Cambridge University Pressorganic Chemistry PDF

G Further organic chemistry
G1 Electrophilic addition reactions Learning objectives
Reactions of alkenes • Explain the electrophilic

addition reactions of alkenes
Most reactions of alkenes involve an electrophilic addition mechanism. • Predict and explain the
formation of the major product
An electrophile is a reagent (a positively charged ion or the when HX reacts with an
positive end of a dipole) which is attracted to regions of high unsymmetrical alkene
electron density and accepts a pair of electrons to form a covalent
bond.
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.
The reaction of ethene with hydrogen bromide

The overall equation is:
H H
H H
heat
C C + H Br H C C H
H H
H Br
bromoethane
H–Br is polar, with the Hδ+ and the Brδ−. The H is thus attracted to the
high electron density in the C=C.
The mechanism is shown in Figure G1.
H H H H
C H C H H C H
δ+ δ– The curly arrow represents
H Br
movement of two electrons.
C H C+ :Br– H C Br
H H
H H
Figure G1 The mechanism of the reaction of ethene with hydrogen bromide.
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 H–Br. At the same time the H–Br
bond breaks – the pair of electrons from the bond goes to the Br. This is
shown in terms of electrons in Figure G2.
pair of electrons from double bond electron from H

HL
H The π bond breaks.
H
H
C1 H C1 H
H Br Br–
C2 H C2+
H electron from C2
H
H
this C has lost an electron therefore

positively charged
Figure G2 Movement of electrons in reaction of ethene with hydrogen bromide.
CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 G FURTHER ORGANIC CHEMISTRY 1
H C2 has lost an electron (this electron is now in the C–H bond) and
HC H thus C2 has a positive charge. The intermediate formed is called a
carbocation (a positively charged organic ion with a positive charge
H C Br
on C). The Br atom has gained an electron from the H–Br bond and is
H
therefore a negatively charged bromide ion. In the second stage the Br−
Figure G3 Electrons in the final compound,
bromoethane. ion is attracted to the C+ and donates a pair of electrons to form a bond.
The electrons in the final compound are shown in Figure G3.
The initial type of bond breaking, when the H–Br bond breaks, is
pair of electrons
from H–Br bond called heterolytic fission since the bond breaks so that both electrons
goes to Br go to the same atom (Figure G4).
H Br
The reaction of propene with HBr
Figure G4 Heterolytic fission.
When HBr adds to propene, two products are possible:
H C H
H H C H minor product
1-bromopropane
H C H H C Br
H C H Br H
C H
H H
H C H
H Br major product
C
2-bromopropane
H C H
The main/major product (the minor product is usually only present in

very small amounts) may be predicted from Markovnikov’s rule:
When H–X adds to the double bond of an alkene, the H atom

becomes attached to the C atom that has the larger number of H
atoms already attached.
Markovnikov’s rule can be used to predict the major product formed

when H–X adds to any unsymmetrical alkene. Thus, when H–Cl adds to
2-methylpropene, the H atom of the HCl becomes attached to C1 as this
‘Those who have shall get more.’ has two H atoms already attached, rather than C2, which has no H atoms
attached.
H H
H C H H C H
2
H Cl 2
H3C C H3C C Cl
1 1
C H C H
H H
H
The explanation for Markovnikov’s rule depends on the stability of

the intermediate carbocation.
2 G FURTHER ORGANIC CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011
The two possible carbocations that can be formed when propene reacts
with H–Br are:
H H
A primary carbocation has one C
H C H H C H
atom attached to the C bearing the
H C H H C+ positive charge.
A secondary carbocation has
H C+ H C H
two C atoms attached to the C
H H bearing the positive charge.
primary secondary
carbocation carbocation
The secondary carbocation is more stable than the primary carbocation.

This is due to the electron-releasing effect of alkyl groups. There are Alkyl groups have an electron-
two alkyl groups next to the positively charged C in the secondary releasing effect. This is also called a
carbocation but only one in the primary carbocation. Two alkyl groups positive inductive effect.
reduce the positive charge on the C more than one alkyl group and thus
stabilise the ion more. Since the secondary carbocation is more stable, it is Extension
more likely to be formed. The electron-releasing effect of the
alkyl group comes from the donation
The electron-releasing effect is roughly independent of the size of electron density from a C–H or a
of the alkyl group, i.e. a methyl group donates approximately the C–C bond into the vacant p orbital
same amount of electron density as an ethyl group. on the carbocation. This is called
σ-conjugation or hyperconjugation.
In general, the more alkyl groups there are attached to C+, the more
stable the carbocation (Figure G5).
Examiner’s tip
CH3 CH3 CH3 When asked to explain which
is the major product when
C+ C+ C+
HX adds to an alkene, always
H H H CH3 H3C CH3
explain it in terms of the
primary carbocation secondary carbocation tertiary carbocation
stability of the intermediate
increasing stability of carbocation
carbocation – it is never
Figure G5 Stability of carbocations. enough to just say ‘due to
Markovnikov’s rule may also be used to explain the products Markovnikov’s rule.’
obtained when interhalogen compounds react with propene (or other
unsymmetrical alkenes). The less electronegative halogen atom behaves
like H and, in the major product, becomes attached to the C that has
more H atoms attached.
For example, the reaction of Br–Cl with propene:
H
H C H
H C Cl major product
H 1-bromo-2-chloropropane
H C Br
H C H
2 Clδ+ Brδ– H
H C
H
1
C
H H H C H
H Br minor product
C
2-bromo-1-chloropropane
H C Cl
Br is less electronegative than Cl and becomes attached to C1, which
has two H atoms already attached, rather than C2, which only has one H
atom already attached.
Reaction of ethene with bromine

Br Br
H H non-polar
C C + Br2 solvent
H C C H
H H
H H
Although the bromine is not originally polar, as it approaches the high

electron density in the C=C it becomes polarised (there is an induced
dipole). The electrons are repelled in the Br2 molecule so that the Br
closest to the C=C has a slight positive charge and the Br further away has
a slight negative charge.
Examiner’s tip The mechanism can be shown in two different ways. The first is exactly
You only need to learn one of analogous to the reaction of H–Br with ethene, i.e. via a carbocation
these mechanisms. intermediate (Figure G6).
H H H H
C δ+ δ–
H C Br H C Br
Br Br
C H C+ :Br– H C Br
H H
H H
Figure G6 The reaction of ethene with bromine.
The mechanism is, however, probably better represented as shown in

Figure G7, where a bromonium ion rather than a carbocation is formed.
H H H H
In the bromonium ion the
bridging Br has donated a lone pair C H C H C Br
to the C+, which stabilises the ion. δ+ δ–
Br Br Br+
C H C H C Br
:Br–
H H
H H
bromonium ion
Figure G7 The reaction of ethene with bromine showing the formation of a

bromonium ion.
Test yourself
1 State the names of the major products formed 2 State the name of the major product formed when
when the following alkenes react with HCl: but-1-ene reacts with ClBr.
a but-1-ene
b 3-methylbut-1-ene
c 2,4-dimethylpent-2-ene
G2 Nucleophilic addition reactions Learning objectives
Like alkenes, aldehydes and ketones also contain a double bond and
undergo addition reactions. This time, however, the type of addition is
• Describe and explain the
nucleophilic addition reactions
nucleophilic addition. of aldehydes and ketones with
HCN
Reaction with hydrogen cyanide
• Write equations for the
The reaction of ethanal with hydrogen cyanide is shown in Figure G8. hydrolysis of cyanohydrins
Just as with the reaction of alkenes, the second component of the double
bond (π component) is broken and the H–CN is added across it; H adds
to the O.
H
H O H O This reaction is important as it
HCN(aq) + alkali introduces an extra C atom into
H C C + HCN H C C H
the carbon chain.
H H H C
N
2-hydroxypropanenitrile
Figure G8 The reaction of ethanal with hydrogen cyanide.
The product of the reaction is called a cyanohydrin.
The reaction is generally speeded up by addition of a small amount of

alkali, which promotes formation of CN−, the nucleophile (HCN is a
very weak acid and, therefore only a very small concentration of CN− is
present in solution). In the laboratory it is much more convenient to use
KCN and add an acid instead of using the dangerous HCN.
The reaction occurs with both aldehydes and ketones. The reaction of
propanone with HCN is shown in Figure G9.
H O H H O H
HCN(aq) + alkali
H C C C H + HCN H C C C H
H H H C H
N
2-hydroxy-2-methylpropanenitrile
Figure G9 The reaction of propanone with HCN.
Mechanism
The C=O is polar with Cδ+ 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 [C N [–
(Figure G10) and this attacks the Cδ+ of the carbonyl (C=O) group. Figure G10 The electrons of the CN− ion.
The mechanism for the nucleophilic addition of HCN to ethanal is
shown in Figure G11.
As the CN− attacks, the second (π) component of the C=O bond
breaks and the pair of electrons goes to the O. This makes the O
H+ from dissociation of HCN
H+ H
δ– –
H O H O H O
H C C δ+ H C C H H C C H
H
H –
C N H C H C
N N
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 C N H
–
H O H O
H C C H H C C H + CN–
H C H C
N N
Figure G12 H+ is removed from the undissociated HCN.
Hydrolysis – breaking a bond with

Nitrile groups may be hydrolysed to form a
water. carboxylic acid
If a nitrile is boiled with aqueous acid it is converted into a carboxylic
acid. The balanced equation for the reaction of ethanenitrile with acid is:
H2O / H+ reflux
O
CH3 C N + H2O + H3O+ CH3 C + NH4+
hydrolysis
O H
The same reaction occurs when the cyanohydrins formed above are
heated with acid:
H H
H O H O
heat under reflux
H C C H + H2O + H3O+ H C C H + NH4+
H C H C
H O O
N
2-hydroxypropanoic acid
Hydrolysis can also be brought about by refluxing with aqueous alkali.

