in acid strength. The pKa value for methanoic acid is approximately
one less than that for ethanoic acid and, therefore, methanoic acid is
roughly ten times stronger than ethanoic acid (Table G2).
pKa
methanoic acid
3.75
ethanoic acid
4.76
propanoic acid
4.87
butanoic acid
4.82
pentanoic acid
4.86
chloroethanoic acid
2.86
dichloroethanoic acid
1.29
trichloroethanoic acid
0.65
iodoethanoic acid
3.17
2-chlorobutanoic acid
2.84
3-chlorobutanoic acid
4.06
4-chlorobutanoic acid
4.52
The dissociation of ethanoic acid and chlorethanoic acid may be shown as:
phenol
10.00
ethanol
16
4-methylphenol
10.26
2,4,6-trinitrophenol
HL
O
R
C
O
H
C
0.42
Cl
C
H
+ H+
Cl
ethanoate ion
Cl
ethanoic acid
H
O
C
O
+ H+
chloroethanoic acid
chloroethanoate ion
O
C
The total negative charge in the anion is still 1 but it is spread out
more over the whole anion in the chloroethanoate ion rather than
being localised on the COO group.
Cl
O
Cl
trichloroethanoic acid
An electron-withdrawing effect
is sometimes called a negative
inductive effect.
22
Cl
O
C
+ H+
Cl
trichloroethanoate ion
Cl
Cl
Cl
O
C
H
O
O
C
iodoethanoic acid
iodoethanoate ion
O
C
O
H
O
methanoic acid
H
H
O
C
+ H+
H
O
ethanoic acid
methanoate ion
O
C
O
+ H+
H
ethanoate ion
23
Extension
Propanoic acid, butanoic acid
and pentanoic acid all have very
similar acid strengths because of the
mechanism by which alkyl groups
donate electrons. This arises because
of the overlap of electron density in
a bond (either CH or CC) with
a p orbital on an adjacent atom
-conjugation/hyperconjugation.
Beyond an ethyl group, the size of the alkyl group makes little
difference to the electron-releasing effect. Thus propanoic acid is slightly
stronger than ethanoic acid (the electron-releasing effect of an ethyl
group is slightly greater than that of a methyl group) but propanoic acid,
butanoic acid and pentanoic acid all have very similar acid strengths.
Cl
O
H
C
O
Cl
Cl
O
C
O
+ H+
2-chlorobutanoic acid
Cl
O
H
C
O
O
C
O
+ H+
4-chlorobutanoic acid
C6H5O + H+
+ H+
phenol
phenoxide ion
ethanol
O+ H+
ethoxide ion
electron density
donated into ring
lone pair on O
O
+ H+
CH3
CH3
4-methylphenol
4-methylphenoxide ion
O
O2N
NO2
O2N
NO2
+ H+
NO2
2,4,6-trinitrophenol
2,4,6-Trinitrophenol is such a
strong acid that its trivial name is
picric acid.
NO2
2,4,6-trinitrophenoxide ion
25
O
N
O
+
Extension
Some of the electron-withdrawing effect of the NO2 group also comes
from a effect where the p orbitals which make up the delocalised system
in the benzene ring overlap with the system of the NO2 group.
Basicity
A base (BrnstedLowry definition) is a proton acceptor. Thus, when a
base is put into water it accepts a proton from water:
B:+ H2O
HB+ + OH
The more the position of equilibrium lies to the right, the stronger the
base.
Methylamine reacts with water to form the methylammonium ion:
CH3NH2 + H2O
methylamine
CH3NH3+
methylammonium
ion
+ OH
pKb is used to quantify the strength of bases. The lower the value of pKb,
the stronger the base (Table G3).
Base
Formula
pKb
ammonia
NH3
4.75
methylamine
CH3NH2
3.36
dimethylamine
(CH3)2NH
3.28
trimethylamine
(CH3)3N
4.20
ethylamine
CH3CH2NH2
3.27
propylamine
CH3CH2CH2NH2
3.16
butylamine
CH3CH2CH2CH2NH2
3.39
phenylamine
C6H5NH2
9.38
26
H
H
H3C
H +
H 3C
H +
H+ ions will thus be attracted to the N and the lone pair of electrons
will be used to form a dative covalent bond to the H+. In general, the
greater the negative charge on the N the more it will attract H+ ions and
the stronger base it will be.