In this case the product is the salt of the acid and ammonia:
OH OH
–
H2O / OH reflux
H3C C H + H2O + NaOH H3C C H + NH3
hydrolysis
CN COO–Na+
Test yourself
3 Draw the structural formulae of the products 4 Draw the structural formulae of the products
formed when the following carbonyl compounds formed when each of the products formed in
react with HCN: Question 3 is boiled with aqueous acid.
a butanal 5 Write balanced chemical equations using
b 4-methylpentan-2-one condensed structural formulae to show the
reaction of propanal with HCN followed by
boiling the product with aqueous acid.
Examiner’s tip δ–
Curly arrow shows a bonding pair becoming
Notes on drawing mechanisms: O a lone pair. The arrow goes from the middle
of the bond to the atom.
1 Curly arrows show the movement of an electron pair and
C δ+
not of anything else.
2 Be clear where the electron pair is moving from and where H
it is going to. For instance, if OH− is attacking, the curly X– pair of electrons going from being a lone pair
arrow should start from a lone pair on the O and not from on X to a bonding pair between C and X
the H. – O has extra electron, therefore

3 In most mechanisms the movement of electron pairs is such O O negatively charged
that a bonding pair of electrons becomes a lone pair of C C
electrons or a lone pair of electrons becomes a bonding pair. H X H
X–
G3 Elimination reactions Learning objectives

Elimination reactions involve the removal of the components of a small
molecule such as HCl or H2O from a molecule without them being
• Describe and explain the
elimination of water from
replaced by other atoms or groups. This results in the formation of a alcohols
C=C double bond. This has already been seen in Chapter 10, page 468
of the Coursebook, where the elimination of a hydrogen halide from a
halogenoalkane was considered, for example:
H H
H Cl H
C H
conc. KOH in ethanol
H C C C H H C C +H Cl
heat under reflux
H3C H
H CH3 H
2-methylprop-1-ene
Alcohols may be dehydrated to produce alkenes

Dehyrdation of an alcohol is an elimination reaction, involving the
elimination of H2O from the molecule.
The alcohol is heated with either concentrated sulfuric acid (H2SO4)
or concentrated phosphoric acid (H3PO4). The H2SO4 or H3PO4 acts as a
dehydrating agent.
For example, ethanol can be dehydrated to ethene by heating with
excess concentrated sulfuric acid:
H
O H
H H
The H and OH are always conc. H2SO4
H C C H C C + H2O
removed from adjacent C atoms. heat
H H
H H
With some alcohols more than one organic product is possible,

See Higher Level section on e.g. when 3-methylbutan-2-ol is dehydrated 3-methylbut-1-ene and
page 487 of Chapter 10 in the 2-methylbut-2-ene are possible products (Figure G13).
Coursebook for an explanation of When butan-2-ol is dehydrated but-1-ene and cis- and trans-but-2-ene
cis and trans. are all possible products.
H
H O H H H H
conc. H3PO4
H C C C C H H C C C C H + H2O
heat
H H CH3 H H H CH3 H
3-methylbut-1-ene
H
H O H H H H
conc. H3PO4
H C C C C H H C C C C H + H2O
heat
H H CH3 H H H CH3 H
2-methylbut-2-ene
Figure G13 Possible products when 3-methylbutan-2-ol is dehydrated.
Mechanism for the elimination of water

The first step in the mechanism is protonation of the O of the OH group
Elimination by this mechanism is
by the sulfuric acid or phosphoric acid. This creates a group that can more
more likely with a tertiary alcohol
readily leave than the OH group. In the third stage a pair of electrons
than with a primary alcohol as a
from the C–H bond is used to form the second component of the C=C.
tertiary alcohol forms a more stable
The H+ is used up in the first step but is regenerated in the last step.
carbocation.
So it is acting as a catalyst – it is not used up in the reaction.
H+ from either H2SO4 or H3PO4

H H+ H H
H O H H O+ H H H
+
H C C C H H C C C H H C C C H+H H
O
H H H H H H H H H
H C H
C C + H+
H +
H reformed
H 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 Addition–elimination reactions Learning objectives
The structure of 2,4-dinitrophenylhydrazine (2,4-DNPH) is shown in
Figure G14.
• Write equations for the reaction
of 2,4-dinitrophenylhydrazine
H
with aldehydes and ketones
H N H
N
NO2
Hydrazine is N2H4.
Phenylhydrazine is a molecule
NO2 of hydrazine where one H has
Figure G14 The structure of 2,4-DNPH. been replaced by a phenyl (C6H5,
benzene ring) group.
2,4-dinitrophenylhydrazine reacts with aldehydes and ketones in an
addition–elimination reaction. The reaction is so-called because the 2,4-
DNPH adds to the aldehyde/ketone with the elimination of a molecule
of water.
The equation for the reaction between 2,4-DNPH and propanone is
H H
C
H H C H
H N H H N C
N N H H
H O H
NO2 NO2
+ H C C C H + O
H H
H H
NO2 NO2
propanone 2,4-dinitrophenylhydrazone
Figure G15 The reaction between 2,4-DNPH and propanone.
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 H
Water is eliminated.
C H H
H C H
C
H O C H C H
N H H H N C
H N H N H H
NO2 NO2
Figure G16 Predicting the product of the reaction between 2,4-DNPH and propanone.
H H The structure of the product formed when butanal
C H (CH3CH2CH2CHO) reacts with 2,4-DNPH is shown in Figure G17.
H C H The reaction with 2,4-DNPH is used as a test for the presence of
H
the carbonyl (C=O) group in aldehydes and ketones. A few drops of
C
the aldehyde or ketone is added to an acidified solution of 2,4-DNPH
H C H in methanol (sometimes called Brady’s reagent). The solution is orange
H N
and when the aldehyde/ketone is added, a yellow-orange precipitate is
N formed. The formation of the precipitate indicates the presence of an
NO2 aldehyde/ketone group.
The product of these reactions is called a hydrazone and is named
as an aldehyde/ketone 2,4-dinitrophenylhydrazone, e.g. propanal
NO2 2,4-dinitrophenylhydrazone.
butanal 2,4-dinitrophenylhydrazone
If the melting point of these hydrazone crystals is determined and the
Figure G17 The structure of the product
values compared with those in tables, exactly which aldehyde/ketone was
formed when butanal reacts with 2,4-DNPH. originally present may be determined. For example, the melting point
of the 2,4-dinitrophenylhydrazone derivative of propanone is 128 °C,
whereas the melting point of the derivative of propanal is 155 °C.
Determination of the melting Test yourself

point of hydrazone is quite an old- 7 Draw the structures of the organic products formed
fashioned method of identifying when the following carbonyl compounds react with
compounds and nowadays infrared/ 2,4-dinitrophenylhydrazine:
nuclear magnetic resonance a pentan-3-one
spectroscopy would be used. b 3-methylbutanal
Learning objectives G5 Arenes

• Explain the evidence for a
Benzene and aromatic compounds
delocalised structure for benzene
• Explain the relative rates of
substitution of halogens atoms Compounds that contain a benzene ring are called aromatic
attached directly to a benzene compounds or arenes.
ring or in the side chain
The structure of benzene

Benzene consists of a planar hexagonal ring of C atoms with one
hydrogen atom joined to each C.
The structure originally proposed for benzene (C6H6) was due to
Kekulé and is usually called Kekulé benzene (Figure G18). In this
structure there are alternating single and double bonds between carbon
atoms. A more systematic name for this molecule would be cyclohexa-
Figure G18 Kekulé benzene.
1,3,5-triene or 1,3,5-cyclohexatriene.
The structure was accepted for many years but eventually the weight
of evidence against it became too great and a modified structure was
proposed. The structure of benzene is nowadays better represented as in
Figure G19.
Each C atom in this structure seems to form just three bonds (two to C
Figure G19 Structure of benzene. atoms and one to an H atom) (Figure G20). The remaining electrons form
a delocalised system of six electrons, which is represented by the circle in H
the centre of this structure. These six electrons are not localised between H H
C
individual C atoms in double bonds but rather spread over the whole ring. C C
C C
Delocalisation – electrons shared between three or more atoms. H C H
H
The ring of electrons is formed when p orbitals overlap side-on to form a HL Figure G20 Benzene ring showing all atoms.
π delocalised system (Figure G21).
Figure G21 Formation of the benzene delocalised system.
Evidence for the structure of benzene

Carbon–carbon bond lengths
All C–C bond lengths are equal in benzene and intermediate in length
between a C–C single bond and a C=C double bond (Table G1).
If the structure of benzene were cyclohexa-1,3,5-triene (Kekulé
benzene) then it would be expected that there would be three short C–C bond lengths may be
C=C bonds (approximately 0.133 nm) and three longer C–C bonds determined by X-ray crystallography.
(approximately 0.154 nm).
Bond Compound Bond length / nm

C=C ethene 0.133
C–C ethane 0.154
C–C benzene 0.139
Table G1 Bond lengths in ethene, ethene and benzene.
The delocalised structure of benzene suggests a C–C bond length

between that of a C–C bond and a C=C double bond as there are on
average three electrons (two from the single bond and one from the
delocalised electrons) between each pair of C atoms compared with four
electrons in C=C and two electrons in C–C.
Thermochemical evidence
When cyclohexene (C6H10) is heated with hydrogen in the presence of a
nickel catalyst cyclohexane (C6H12) is formed. This is an addition reaction
and hydrogen adds across the C=C double bond of the cyclohexene.
The enthalpy change for this reaction is approximately −120 kJ mol−1.
+ H2 ∆H = −120 kJ mol−1
cyclohexene cyclohexane (C6H12)
Cyclohexene contains one C=C whereas cyclohexa-1,3,5-triene (Kekulé

benzene) contains three C=C. It would, therefore be expected that the
enthalpy change for the complete hydrogenation of cyclohexa-1,3,5-triene
(Kekulé benzene) to cyclohexane would be 3 × −120, i.e. −360 kJ mol−1.
+ 3H2 ∆H = −360 kJ mol−1
cyclohexa-1,3,5-triene cyclohexane (C6H12)
The enthalpy change when benzene undergoes complete

hydrogenation to cyclohexane is, however, only −205 kJ mol−1.
+ 3H2 ∆H = −205 kJ mol−1
benzene cyclohexane (C6H12)
If an enthalpy level diagram is drawn for the hydrogenation reactions

of benzene and cyclohexa-1,3,5-triene (Kekulé benzene) it is seen that
benzene is 155 kJ mol−1 more stable than ‘expected’, i.e. 155 kJ mol−1 more
stable than would be predicted if it had the structure with alternating
single and double carbon–carbon bonds (Figure G22).
The extra stability of benzene compared to the structure with
alternating double and single bonds is due to the delocalisation of electrons.
The enthalpy change of hydrogenation of cyclohexa-1,3-diene
(1,3-cyclohexadiene) to cyclohexane is approximately −227 kJ mol−1.
This is reasonably close to 2 × −120 kJ mol−1 and although there is some
155 kJ mol–1
Enthalpy
∆H = –360 kJ mol–1
∆H = –205 kJ mol–1
cyclohexane
Figure G22 Comparative enthalpy changes for the hydrogenation reactions of

benzene and Kekulé benzene.
delocalisation of electrons in this structure, it is not nearly as extensive as
in benzene.
+ 2H2 ∆H = −227 kJ mol−1
cyclohexa-1,3-diene cyclohexane (C6H12)
The number of isomers of C6H4Cl2

Further evidence for a delocalised structure for benzene comes from
examining the number of isomers that are possible for C6H4X2 if we
assume a Kekulé or a delocalised structure (Figure G23).
Only three isomers have ever been found for C6H4Cl2 but the structure
with alternating double and single bonds would suggest that there should
be four. The difference comes because two Cl atoms which are next to
each other in the ring can either be separated by a C–C single bond or a
C=C double bond.
Benzene Kekulé benzene

Cl Cl Cl Cl
Cl Cl Cl
Cl Cl
Cl Cl
Cl Cl
Cl
Figure G23 Possible isomers for C6H4Cl2.
Reactions of benzene
Cyclohexa-1,3,5-triene (Kekulé 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
Examiner’s tip
means that it is regenerated in reactions, therefore benzene undergoes
The evidence for the structure
substitution reactions.
of benzene can be classified
For example, benzene reacts with chlorine in the presence of a catalyst
as either chemical (enthalpy
such as aluminium chloride to form chlorobenzene, C6H5Cl:
changes of hydrogenation
Cl and substitution reactions) or
physical (C–C bond lengths,
AlCl3
+ Cl2 + HCl number of isomers).
Naming aromatic compounds/arenes
The names of some simple aromatic compounds are shown here.
O
CH3 NO2 OH C OH
Cl
methylbenzene nitrobenzene phenol chlorobenzene benzoic acid / benzene carboxylic acid
Relative rates of hydrolysis of halogenated

benzene compounds
We have already seen in Chapter 10, page 468 of the Coursebook that
halogenoalkanes will undergo hydrolysis when heated with aqueous
sodium hydroxide solution:
Cl H OH H
NaOH(aq)
H C C H + OH– H C C H + Cl–
heat
H H H H
Chlorobenzene does not undergo hydrolysis (nucleophilic substitution)

reactions with sodium hydroxide under normal conditions.
Cl
Halogen atom attached directly to + NaOH NO REACTION under normal conditions

the ring.
To all extents and purposes halogenated benzene compounds

with the halogen atom attached directly to the ring are inert to
nucleophilic substitution.
When the halogen atom is not attached directly to the benzene ring,
but is rather in the side-chain, hydrolysis occurs much more readily, e.g.
H H H H
Here the halogen atom is said to be C Cl C OH
NaOH(aq)
in the side-chain. C + OH–
C + Cl–
heat
H H H H
Worked example
What is the organic product formed when the compound shown is H H H
H
heated with excess aqueous sodium hydroxide solution?
Cl C C C H
H Cl
Cl
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 H H H H H
H H
Cl C C C H Cl C C C H + Cl–
–
OH
H Cl H OH
attached directly will be substituted

to benzene ring
Cl Cl
NOT substituted
The reason that halogen atoms attached directly to the benzene ring are HL
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.
overlap of lone pair
with benzene π system
lone pair on CI
This has two effects:

• it strengthens the C–Cl bond, so that it is less easily broken (the
reaction involves breaking the C–Cl bond)
• nucleophiles (OH− is negatively charged) are repelled by the electrons
in the extended delocalised system.
nucleophile repelled by
electrons of delocalised system
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 carbon–halogen 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.
Test yourself
8 Give the structure of the organic products formed when the
following molecules are heated with excess aqueous sodium
hydroxide:
a H H b ClH2C CH2Cl
C C Cl
H H
Cl
Cl
Learning objectives G6 Organometallic chemistry

Organometallic compounds are organic molecules which also contain a
• Describe the formation of
metal atom. More precisely, they contain a bond between a carbon atom
Grignard reagents
and a metal atom. These are useful in organic synthesis.
• Write equations for reactions of
The most commonly used organometallic reagents are Grignard
Grignard reagents
reagents. These may be formed when a halogenoalkane is reacted with
magnesium turnings using a dry ether (usually ethoxyethane, (C2H5)2O)
Organolithium compounds are also as the solvent.
commonly used. H H H H
H C C O C C H
Grignard is pronounced as H H H H
grin-yard. ethoxyethane
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
The Grignard reagent cannot be RX + Mg ⎯⎯⎯⎯→ RMgX
isolated from solution.
For example:
dry ethoxyethane
H H C2H5Br + Mg ⎯⎯⎯⎯→ C2H5MgBr
ethylmagnesium
H C C Mg Br bromide
H H The structure of the Grignard reagent is shown in Figure G24. There is a

Figure G24 Grignard reagent structure. 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
This would, however, be rather a An alkane is formed, e.g.
waste of a Grignard reagent!
C2H5MgI + H2O → C2H6 + Mg(OH)I
2 Reaction of Grignard reagents with carbon dioxide
A carboxylic acid is produced. The salt of the carboxylic acid is first The conditions for the first
formed and then the acid is generated by adding a dilute strong acid step must be completely free of
such as sulfuric acid, e.g. water – pass dry CO2 through
the Grignard dissolved in dry
C3H7MgBr + CO2 → C3H7COOMgBr ethoxyethane.
propylmagnesium
bromide
H+ Note that the length of the carbon

C3H7COOMgBr + H2O → C3H7COOH + Mg(OH)Br chain has increased by one C.
butanoic acid
This can be shown more conveniently in a reaction scheme by putting

the reagents for both steps on one arrow:
H H H
(i) CO2 O
C3H7MgBr H C C C C
(ii) H+ / H2O O H
H H H
Examiner’s tip
The reactions of Grignard reagents may be more easily understood and The mechanism is not required
remembered if we consider the first stage of the mechanism. The electrons for the examination.
from the C–Mg bond are used to form a bond to a δ+ C atom.
δ–
O
C δ+
H H H O δ– H H H
O
H C C C Mg Br H C C C C
O–
H H H H H H
We could also show this more simply as a negatively charged alkyl

group attacking a δ+ C.
δ–
H H H O
H C C C– C δ+
H H H O δ–
3 Reaction of Grignard reagents with aldehydes and ketones