CH3 is an electron-releasing group (positive inductive effect) and
so will push electron density onto the N, making it more negative and
therefore more likely to attract H+. Methylamine is thus a stronger base
than ammonia (Figure G33).
Similarly, dimethylamine is a stronger base than methylamine as it has
two electron-releasing alkyl groups which donate electrons to the N
making it even more negative (Figure G34).
It would therefore be expected that trimethylamine would be a
stronger base than dimethylamine. However, although it is a stronger base
than ammonia it is a weaker base than methylamine and dimethylamine.
This is due to greater stabilisation of the protonated form by hydrogen
bonding with water (the solvent) in the dimethylammonium ion than in
the trimethylammonium ion. There are two H atoms that can hydrogen
bond to water in the dimethylammonium ion but only one in the
trimethylammonium ion (Figure G35). The protonated form is thus
stabilised to a greater extent for dimethylamine than for trimethylamine
and this outweighs the extra electron-releasing effect of the extra alkyl
group. This means that the protonated form is more likely to be formed
for dimethylamine and it is therefore ionised to a greater extent and a
stronger base.
H +
Figure G33 Methylamine.
H3C
+
CH3
Figure G34 Dimethylamine.
O
H +
CH3
N+
H
+
CH3
O
H
O
H +
CH3
N+
CH3
CH3
C6H5NH3+
phenylammonium
ion
+ OH
This is because of the overlap of the lone pair on the N with the benzene
delocalised system, which makes the lone pair less available for donation
to H+.
Formation of salts
Amines, like ammonia, form salts with acids, e.g.
NH3 + HCl NH4+Cl
ammonium
chloride
27
Test yourself
13 Arrange the following in order of acid strength (weakest first):
phenol
propanoic acid
2-chloropropanoic acid
2,2-dichloropropanoic acid
ethanol
2,2-difluoropropanoic acid
3-chloropropanoic acid
2-methylphenol
Learning objectives
HL
G9 Additionelimination reactions
Acyl chlorides (acid chlorides)
The basic structure of an acyl chloride is:
O
R
C
Cl
O
C
Cl
O
H
CH3 H
O
C
Cl
H
ethanoyl chloride
butanoyl chloride
Cl
3-methylbutanoyl chloride
acyl group
+
Cl
28
O
H
O
H
O
C
ethanoyl chloride
ethanoic acid
+ H
Cl
In all the reactions we will meet the acyl group will be added to the
most electronegative atom of the nucleophile (N or O) and H (from
the nucleophile) and Cl (from the acyl chloride) will be eliminated
(Figure G36).
2 Reaction with alcohols
Acyl chlorides react with alcohols to form esters.
H
+ O
O
C
HL
H
Cl H
HCl eliminated
H + H
Cl
Cl
H
butanoyl chloride
ethyl butanoate
O
O
OH
Cl
+ H
Cl
phenyl benzoate
O
C
Cl
+
H
H
H
O
C
+ H
Cl
NH2
propanamide
O
C
+
Cl
H
H
+ H
Cl
ethylamine
N-ethylpropanamide
29
HL
C +
H
Cl
Cl
+ Cl
X
C +
H
Cl
H+
O+
H
H
H+
Cl
H
H
O
H
O
H
Cl
+ Cl
O
H
H
The second stage could also have been shown more simply as loss of a
proton (H+):
O+
H
Cl
Cl
+ H+
C +
H
Cl
H+
H +
H+
Cl
H H N+
H
H
N
H
N
H
Cl
H
H
+ Cl
N
N+ H
H
H
Acid anhydrides
The basic structure of an acid anhydride is:
O
R
O
O
30
H
H
O
C
H
O
H3C
CH3CH2
H3C
ethanoic anhydride
O
H3C
O
H
O
C
propanoic anhydride
C
O +
C
H
Mixed anhydrides are also possible and they would be named as, e.g.
ethanoic propanoic anhydride.
Like acyl chlorides, acid anhydrides are acylating agents they react
by adding the acyl group to other species. This time it is a molecule of
carboxylic acid that is eliminated.
The reactions of acid anhydrides are basically the same as those of acyl
chlorides.