Alcohols are formed. The product of the initial reaction is the anion of
the alcohol and this is protonated by the addition of aqueous acid to
form the alcohol. The reaction between ethylmagnesium iodide and
propanal forms pentan-3-ol:
(i)
H H O
H
H C C C
H H H O H H
H H
C2H5Mgl H C C C C C H + Mg(OH)l
(ii) H+ / H2O
H H H H H
pentan-3-ol
Note the increase in the length of the carbon chain.
Aldehydes (with the exception of methanal) will form secondary
alcohols when reacted with a Grignard reagent. Methanal forms a
primary alcohol:
Br (i) O
Mg H H C H H H H H
H H
H C C C H O C C C C H + Mg(OH)Br
(ii) H+ / H2O
H H H H H H H
butan-1-ol
Ketones form tertiary alcohols when reacted with Grignard reagents:
(i)
H O H H H
Br H
H C C C C C H
Mg H H O H H H
H H H H
H C C H H C C C C C H + Mg(OH)Br
(ii) H+ / H2O
H H H H H H
H C H
H C H
H
3-methylhexan-3-ol
Again, these reactions can be understood more easily from a

consideration of the initial stage in the mechanism, which can be
regarded as involving a negatively-charged alkyl group attacking the
δ+ C of the carbonyl group (Figure G25).
Some reactions of Grignard reagents are shown in Figures G26 and G27.
H H H
δ+ δ–
H C C– C O
H H H C H
H C 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 aldehyde
primary alcohol Grignard reagent secondary alcohol
Mg ne H2O CO2
tha
h oxye
t
dr ye
halogenoalkane alkane carboxylic acid
Figure G26 Some reactions of Grignard reagents.
H
H O H H
H H H H H H H
H C C C H R1 C C R1 C C
H C C C H H C C C H conc. H3PO4 / heat H H
H H H C C R2 H C C
elimination mechanism
H H H H H C R2 R2
H H H
C R2 H C R2
H C R1
H C R1 H C R1
elimination mechanism
H tertiary alcohol
conc. H3PO4 / heat

H H (i) H O H
H C C C H
ketone
H H
(ii) H+/H2O
H
Br O H H
H H H C O H (i) O (i)
R1 C O H
R1 C C H H H
C H R1 Mg
H R1 C C
H C C R2 conc. H3PO4 / heat H C C R2 H methanal H aldehyde
H C C R2 H
elimination mechanism (ii) H+/H2O (ii) H+/H2O H C C R2
H H H
primary alcohol
H H
electrophilic HBr H H
addition Markovnikov’s rule (i) CO2
secondary alcohol
ane +
(ii) H /H2O
eth
H2O
Mg
O
oxy
H H
eth
H H H H R1 C O H
dry
R1 C R1 C
R1 Br R1 R2 H C C R2
Mg
H C C R2 H C C R2
dry ethoxyethane H C C H H C C H H H
H Br H Mg
H R2 H H
Br
Figure G27 Reaction pathways for Grignard reagents and dehydration of alcohols.
Test yourself
9 Draw the structure of the final organic products 10 a Name two aldehydes that could be reacted
formed when CH3CH2CH2MgBr reacts with the with suitable Grignard reagents to produce
following compounds: pentan-2-ol.
a CO2 b True or false? 2-Methylpropan-2-ol can be
b propanone made by reacting propanal with a suitable
c CH3CH2CHO Grignard reagent.
c Give the structural formula of a Grignard
reagent that can be reacted with propanone
to form 2-methylhexan-2-ol.
Learning objectives G7 Reaction pathways
We can use the reactions discussed in the previous section to design
• Deduce reaction pathways using
reaction pathways.
the reactions in the sections
above.
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 H Br H H H Mg
dry ethoxyethane
H C C C C H + Mg H C C C C H
H H H H H H H H
(i) CO2
(ii) H+ / H2O
H H H H
O
H C C C C C + Mg(OH)Br
O H
H H H 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 H O H H
H C C C C C H
Br
H H H H
H C H H C H
A B
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 O H H H H O H H
from ketone
H C C C C C H H C C C C C H
H H H H H H H H
H C H
from Grignard
reagent
The Grignard reagent must therefore be reacted with pentan-3-one.

H
H H O H H
Br
H C C C C C H
Br Mg (i)
H H O H H
H H H H
H C H H C H H C C C C C H H C H
dry ethoxyethane H H H H
A + Mg B + Mg(OH)Br
(ii) H+ / H2O
Test yourself
11 Give reaction sequences for the following 12 Give reaction sequences for the following
transformations: transformations:
a chloroethane to propanoic acid a 2-chloropropane to propane
b ethanal to 2-hydroxypropanoic acid b 2-chloropropane to 2-methylpropanoic acid
c ethanal to butan-2-ol c propan-1-ol to 2-chloropropane
G8 Acids and bases Learning objectives
Acidity • Explain the relative acidities of

substituted carboxylic acids
Carboxylic acids are weak acids that dissociate partially in aqueous
• Explain the relative acidities of
solution according to the equation: substituted phenols
O H O–
• Explain the relative basicities of
R C + H2O R C + H3O + ammonia and amines
O O
carboxylate ion
The stronger an acid the more it dissociates in aqueous solution (position

of equilibrium lies more to the right). Acid strength is sometimes described
using the pKa value. The lower the pKa value the stronger the acid. pKa is
a log scale and therefore a change in pKa of one unit indicates a ten-fold
change in acid strength. The pKa value for methanoic acid is approximately
Acid pKa
one less than that for ethanoic acid and, therefore, methanoic acid is
methanoic acid 3.75 roughly ten times stronger than ethanoic acid (Table G2).
ethanoic acid 4.76
propanoic acid 4.87 HL
The carboxylate ion actually has both C–O distances equal and
butanoic acid 4.82 between the length of a C–O single bond and a C=O double bond.
pentanoic acid 4.86 It is, therefore, better described by the delocalised structure:
chloroethanoic acid 2.86 O
dichloroethanoic acid 1.29 R C–
trichloroethanoic acid 0.65 O
iodoethanoic acid 3.17
2-chlorobutanoic acid 2.84
3-chlorobutanoic acid 4.06 Chloroethanoic acid is a stronger acid than ethanoic acid
4-chlorobutanoic acid 4.52 The dissociation of ethanoic acid and chlorethanoic acid may be shown as:
phenol 10.00
H H
ethanol 16 O O
4-methylphenol 10.26 H C C H C C + H+
O H O–
2,4,6-trinitrophenol 0.42 H H
ethanoic acid ethanoate ion
Table G2 pKa values.
Cl Cl
O O
The greater acidity of H C C H C C + H+
chloroethanoic acid is sometimes O H O–
H H
explained in terms of the stability chloroethanoic acid chloroethanoate ion
of the acid. The Cl atom is
electron-withdrawing and pulls
The difference in acidity can be explained by considering the stability
electron density from the COOH
of the anion (conjugate base) formed. The Cl is a very electronegative
group. This makes the H of the
atom and, in the chloroethanoate ion, pulls electron density away from
COOH group more positive and
the COO− group (Figure G28). Since the COO group is less negative,
thus more likely to be lost as a
it attracts the H+ ion back less strongly. The conjugate base is, therefore,
proton.
more stable. A more stable conjugate base indicates a greater tendency to
dissociate and, therefore a stronger acid.
Cl
O
H C C
O–
The total negative charge in the anion is still 1− but it is spread out
H more over the whole anion in the chloroethanoate ion rather than
electron density withdrawn being localised on the COO− group.
from COO– group
Figure G28 The chloroethanoate ion.
Trichloroethanoic acid is a stronger acid than chloroethanoic
acid
Cl Cl
O O
Cl C C Cl C C + H+
O H O–
Cl Cl
trichloroethanoic acid trichloroethanoate ion
An electron-withdrawing effect Again, we will consider the stability of the anion/conjugate base
is sometimes called a negative formed. Three very electronegative Cl atoms have a greater electron-
inductive effect. withdrawing effect than just one. More electron density is thus pulled
away from the COO− group making it less negative and less likely
to attract back the H+ (Figure G29). The trichloroethanoate ion Cl
O
is thus relatively more stable than the chloroethanoate ion and so
Cl C C
trichloroethanoic acid dissociates more. O–
Cl
Chloroethanoic acid is a stronger acid than iodoethanoic acid more electron density
withdrawn from COO– group
I I Figure G29 The trichloroethanoate ion.
O O
H C C H C C + H+
O H O–
H H
iodoethanoic acid iodoethanoate ion
Iodine is a less electronegative atom than chlorine and thus withdraws

less electron density from the COO− group. The COO group is thus
more negative in the iodoethanoate ion and the H+ ion is attracted back
more strongly. The conjugate base is less stable and the acid is weaker.
Iodoethanoic acid is, however, still a stronger acid than ethanoic acid
because of the electron-withdrawing nature of the I atom.
In general, for compounds of the form:
X
O
H C C
O H
H
if X is an electron-withdrawing group, the acid will be a stronger acid
than ethanoic acid due to stabilisation of the anion/conjugate base formed
when the acid dissociates. If X is an electron-releasing group the acid will
be a weaker acid than ethanoic acid due to destabilisation of the anion/
conjugate base formed.
An electron-releasing group will increase the electron density on the
COO group in the anion and the H+ ion will thus be attracted back more
strongly. The conjugate base is therefore less stable and the acid weaker.
H
Ethanoic acid is a weaker acid than methanoic acid O
Ethanoic acid has an electron-releasing group attached to the H C C
O–
COO−group in the anion. This increases the electron density on the H
COO group and therefore the H+ is attracted back more strongly (Figure electron density donated
G30). This means that the conjugate base is less stable for ethanoic acid to COO– group
and, it is, therefore a weaker acid. Figure G30 The ethanoate ion.
O O
H C H C + H+
O H O–
methanoic acid methanoate ion
H H
O O
H C C H C C + H+
–
O H O
H H
ethanoic acid ethanoate ion
The electron-releasing effect of an alkyl group is often called a

positive inductive effect.
Extension Beyond an ethyl group, the size of the alkyl group makes little
difference to the electron-releasing effect. Thus propanoic acid is slightly
Propanoic acid, butanoic acid stronger than ethanoic acid (the electron-releasing effect of an ethyl
and pentanoic acid all have very
group is slightly greater than that of a methyl group) but propanoic acid,
similar acid strengths because of the
butanoic acid and pentanoic acid all have very similar acid strengths.
mechanism by which alkyl groups
donate electrons. This arises because
The effect of distance of the Cl group from the COOH group on
of the overlap of electron density in
acid strength
a σ bond (either C–H or C–C) with
a p orbital on an adjacent atom – 2-Chlorobutanoic acid is a stronger acid than 4-chlorobutanoic acid.
σ-conjugation/hyperconjugation. The further the Cl is from the COO− group in the anion, the smaller
the electron-withdrawing effect it has on it.
H H Cl H H Cl
O O
H C C C C H C C C C + H+
–
O H O
H H H H H H
2-chlorobutanoic acid
Cl H H Cl H H
O O
H C C C C H C C C C + H+
–
O H O
H H H H H H
4-chlorobutanoic acid
Phenol is a significantly stronger acid than aliphatic alcohols

Phenol reacts with blue litmus and
such as ethanol
forms salts with sodium hydroxide.
It is still however a weaker The dissociation of phenol may be shown as:
acid than carboxylic acids. C6H5OH C6H5O− + H+
Phenol may be distinguished from
carboxylic acids by the fact that it or, showing structures:
will not liberate CO2 from sodium H
hydrogencarbonate solutions, i.e. it O O–
is a weaker acid than carbonic acid.
+ H+
Phenol is more soluble in sodium phenol phenoxide ion

hydroxide solution than in water. It
reacts with the sodium hydroxide The dissociation of ethanol is:
to form an ionic salt (C6H5O−Na+)
and therefore there are stronger H H H H H
interactions with water molecules. H C C O H C C O–+ H+
H H H H
ethanol ethoxide ion
Again we will consider the stability of the anion/conjugate base. The

lone pair on the O− in the phenoxide ion overlaps with the delocalised
system in the benzene ring (Figure G31). This spreads out the negative
charge in the ion. The O is thus less negative and the H+ is not attracted
back as strongly. The anion is thus stabilised and phenol is a stronger acid
than ethanol. In ethanol this delocalisation does not occur and indeed the
negative charge on the O in the ethoxide ion is increased by the electron-
donating alkyl group.
electron density
donated into ring
lone pair on O
Figure G31 The negative charge on O is delocalised into the ring.
Acidity of substituted phenols

In general, for compounds of the form
OH
if X (in any position) is an electron-withdrawing group the compound

will be a stronger acid than phenol. The electron-withdrawing group
reduces the amount of electron density on the O in the conjugate base
– the charge is more delocalised in the anion – meaning that the H+ is
less strongly attracted and the anion is more stable. If X is an electron-
donating group the compound will be a weaker acid than phenol. In
this case the charge is less delocalised in the anion. With the charge more
localised on the O, the H+ is attracted back more strongly and the anion is
less stable.
4-methylphenol is a weaker acid than phenol

H
O O–
+ H+
CH3 CH3
4-methylphenol 4-methylphenoxide ion
The methyl group is electron-releasing (positive inductive effect)

and increases the amount of electron density in the aromatic ring.
Delocalisation of the negative charge on O in the anion of 4-methylphenol
is reduced as the ring is more negative than in phenol. There is thus more
electron density on the O in the 4-methylphenoxide ion so that the H+ is
attracted back more strongly and the anion is less stable.
2,4,6-trinitrophenol is a stronger acid than phenol
H
O O– 2,4,6-Trinitrophenol is such a
O2N NO2 O2N NO2 strong acid that its trivial name is
picric acid.
+ H+
NO2 NO2
2,4,6-trinitrophenol 2,4,6-trinitrophenoxide ion
The NO2 group is electron-withdrawing and will therefore reduce
the amount of electron density in the aromatic ring. There is thus greater
delocalisation of the negative charge from the O− into the ring. With
lower charge on the O the H+ is attracted back less strongly and the anion
is more stable for 2,4,6-trinitrophenol.
a b
– The NO2 group is electron-withdrawing because it consists of three
O O O O very electronegative atoms and there is no lone pair on the N that could
+
N N be drawn into the ring. The Lewis structure for the NO2 group attached
to a benzene ring is shown in Figure G32a. A dative covalent bond is
formed from the N to the left hand O in this diagram and so the N
Figure G32 Lewis structure for (a) the NO2
group attached to a benzene ring and (b) is often shown with a positive charge (as it is has essentially given one
showing the charges. electron to the O) (Figure G32b).
Extension
Some of the electron-withdrawing effect of the NO2 group also comes
from a π effect where the p orbitals which make up the delocalised system
in the benzene ring overlap with the π system of the NO2 group.
Basicity
A base (Brønsted–Lowry 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 CH3NH3+ + OH−

methylamine methylammonium
ion
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
Table G3 The formula and pKb of various bases.
In all of these compounds the N is the most electronegative atom and
will have a small negative charge.
δ+
H H3C
H 3C
δ+ δ– δ+ δ– δ+ δ–
H N H N H N
H δ+ H δ+ H δ+
H+ ions will thus be attracted to the N and the lone pair of electrons Figure G33 Methylamine.
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 H3C
δ+ δ–
the stronger base it will be. H N
CH3 is an electron-releasing group (positive inductive effect) and
so will push electron density onto the N, making it more negative and CH3
therefore more likely to attract H+. Methylamine is thus a stronger base Figure G34 Dimethylamine.
than ammonia (Figure G33).
Similarly, dimethylamine is a stronger base than methylamine as it has
a
two electron-releasing alkyl groups which donate electrons to the N
δ+ δ+
making it even more negative (Figure G34). H CH3 H
It would therefore be expected that trimethylamine would be a δ– δ+ δ+
stronger base than dimethylamine. However, although it is a stronger base O H N+ H O δ–
than ammonia it is a weaker base than methylamine and dimethylamine. δ+
H δ+ CH3 H
This is due to greater stabilisation of the protonated form by hydrogen
bonding with water (the solvent) in the dimethylammonium ion than in
b
the trimethylammonium ion. There are two H atoms that can hydrogen
δ+
bond to water in the dimethylammonium ion but only one in the H CH3
trimethylammonium ion (Figure G35). The protonated form is thus δ– δ+
O H N+ CH3
stabilised to a greater extent for dimethylamine than for trimethylamine
and this outweighs the extra electron-releasing effect of the extra alkyl H δ+ CH3
group. This means that the protonated form is more likely to be formed
Figure G35 Hydrogen bonding of the H
for dimethylamine and it is therefore ionised to a greater extent and a atoms in the (a) dimethylammonium ion
stronger base. and (b) trimethylammonium ion with water.
This can also explain why methylamine is a lot stronger than

ammonia but dimethylamine is only slightly stronger than
methylamine.
Phenylamine is a significantly weaker base than ammonia
C6H5NH2 + H2O C6H5NH3+ + OH−

phenylamine phenylammonium
ion
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+.
Amines are more soluble in
Formation of salts hydrochloric acid than in water
Amines, like ammonia, form salts with acids, e.g. due to the formation of the
NH3 + HCl → NH4+Cl− ionic salt and, therefore, stronger
ammonium interactions with water molecules.
chloride
CH3NH2 + HCl → CH3NH3+Cl−
methylammonium
chloride
An alkylammonium salt can be converted back to an amine by reaction

with a strong base such as sodium hydroxide:
CH3NH3+Cl− + NaOH → CH3NH2 + H2O + NaCl

The alkylammonium ion is acting
as a Brønsted–Lowry acid. NaOH This can be shown as an ionic equation:
is a stronger base than the amine
CH3NH3+ + OH− → CH3NH2 + H2O
and therefore can take the proton
away from it.
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 Addition–elimination reactions
• Describe the reactions of acyl
Acyl chlorides (acid chlorides)
chlorides with nucleophiles
• Explain the mechanism for the The basic structure of an acyl chloride is:
reaction of acyl chlorides with O
nucleophiles R C
Cl
• Describe the reactions of acid
anhydrides with nucleophiles
Acyl chlorides may be prepared by reacting carboxylic acids with
SOCl2 or PCl5.
They are named as alkanoyl chloride, e.g.
H H H H H CH3 H
O O O
H C C H C C C C H C C C C
Cl Cl Cl
H H H H H H H
ethanoyl chloride butanoyl chloride 3-methylbutanoyl chloride
These are extremely reactive and react to add an acyl group to

nucleophiles with the elimination of HCl.
O
R C
acyl group
1 Reaction with water

Acyl chlorides react violently with water to from carboxylic acids.
H H
O O
H C C + O H C C + H Cl
Cl H H O H
H H
ethanoyl chloride ethanoic acid
In all the reactions we will meet the acyl group will be added to the HL H O
acyl group added to O
most electronegative atom of the nucleophile (N or O) and H (from
H C C O H
the nucleophile) and Cl (from the acyl chloride) will be eliminated Cl H
(Figure G36). H
HCl eliminated
2 Reaction with alcohols Figure G36 Reaction of an acyl chloride with
Acyl chlorides react with alcohols to form esters. water.
H H H H H H H H H O H H
O
H C C C C + O C C H H C C C C O C C H + H Cl
Cl
H H H H H H H H H H
butanoyl chloride ethyl butanoate This reaction is usually carried out
in the presence of a base such as
An alkaline solution of phenol reacts with benzoyl chloride to form pyridine (C5H5N).
phenyl benzoate:
O
OH C O
Cl O C
+ + H Cl
phenyl benzoate
3 Reactions with ammonia