1 Reaction with water
Acid anhydrides react when warmed with water to form carboxylic
acids:
H3C
CH3CH2
O
H
H
H
ethanoic anhydride
+ H
O
O
H
O
C
O
ethanoic acid
ethanoic acid
CH3CH2
O + O
H + H
ethyl propanoate
propanoic anhydride
O
O
H3C
H3C
C
O +
propanoic acid
O
C
C
O
C
O
C
H
H
+H
O
C
O O
aspirin
ethanoic acid
31
CH3CH2
CH3CH2
O +
H
O
H
H
O
C
NH2
+ H
propanamide
propanoic anhydride
O
C
O
propanoic acid
CH3CH2
O +
H
O
propanoic anhydride
ethylamine
ethanamine
+ H
N-ethylpropanamide
O
C
O
propanoic acid
C
O
OH
+H
ethanoic
anhydride
C
H
O
H3C
O
C
O
ethanoic acid
paracetamol
Test yourself
14 All the following compounds can be made in a single step
using either an acyl chloride or an acid anhydride. Give the
names of two compounds from which each of the following
compounds could be made:
a butyl ethanoate
b pentanamide
c N-ethylbutanamide
32
X+
X + H+
HL
Learning objectives
electrophile
X
H
Figure G38 Partial delocalisation in the intermediate in an electrophilic substitution
reaction.
In the second step the CH bond breaks. This releases an orbital and a
pair of electrons to complete the delocalised system again.
+ HNO3
NO2
conc. HNO3
conc. H2SO4
heat under reflux
60C
C6H6 + HNO3
+ H2O
nitrobenzene
C6H5NO2 + H2O
33
HL
electrophile
NO2
H
NO2 + H+
The second stage may also be shown slightly differently with the
HSO4 ion (formed when the electrophile was formed) removing the H+
ion. The H2SO4 is thus re-formed and can be regarded as a catalyst in this
reaction.
NO2
H
H
O
NO2 + H2SO4
S
O
Chlorination of benzene
The overall equation for the reaction between benzene and chlorine is:
C6H6 + Cl2 C6H5Cl + HCl
The reaction must be carried out in the absence of direct sunlight;
otherwise a free-radical reaction can occur to produce C6H6Cl6.
For bromination, iron or pyridine
could be used.
Benzene does not react with halogens in the dark because the halogen
molecule is non-polar and not a sufficiently strong electrophile. Therefore
a catalyst is required which polarises the molecule. The catalysts used are
AlCl3 or iron (forms FeCl3); these are known as halogen carriers.
Extension
Actually it is unlikely that Cl+ is actually formed in the reaction mixture
and it is more likely that the Cl2 is just very polarised by coordination to
the AlCl3.
Cl
Cl
34
Cl
Al
Cl
Cl
Cl
H
electrophile
Cl + H+
The second step can also be shown with the [AlCl4] removing the
proton to reform the catalyst.
+
Cl
H
HL
Cl + HCl + AlCl3
catalyst re-formed
Cl
Cl
Al
Cl
Cl
CH3
CH3
C
+ H3C
CH3
AlCl3
5 C
+ HCl
Cl
(1,1-dimethylethyl)benzene
CH3
+C
CH3
C
H
CH3
CH3
CH3
CH3
CH3 + H+
CH3
electrophile
Again, the second step could be shown with [AlCl4] removing the H+
to reform the catalyst.
CH3
+
C
H
CH3
CH3
CH3
C
Cl
Cl
Al
CH3
Cl
Cl
35
HL
H
H
+H
AlCl3
50
C
Cl
O
C
H
+ HCl
phenylethanone
O
+C
C
H
O
C
CH3
+ H+
CH3
CH3
electrophile
Again, the second step could be shown with [AlCl4] removing the H+
to reform the catalyst.
Reactions of methylbenzene
Methylbenzene reacts in the same way as benzene, via an electrophilicsubstitution mechanism. The conditions for the reactions of
methylbenzene are slightly milder than those for the reactions of benzene
as the methyl group is an activating group. The methyl group donates
electron density into the benzene ring (positive inductive effect). This
increases the amount of electron density in the ring so that it is more
attractive to electrophiles and reacts more readily.
The methyl group is a 2,4-directing group and so the major products
of substitution are:
CH3
CH3
X
36
CH3
O
C
HL
CH3
CH3
H
H3C
O
C
H
O
Cl
H
AlCl3
CH3
CH3
CH3
conc. HNO3
conc. H2SO4
NO2
AlCl3
C2H5Cl
Cl2
NO2
AlCl3
CH3
CH3
Cl
CH3
CH3
CH2CH3
Cl
CH2CH3
Figure G39 Electrophilic substitution reactions of methylbenzene.