When concentrated ammonia solution is added to an acyl chloride at
0 °C a primary amide is formed.
H H H H
O O
H C C C + N H C C C + H Cl
Cl H H NH2
H H H H H
propanamide
A more accurate way of writing this reaction would be as:
CH3CH2COCl + 2NH3 → CH3CH2CONH2 + NH4Cl
HCl would not be formed in the presence of a base such as

ammonia but rather the salt ammonium chloride.
4 Reactions with amines

When acyl chlorides are reacted with amines (again at low
temperature) N-substituted amides are formed.
H H H H H H
O H O H H
H C C C + N C C H H C C C + H Cl
Cl H N C C H
H H H H H H H
ethylamine H H
N-ethylpropanamide
Again, the balanced equation should, more correctly, be written as:
CH3CH2COCl + 2CH3CH2NH2
→ CH3CH2CONHCH2CH3 + CH3CH2NH3Cl
HL The addition–elimination mechanism
The mechanism of these reactions involves two steps:
1 initial addition of the nucleophile
2 elimination of the elements of HCl.
The basic mechanism can be illustrated by representing the nucleophile
as X−:
δ– –
H O H O H O
H C C δ+ H C C Cl H C C + Cl–
Cl X
H X– H X H
The nucleophile attacks the δ+ C of the C=O group. The π

component of the C=O breaks with the pair of electrons going to the
O to generate O−. A lone pair from the O then is used to re-form the
double bond and at the same time the C–Cl bond breaks.
Now, if we look at the reaction with water:
δ– – –
H O H O H O H O
H C C δ+ H C C Cl H C C Cl H C C + Cl–
Cl O H
H Hδ+ H O+ H O H
O H H H +
O O H
Hδ+ H H H H
The second stage could also have been shown more simply as loss of a
proton (H+):
– –
H O H O
H C C Cl H C C Cl
H O+ H O + H+
H H H
In the second stage H+ is removed by interaction with a base. In the

reaction of an alcohol with an acyl chloride the reaction is conducted
in the presence of a base. In the reaction with ammonia the proton is
removed by the ammonia/amine.
δ–
H O H O– H O– H O
H C C δ+ H C C Cl H C C Cl H C C + Cl–
Cl N H
H δ– Hδ+ H H N+ H N H
N H δ+ H H N H H H H
Hδ+ H H +
H N+ H
H H
Acid anhydrides
The basic structure of an acid anhydride is:
O
R C
O
R C
O
This can be regarded as being formed from two molecules of carboxylic HL H
O
acid with water removed (Figure G37).
H C C
Acid anhydrides are named according to the carboxylic acid from O H
which they are derived, e.g. H
H
O O O H
H3C C CH3CH2 C H C C
O O O
H
H3C C CH3CH2 C
O O Figure G37 Formation of an acid anhydride.
ethanoic anhydride propanoic anhydride
Acid anhydrides are actually made
Mixed anhydrides are also possible and they would be named as, e.g. by the reaction between an acyl
ethanoic propanoic anhydride. chloride and the sodium salt of a
Like acyl chlorides, acid anhydrides are acylating agents – they react carboxylic acid.
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. Note that acid anhydrides are less
1 Reaction with water reactive than acyl chlorides.
Acid anhydrides react when warmed with water to form carboxylic
acids:
O H H
H3C C O O
O + O H C C + H C C
H3C C H H O H O H
O H H
ethanoic anhydride ethanoic acid ethanoic acid
2 Reaction with alcohols

Acid anhydrides react when heated with alcohols to form esters:
O H H H H H O H H H H
CH3CH2 C O
O + O C C H H C C C O C C H + H C C C
CH3CH2 C O H
O H H H H H H H H
propanoic anhydride ethyl propanoate propanoic acid
Ethanoic anhydride can be heated with 2-hydroxybenzoic acid to make

aspirin: Aspirin contains an ester linkage.
H H
H
O O O O O
O C C H
C C H
H3C C O H O O
O + H +H C C
H3C C O H
The systematic name of aspirin is
O H 2-ethanoyloxybenzenecarboxylic
ethanoic 2-hydroxybenzoic acid aspirin ethanoic acid acid!
anhydride
HL 3 Reactions with ammonia
When excess concentrated aqueous ammonia solution is reacted with
an acid anhydride a primary amide is formed:
O H H H H
CH3CH2 C O O
O + N H C C C + H C C C
CH3CH2 C H H NH2 O H
O H H H H H
propanoic anhydride propanamide propanoic acid
4 Reactions with amines

When acid anhydrides are reacted with amines N-substituted amides
are formed:
O H H H H H H
CH3CH2 C H O H H O
O + N C C H H C C C + H C C C
CH3CH2 C H N C C H O H
O H H H H H H H
H H
propanoic anhydride ethylamine N-ethylpropanamide propanoic acid
ethanamine
Ethanoic anhydride reacts with 4-aminophenol at room temperature to

form paracetamol:
OH OH
O H
H3C C O
+ O +H C C
H3C C O H
O H
The systematic name NH2 H3C N
ethanoic
of paracetamol is N-(4- C H
4-aminophenol anhydride ethanoic acid
hydroxyphenyl)ethanamide! O
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
G10 Electrophilic substitution reactions HL
Learning objectives
Benzene reacts with electrophiles via an electrophilic substitution reaction.
The general mechanism is:
• Describe the chlorination,
alkylation, acylation and
nitration reactions of benzene
X • Explain the mechanism for
X+ + X + H+ electrophilic substitution
H
electrophile • Describe the chlorination,
alkylation, acylation and
nitration reactions of
In the first step a pair of electrons from the benzene π delocalised
methylbenzene
system is used to form a bond to the electrophile. In order to form a bond
the C atom must use one of the orbitals that was previously forming part • Explain the relative rate of
electrophilic substitution in
of the π delocalised system. The delocalised system can then only extend
benzene and substituted benzene
over the other five C atoms (Figure G38). This is shown by the partial
rings
ring. There were originally six electrons in the π delocalised system (one
from each C atom) but two are now used to form the C–X bond, which • Explain the position of
substitution in substituted
leaves only four electrons shared over five C atoms; the ring thus has a
benzene rings
positive charge.
X
H
Another way of thinking about this
Figure G38 Partial delocalisation in the intermediate in an electrophilic substitution
reaction. is that the initial reaction involved
a neutral species reacting with a
positively charged species, therefore
In the second step the C–H bond breaks. This releases an orbital and a the intermediate must also have a
pair of electrons to complete the π delocalised system again. positive charge.
The nitration of benzene

When benzene is heated with a mixture of concentrated nitric and
sulfuric acids, nitrobenzene is formed:
conc. HNO3 NO2

conc. H2SO4
+ HNO3 + H2O
heat under reflux
60°C
nitrobenzene
C6H6 + HNO3 → C6H5NO2 + H2O
Formation of the electrophile

The electrophile in this reaction is the NO2+ ion, which is formed when
the concentrated sulfuric acid reacts with the concentrated nitric acid:
HNO3 + 2H2SO4 → NO2+ + H3O+ + 2HSO4−
A simpler version of this equation is:
HNO3 + H2SO4 → NO2+ + H2O + HSO4−
HL The mechanism is basically the same as shown in the general
mechanism on page 33:
NO2
NO2+ + NO2 + H+
H
electrophile
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.
H
NO2
+ NO2 + H2SO4
H O– O
S
O 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 Benzene does not react with halogens in the dark because the halogen
could be used. 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.
All reactions involving AlCl3 must
be carried out in the absence of Formation of the electrophile
water as AlCl3 reacts with this. Aluminium chloride is electron deficient (only six electrons in the outer
shell of the Al) and accepts a pair of electrons from the Cl2. This is often
shown as:
Examiner’s tip
This is the equation you need Cl2 + AlCl3 → [AlCl4]− + Cl+
for the examination.
AlCl3 acts as a Lewis acid.
Cl+ is the electrophile.
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
δ+
Cl Cl Al Cl
Cl
The mechanism is basically the same as the general mechanism given HL
on page 33: The first stage in this mechanism
can be regarded as a Lewis acid–
Cl base reaction: the benzene ring
Cl+ + Cl + H+
electrophile
H is the Lewis base (electron pair
donor) and the Cl+ the Lewis acid
The second step can also be shown with the [AlCl4]− removing the (elecron pair acceptor).
proton to reform the catalyst.
Cl
+ Cl + HCl + AlCl3
H
catalyst re-formed
Cl
–
Cl Al Cl
Cl
Alkylation (also known as Friedel–Crafts alkylation)