Chlorination of methylbenzene
If methylbenzene is reacted with chlorine in the presence of a halogen
carrier catalyst (AlCl3) at room temperature 2-chloromethylbenzene and
4-chloromethylbenzene are formed. This is chlorination in the ring.
CH3
CH3
CH3
Cl
Cl2
AlCl3
2-chloromethylbenzene
+ HCl
Cl
4-chloromethylbenzene
H
H
H
Cl2
UV
Cl
Examiners tip
The mechanism here is as for
alkanes (see Chapter 10, page 434
of the Coursebook) and can be
summarised as
UV
Cl2
2Cl
+ HCl
(chloromethyl)benzene
37
HL
H
H
Cl
H
Cl
Cl
Cl
Cl
Cl2
Cl2
Cl2
UV
UV
UV
(chloromethyl)
benzene
(dichloromethyl)
benzene
Cl
(trichloromethyl)
benzene
Cl
Cl
Cl2
UV
CH3
NO2
CH3
NO2
1,2-dimethylbenzene
1,3-dinitrobenzene
CH3
1,4-dimethylbenzene
When the groups are different, various ways of naming the compound
are usually accepted. The IUPAC system involves giving the substituent
that comes first in the alphabet the number 1 and numbering other
substituents relative to that. The numbers are chosen to give the lowest
possible numbers. Some examples are shown in Table G4. Commonly
used alternative names are also given in the table. Derivatives of phenol
are named so that the OH group of the phenol is counted as position 1.
Cl
OH
CH3
CH3
NO2
Cl
2-chloromethylbenzene
2-nitromethylbenzene
2-methylchlorobenzene
2-methylnitrobenzene
4-chlorophenol
38
HL
Rate of 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.
Thus methylbenzene reacts more readily than benzene due to the
electron-releasing effect of the CH3 group (positive inductive
effect). The methyl group activates the ring towards electrophilic
substitution by donating electron density into the ring. This makes the
Substituent
CH3
and other alkyl
group
CH3
OH
OH
CH3
Rate of substitution
relative to benzene
faster
faster
slower
Cl
Cl
OH
Cl
OH
Cl
Cl
NO2
CH3
NO2
Cl
Cl
Cl
Table G5 Reactions of substituted benzene rings.
39
C
C
C
C
O
donation
into ring
At first sight we might expect the OH group to be electronwithdrawing due to the high electronegativity of O. However, the OH
group also possesses a lone pair of electrons and overlap of this lone
pair into the ring activates the benzene ring (Figure G40).
This donation into the ring is a bigger effect than the -withdrawing
effect (due to the electronegativity of O). Therefore there is net
donation of electron density into the ring and the ring will
attract electrophiles more strongly.
OH
Cl
Cl
+ 3Cl2
+ 3HCl
Cl
2,4,6-trichlorophenol
substitution
at position 2
X
H
O
+
X+
N
X
H
X
H
2 positive charges
next to each other
curly arrows represent delocalisation of electrons
+
+
X+
2 positive charges
next to each other
substitution
at position 4
X+
N
+
X
H
N
+
X
H
X
H
substitution
at position 3
O+
X+
substitution
at position 2
X
H
X
H
intermediate stabilised
by donation of lone pair
into ring
41
HL
O+
+
X+
substitution
at position 4
intermediate stabilised
by donation of lone pair
into ring
X
H
substitution
at position 3
C
C
donation
into ring
H
H
C
C
Examiners tip
A summary of the explanations
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.
42
C
X+
substitution
at position 2
X
H
intermediate stabilised by
donation of electrons into ring
O+
O
N
electron-withdrawing
group
electrophile
more attracted
electrophile
more attracted
Steric effects
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
there are two position 2s but only one position 4. For nitration of methyl
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
results in over four times more of the 4-substituted product. The bulky
C(CH3)3 group blocks the approach of the electrophile to position 2 (or
6) more effectively than the CH3 group.
Acylation of methylbenzene usually results in a very high proportion
of the 4-substituted product. The can be also explained by steric effects,
where the methyl group hinders the approach of the electrophile to
positions 2 or 6.
Test yourself
15 Name the following molecules:
OH
CH3
Cl
NO2
43
HL
Learning objectives
NaOH(aq)
heat
CH3
CH3
CH3
O
H
CH2Cl
CH2MgCl
Cl
no reaction
NaOH(aq)
Cl2
Cl2
Mg
(i) CO2
heat
AlCl3
UV light
dry ethoxyethane
(ii) H+ / H2O
Cl
CH3Cl
Cl
NO2
Cl2
AlCl3
AlCl3
CH3Cl
H
H
H
base
H
H
NO2
conc. HNO3
conc. H2SO4
CH3
H
H
AlCl3
H2O
Cl
H
cold
NH2
AlCl3
NH3
cold
conc. NH3(aq)
O
C
Cl
H
H
H
AlCl3
OH
O
O
O
C
NH2
44
Worked examples
Design a reaction pathway showing all reagents and conditions
for the conversion of benzene to 1-methyl-2-nitrobenzene.
1-methyl-2-nitrobenzene is also
called 2-nitromethylbenzene.
The molecule has one group substituted at position 2 relative to the other, therefore the methyl group must be put
on the ring first as it is a 2,4-directing group.
CH3
CH3Cl
conc. HNO3
conc. H2SO4
AlCl3
CH3
NO2
Design a reaction pathway showing all reagents and conditions for the conversion of benzene to
3-nitromethylbenzene.
This time the groups are 1,3 relative to each other and therefore the nitro group must go on first as it is a
3-directing group.
NO2
conc. HNO3
conc. H2SO4
NO2
CH3Cl
AlCl3
CH3
Design a reaction pathway showing all reagents and conditions for the conversion of ethane to ethylbenzene.
Ethane is not very reactive and must be converted to something else before it can be reacted with benzene. The
only reaction that allows us to convert it to something more reactive is free-radical substitution with chlorine in
the presence of UV light. The chloroethane produced can then be reacted with benzene in the presence of an
AlCl3 catalyst.
H
Cl2
UV light
H
Cl
AlCl3
45
Exam-style questions
1 a Draw the full structural formula of 2-methylpent-2-ene.
b
i Draw the full structural formula of the major product formed when 2-methylpent-2-ene reacts with
hydrogen bromide in the dark.
ii Write the mechanism for this reaction and explain the formation of the major product.
c 2-methylpent-2-ene can be formed when an alcohol is heated with concentrated phosphoric acid.
i Name the type of reaction that occurs.
ii Give the structures of two possible alcohols that would produce 2-methylpent-2-ene via this reaction.
iii In each case another alkene will also be formed in the reaction. For each of the alcohols in part ii
draw the structure of the other alkene formed.
iv Describe using curly arrows the mechanism for the formation of 2-methylpent-2-ene from one of the
alcohols in part ii.
v One of the alcohols in part ii can be formed from the reaction between a Grignard reagent and
a ketone. Draw the structure of the Grignard reagent and the ketone that could be reacted together.
[1]
[1]
[5]
[1]
[2]
[2]
[4]
[2]
2 A laboratory test for the presence of a carbonyl group involves reaction with 2,4-dinitrophenylhydrazine.
a Draw the structure of 2,4-dinitrophenylhydrazine.
[1]
b Write an equation using structural formulae for the reaction between 2,4-dinitrophenylhydrazine
and ethanal.
[2]
[1]
[4]
[2]
[4]
[1]
[3]
[2]
[2]
[3]
[2]
46
a State the reagents and conditions for the conversion of 2-chloropropane to a Grignard reagent.
[2]
[1]
c The Grignard reagent formed from 2-chloropropane reacts under appropriate conditions with
carbon dioxide. Draw the full structural formula of the final product of this reaction.
[1]
d Complete the following equation by drawing the structure of the organic product formed.
(i) H
C2H5Mgl
[1]
H
+
(ii) H / H2O
HL 6 Ethanoyl chloride and ethanoic anhydride react in the same way with nucleophiles.
[1]
[1]
[2]
[1]
[4]
[2]
O
C
i Write an equation, showing all reagents and conditions for the formation of this compound
from benzene.
ii Draw the mechanism for the reaction in part i.
[2]
[3]
b Explain why phenol reacts more rapidly with chlorine than benzene does.
[2]
c Nitrobenzene reacts with a mixture of concentrated sulfuric and concentrated nitric acid to form
a compound with the molecular formula C6H4N2O4. Draw the structural formula of the product.
[1]
d 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.
[4]
CH3
H3C
CH3
X
NO2
47