Halogenoalkanes react with benzene in the presence of a halogen carrier
catalyst. Consider the reaction between 2-chloro-2-methylpropane and
benzene:
(CH3)3CCl + C6H6 → C6H5C(CH3)3 + HCl

CH3
H3C C CH3
CH3
AlCl3
+ H3C C CH3 + HCl
5 °C
Cl
(1,1-dimethylethyl)benzene
(CH3)3CCl + AlCl3 → (CH3)3C+ + [AlCl4]−
For tertiary halogenoalkanes it is likely that the electrophile is the

carbocation, but for secondary and primary halogenoalkanes it is
probably a highly polarised complex. For the examinations, however, the
electrophile can be regarded as R+ where R is the alkyl group of the
halogenoalkane.
The mechanism is the same as for halogenation.
CH3
CH3 CH3
C CH3
+C CH3 + C CH3 + H+
H CH3
CH3 CH3
electrophile
Again, the second step could be shown with [AlCl4]− removing the H+
to reform the catalyst.
CH3
CH3
C CH3
+ C CH3 + HCl + AlCl3
H CH3
catalyst re-formed
Cl CH3
Cl Al– Cl
Cl
HL Acylation (also known as Friedel–Crafts acylation)
Acyl halides react with benzene in the presence of a halogen carrier
catalyst. Consider the reaction of ethanoyl chloride with benzene:
CH3COCl + C6H6 → C6H5COCH3 + HCl
The benzene ring here is named as H

O
a phenyl substituent. H C C
H
O H
AlCl3
+H C C + HCl
Cl 50 °C
H
phenylethanone

This is a similar reaction to that already seen on pages 34–35 for the
formation of the electrophiles for chlorination and alkylation.
CH3COCl + AlCl3 → CH3CO+ + [AlCl4]−
The mechanism is the same as for alkylation.
O
O
C O
+C + C + H+
H CH3
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 electrophilic-
substitution mechanism. The conditions for the reactions of
methylbenzene are slightly milder than those for the reactions of benzene
as the methyl group is an activating group. The methyl group donates
electron density into the benzene ring (positive inductive effect). This
increases the amount of electron density in the ring so that it is more
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
Some of the electrophilic substitution reactions of methylbenzene are

O HL
CH3 CH3
C CH3
H
O
H3C C H C C
O Cl
H
AlCl3 CH3 CH3 CH3
conc. HNO3 NO2
conc. H2SO4
heat under reflux
AlCl3 NO2
AlCl3 Cl2
C2H5Cl
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
+ + HCl
AlCl3
2-chloromethylbenzene
Cl
4-chloromethylbenzene
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 here is as for
substitution mechanism as for alkanes. alkanes (see Chapter 10, page 434
H H
of the Coursebook) and can be
summarised as
H C H H C Cl UV
Cl2 ⎯
→ 2Cl•
Cl2
+ HCl RCH3 + Cl• → RCH2• + HCl
UV
(chloromethyl)benzene RCH2• + Cl2 → RCH2Cl + Cl•
plus a termination step.
HL Multiple substitution can occur to form (dichloromethyl)benzene and
(trichloromethyl)benzene.
H H Cl Cl
H C H H C Cl H C Cl Cl C Cl
Cl2 Cl2 Cl2

UV UV UV
(chloromethyl) (dichloromethyl) (trichloromethyl)
benzene benzene benzene
This reaction occurs more generally when an alkyl group attached to

a benzene ring reacts with a halogen in the presence of UV light. Thus
ethylbenzene would react with chlorine in the presence of UV light to
form a mixture of monochlorinated products:
H H H
H C H H C H H C Cl
H C H H C Cl H C H
Cl2
+
UV
Naming multi-substituted benzene rings

Names of some simple molecules, where both groups are the same, are
shown here.
CH3 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 CH3 OH
1 CH3 1 NO2
2 2
Cl
IUPAC name 1-chloro-2-methylbenzene 1-methyl-2-nitrobenzene 4-chlorophenol
Alternative 2-chloromethylbenzene 2-nitromethylbenzene
names
2-methylchlorobenzene 2-methylnitrobenzene
Table G4 Naming multi-substituted benzene rings.
Reactions of substituted benzene rings HL
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).
Substituents that cause substitution faster than with benzene are called
activating groups and those that cause substitution to occur more slowly
than with benzene are called deactivating groups (Table G5).
2,4-directing groups usually cause substitution faster than benzene

and 3-directing groups 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).
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 CH3
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 Main product of chlorination Rate of substitution Nature of effect on electrophilic

relative to benzene substitution
–CH3 CH3 CH3 faster activating and 2,4-directing
and other alkyl Cl
group
Cl
–OH OH OH OH faster activating and 2,4-directing
Cl Cl Cl
Cl Cl
–NO2 NO2 slower deactivating and 3-directing
Cl
Table G5 Reactions of substituted benzene rings.
HL ring more negative, i.e. more attractive towards electrophiles and
the reaction occurs more quickly than with benzene.
Why does phenol react more readily than benzene?

At first sight we might expect the –OH group to be electron-
withdrawing due to the high electronegativity of O. However, the –OH
lone pair
group also possesses a lone pair of electrons and overlap of this lone
C C
pair into the ring activates the benzene ring (Figure G40).
C C O H
This π donation into the ring is a bigger effect than the σ-withdrawing
C C effect (due to the electronegativity of O). Therefore there is net
π donation
into ring donation of electron density into the ring and the ring will
Figure G40 Activation of the benzene ring. attract electrophiles more strongly.
Reaction of phenol with chlorine

One particularly good example of the ease of reactivity of phenol is in its
reaction with chlorine.
Phenol reacts with chlorine water – Cl2(aq) – to form
Phenol is also made more reactive
2,4,6-trichlorophenol (no halogen carrier required):
in water since it is acidic and
produces the phenoxide ion OH OH
C6H5O−. The negative charge Cl Cl
on the O means σ withdrawal + 3Cl2 + 3HCl
is reduced and π donation is
increased, therefore the ring is
Cl
more attractive to electrophiles.
2,4,6-trichlorophenol
Nitrobenzene reacts more slowly than benzene

The NO2 group is electron-withdrawing and deactivates the benzene
ring. With less electron density in the ring it attracts electrophiles less
strongly, therefore nitrobenzene reacts more slowly than benzene. NO2 is
electron-withdrawing because of the high electronegativity of the atoms
in the group and, unlike the O in phenol, it does not possess a lone pair
of electrons on the N that can be donated into the ring. There is also
delocalisation of the π electrons from the ring onto the NO2 group.
Position of substitution in arenes

The position of substitution is determined by the charge distribution in
the intermediate. The more stable the intermediate the more likely it is to
be formed.
This is most usually explained using the Kekulé structure of benzene
but to understand the explanation we must first understand something
about resonance.
Two possible Lewis structures may be drawn for benzene, with the
double bonds between different atoms (Figure G41). These are called
resonance structures. The actual structure of benzene is regarded as a
Figure G41 Resonance structures of resonance hybrid of these two structures – not one or the other but
benzene. somewhere in between.
The position of substitution in nitrobenzene

The position of substitution in nitrobenzene can be explained in terms
of the stability of the intermediate carbocation formed.
The structure of nitrobenzene showing the bonds involved is shown in HL –
O O
Figure G42. The nitrogen forms a dative covalent bond to one of the O +
N
atoms, therefore there is a positive charge on the N.
If substitution were to occur at position 2 then one of the resonance
forms that contributes to the intermediate has two positive charges next
to each other, which makes the intermediate less stable.
Figure G42 The structure of nitrobenzene
showing charge on N.
some resonance forms of the intermediate
– – – –
O O O O O O O O
+ + + +
N N N N
+ X X X
X+
H H H
+ +
substitution 2 positive charges
at position 2 next to each other
curly arrows represent delocalisation of electrons
A similar situation occurs if substitution occurs at position 4.
– – – –
O O O O O O O O
+ + + +
N N N N
+ +
X+ X H X H X H
2 positive charges
substitution
next to each other
at position 4
However, when substitution occurs at position 3 it is not possible for

the two positive charges to be next to each other and the intermediate is
more stable and more likely to be formed.
– – – –
O O O O O O O O
+ + + +
N N N N
+ +
X X X
+ H H H
X+
substitution
at position 3
Position of substitution in phenol

When substitution occurs at position 2 the intermediate is stabilised by
donation of the lone pair into the ring.
H H H
O O O+
+ X X
X+
H H
intermediate stabilised
substitution by donation of lone pair
at position 2 into ring
HL The same stabilisation is possible when substitution occurs at position 4.
H H H
O O O+
X+ X H X H
substitution intermediate stabilised
at position 4 by donation of lone pair
into ring
If substitution were to occur at position 3, stabilisation of the positively

charged intermediate is not possible by donation of the lone pair on the
O into the ring.
H H
O O
X
+ + H
X
substitution delocalisation not possible
at position 3 as C has 4 bonds
donation
into ring
H Position of substitution in methyl benzene
C C The methyl group has an electron-releasing effect and this also stabilises
C C C H the intermediate when substitution occurs at positions 2 and 4.
C C H The electron-releasing effect of the methyl group comes from the
overlap of the electron density in the C–H σ bond with a p orbital on an
adjacent atom (Figure G43).
Figure G43 The electron-releasing effect of
the methyl group. The stabilising effect of the methyl group on the intermediate can be
shown as:
Examiner’s tip H H
H H H H
A summary of the explanations C C
is that an electron-releasing X
+
group stabilises the X+
H
intermediate by electron
donation into the ring. This
substitution intermediate stabilised by
stabilisation is only possible at position 2 donation of electrons into ring
when substitution occurs
at positions 2, 4 and 6. An As for phenol, this stabilisation is only possible when substitution
electron-withdrawing group occurs at positions 2 or 4.
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.
An alternative way of explaining the directing This can also be shown using resonance forms.
effect of substituent groups (not for examinations) H H – –
O O O O–
is in terms of the charge distribution in the initial +
O O+ N N
compound. An electron-releasing group will
increase the electron density at positions 2, 4 and – +
6 and therefore the electrophile is more attracted
to these positions. An electron-withdrawing group
withdraws electron density from positions 2, 4 and electron density increased electron density reduced
at position 2 at position 2
6 and, therefore, there is more electron density at
positions 3 and 5 and an electrophile is attracted to
these positions.
electron-releasing electron-withdrawing
X group X group
δ– δ– δ+ δ+
electrophile
more attracted
δ– δ+ 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: 16 The molecule in Question 15a can react with
H H
chlorine under suitable conditions to form five
possible monochlorinated products. Draw the
H C C H CH3 OH structures of the possible products and suggest
H Cl which is least likely to be formed when the
molecule reacts with chlorine.
NO2
a b c
Learning objectives
HL G11 Reaction pathways
• Deduce reaction pathways using
Reaction pathways
the reactions in the sections
above. Some reactions of aromatic compounds and acyl chlorides are summarised
in Figure G44.
CH2OH
NaOH(aq) O
heat H O C
CH3 CH3 CH3 CH2Cl CH2MgCl H C H

Cl
NaOH(aq) Cl2 Cl2 Mg (i) CO2
no reaction
heat AlCl3 UV light dry ethoxyethane (ii) H+ / H2O
Cl
CH3Cl AlCl3
Cl NO2 NO2
conc. HNO3
Cl2 conc. H2SO4 AlCl3
AlCl3 heat under reflux CH3Cl

CH3
H
O H H H
H C C O
H H AlCl3
O C C H H C C
H H C C OH Cl
H H H
H
H H O
base H C C
H H
O O H
H2O
H C C H C C
O H Cl AlCl3
H H H H
NH3
H C C NH2 cold
conc. NH3(aq) H
H H O
cold H C C
NH2
H H
O H H
H C C
N C C H
H
H H H
Figure G44 Summary of reactions of aromatic compounds and acyl chlorides.
Worked examples
Design a reaction pathway showing all reagents and conditions
1-methyl-2-nitrobenzene is also
for the conversion of benzene to 1-methyl-2-nitrobenzene.
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 CH3
conc. HNO3
conc. H2SO4 NO2
CH3Cl
AlCl3 heat under reflux
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 NO2
conc. HNO3
conc. H2SO4 CH3Cl
heat under reflux 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 H
H C C H
H H H H
Cl2 H
H C C H H C C Cl
UV light AlCl3
H H H H
Exam-style questions
1 a Draw the full structural formula of 2-methylpent-2-ene. [1]

b i Draw the full structural formula of the major product formed when 2-methylpent-2-ene reacts with
hydrogen bromide in the dark. [1]
ii Write the mechanism for this reaction and explain the formation of the major product. [5]
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. [1]
ii Give the structures of two possible alcohols that would produce 2-methylpent-2-ene via this reaction. [2]
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. [2]
iv Describe using curly arrows the mechanism for the formation of 2-methylpent-2-ene from one of the
alcohols in part ii. [4]
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. [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]
c State the type of reaction between 2,4-dinitrophenylhydrazine and ethanal. [1]
d Ethanal reacts with hydrogen cyanide.
i Write the mechanism for this reaction using curly arrows. [4]
ii Write a balanced equation for the reaction that occurs when the organic product of this reaction
is boiled with aqueous acid. [2]
3 a Draw the isomers of C6H4Cl2 and explain how the number of isomers provides evidence for a
delocalised structure of benzene. [4]
b There are several isomers of C7H7Cl that contain a benzene ring.
i Draw the structure of one isomer that will react with aqueous sodium hydroxide to form a
compound with molecular formula C7H8O. [1]
ii Draw the structure of one isomer which will not react with aqueous sodium hydroxide and explain
why it does not react. [3]
4 a Explain why chloroethanoic acid is a stronger acid than ethanoic acid. [2]
b i Write an equation for the dissociation of phenol in aqueous solution. [2]
ii Predict and explain the relative acidities of 2-methylphenol and phenol. [3]
c Explain why dimethylamine is a stronger base than methylamine. [2]
5 2-chloropropane can form a Grignard reagent.

a State the reagents and conditions for the conversion of 2-chloropropane to a Grignard reagent. [2]
b Draw the full structural formula of the Grignard reagent formed. [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. [1]
H H O H
(i) H C C C C H
H H H
C2H5Mgl +
(ii) H / H2O
HL 6 Ethanoyl chloride and ethanoic anhydride react in the same way with nucleophiles.
a i Draw the structure of ethanoyl chloride. [1]
ii Write an equation showing full structural formulas for the reaction between ethanoyl chloride
and propan-2-ol. [2]
iii To what class of compounds does the organic product in part ii belong? [1]
iv Draw out the mechanism for the reaction between ethanoyl chloride and water. [4]
b i Draw the structure of propanoic anhydride. [1]
ii Draw the full structural formulas of both organic products of the reaction between
propanoic anhydride and ammonia. [2]
7 a The compound shown can be formed from benzene in a single step.

H H O
H C C C
H H
i Write an equation, showing all reagents and conditions for the formation of this compound
from benzene. [2]
ii Draw the mechanism for the reaction in part i. [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 C CH3
NO2

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G Further organic chemistry

G1 Electrophilic addition reactions Learning objectives

Reactions of alkenes • Explain the electrophilic

The reaction of ethene with hydrogen bromide

pair of electrons from double bond electron from H

this C has lost an electron therefore

Figure G2 Movement of electrons in reaction of ethene with hydrogen bromide.

The main/major product (the minor product is usually only present in

When H–X adds to the double bond of an alkene, the H atom

Markovnikov’s rule can be used to predict the major product formed

The explanation for Markovnikov’s rule depends on the stability of

The secondary carbocation is more stable than the primary carbocation.

Reaction of ethene with bromine

Although the bromine is not originally polar, as it approaches the high

The mechanism is, however, probably better represented as shown in

Figure G7 The reaction of ethene with bromine showing the formation of a

Figure G8 The reaction of ethanal with hydrogen cyanide.

The product of the reaction is called a cyanohydrin.

The reaction is generally speeded up by addition of a small amount of

Figure G9 The reaction of propanone with HCN.

Hydrolysis – breaking a bond with

Hydrolysis can also be brought about by refluxing with aqueous alkali.

the H. – O has extra electron, therefore

G3 Elimination reactions Learning objectives

Alcohols may be dehydrated to produce alkenes

With some alcohols more than one organic product is possible,

Figure G13 Possible products when 3-methylbutan-2-ol is dehydrated.

Mechanism for the elimination of water

H+ from either H2SO4 or H3PO4

Figure G15 The reaction between 2,4-DNPH and propanone.

Determination of the melting Test yourself

Learning objectives G5 Arenes

The structure of benzene

Figure G21 Formation of the benzene delocalised system.

Evidence for the structure of benzene

Bond Compound Bond length / nm

The delocalised structure of benzene suggests a C–C bond length

cyclohexene cyclohexane (C6H12)

Cyclohexene contains one C=C whereas cyclohexa-1,3,5-triene (Kekulé

+ 3H2 ∆H = −360 kJ mol−1

cyclohexa-1,3,5-triene cyclohexane (C6H12)

The enthalpy change when benzene undergoes complete

+ 3H2 ∆H = −205 kJ mol−1

benzene cyclohexane (C6H12)

If an enthalpy level diagram is drawn for the hydrogenation reactions

Figure G22 Comparative enthalpy changes for the hydrogenation reactions of

+ 2H2 ∆H = −227 kJ mol−1

cyclohexa-1,3-diene cyclohexane (C6H12)

The number of isomers of C6H4Cl2

Benzene Kekulé benzene

methylbenzene nitrobenzene phenol chlorobenzene benzoic acid / benzene carboxylic acid

Relative rates of hydrolysis of halogenated

Chlorobenzene does not undergo hydrolysis (nucleophilic substitution)

Halogen atom attached directly to + NaOH NO REACTION under normal conditions

To all extents and purposes halogenated benzene compounds

attached directly will be substituted

This has two effects:

Learning objectives G6 Organometallic chemistry

The solvent must be dry as Grignard reagents react vigorously with

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

H H The structure of the Grignard reagent is shown in Figure G24. There is a

H+ Note that the length of the carbon

This can be shown more conveniently in a reaction scheme by putting