You are on page 1of 47

G Further organic chemistry

G1 Electrophilic addition reactions

Learning objectives

Reactions of alkenes

Most reactions of alkenes involve an electrophilic addition mechanism.

An electrophile is a reagent (a positively charged ion or the


positive end of a dipole) which is attracted to regions of high
electron density and accepts a pair of electrons to form a covalent
bond.

Explain the electrophilic


addition reactions of alkenes
Predict and explain the
formation of the major product
when HX reacts with an
unsymmetrical alkene

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
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

The curly arrow represents


movement of two electrons.

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 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.

pair of electrons from double bond

C1
C2

H Br

electron from H

H
H C1 H
Br
H C2+
electron from C2
H

HL

The bond breaks.

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

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

Figure G4 Heterolytic ssion.

C2 has lost an electron (this electron is now in the CH bond) and


thus C2 has a positive charge. The intermediate formed is called a
carbocation (a positively charged organic ion with a positive charge
on C). The Br atom has gained an electron from the HBr bond and is
therefore a negatively charged bromide ion. In the second stage the Br
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 HBr bond breaks, is
called heterolytic fission since the bond breaks so that both electrons
go to the same atom (Figure G4).

The reaction of propene with HBr


When HBr adds to propene, two products are possible:
H

H
H

H
H

Br

Br

C
H

minor product
1-bromopropane

Br

major product
2-bromopropane

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


very small amounts) may be predicted from Markovnikovs rule:
When HX 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.

Those who have shall get more.

Markovnikovs rule can be used to predict the major product formed


when HX adds to any unsymmetrical alkene. Thus, when HCl adds to
2-methylpropene, the H atom of the HCl becomes attached to C1 as this
has two H atoms already attached, rather than C2, which has no H atoms
attached.
H
C

H
H3C

H
H

H
H

Cl

H3C

Cl

C
H

The explanation for Markovnikovs 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 HBr are:
H

C+

C+

A primary carbocation has one C


atom attached to the C bearing the
positive charge.
A secondary carbocation has
two C atoms attached to the C
bearing the positive charge.

primary
carbocation

secondary
carbocation

The secondary carbocation is more stable than the primary carbocation.


This is due to the electron-releasing effect of alkyl groups. There are
two alkyl groups next to the positively charged C in the secondary
carbocation but only one in the primary carbocation. Two alkyl groups
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
more likely to be formed.
The electron-releasing effect is roughly independent of the size
of the alkyl group, i.e. a methyl group donates approximately the
same amount of electron density as an ethyl group.
In general, the more alkyl groups there are attached to C+, the more
stable the carbocation (Figure G5).

CH3

CH3

CH3

C+

C+

C+

primary carbocation

CH3

H3C

secondary carbocation

CH3

tertiary carbocation

increasing stability of carbocation

Figure G5 Stability of carbocations.

Markovnikovs rule may also be used to explain the products


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 BrCl with propene:

Alkyl groups have an electronreleasing effect. This is also called a


positive inductive effect.

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

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

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

Examiners tip
You only need to learn one of
these mechanisms.

H
H

+ Br2

non-polar

solvent

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.
The mechanism can be shown in two different ways. The first is exactly
analogous to the reaction of HBr with ethene, i.e. via a carbocation
intermediate (Figure G6).

H
C

Br

Br

C+

H
Br
:Br

Br

Br

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
C
C
H

In the bromonium ion the


bridging Br has donated a lone pair
to the C+, which stabilises the ion.

Br
H

Br

H
Br+
:Br

Br

Br

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
when the following alkenes react with HCl:
a but-1-ene
b 3-methylbut-1-ene
c 2,4-dimethylpent-2-ene

G FURTHER ORGANIC CHEMISTRY

2 State the name of the major product formed when


but-1-ene reacts with ClBr.

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

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
nucleophilic addition.

Reaction with hydrogen cyanide


The reaction of ethanal with hydrogen cyanide is shown in Figure G8.
Just as with the reaction of alkenes, the second component of the double
bond ( component) is broken and the HCN is added across it; H adds
to the O.
H
H

O
C

+ HCN

HCN(aq) + alkali

Describe and explain the


nucleophilic addition reactions
of aldehydes and ketones with
HCN
Write equations for the
hydrolysis of cyanohydrins

This reaction is important as it


introduces an extra C atom into
the carbon chain.

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
H
H

C
H

O
C

H
C

H + HCN

HCN(aq) + alkali

N
2-hydroxy-2-methylpropanenitrile

Figure G9 The reaction of propanone with HCN.

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 [

Figure G10 The electrons of the CN ion.

G FURTHER ORGANIC CHEMISTRY

H+ from dissociation of HCN

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

Figure G12 H+ is removed from the undissociated HCN.

Hydrolysis breaking a bond with


water.

Nitrile groups may be hydrolysed to form a


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:
CH3

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

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

H3C

C
CN

G FURTHER ORGANIC CHEMISTRY

H + H2O + NaOH

H2O / OH reflux
hydrolysis

H3C

H + NH3

COONa+

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

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

4 Draw the structural formulae of the products


formed when each of the products formed in
Question 3 is boiled with aqueous acid.
5 Write balanced chemical equations using
condensed structural formulae to show the
reaction of propanal with HCN followed by
boiling the product with aqueous acid.

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.

Curly arrow shows a bonding pair becoming


a lone pair. The arrow goes from the middle
of the bond to the atom.

C +
H
X
O
C

pair of electrons going from being a lone pair


on X to a bonding pair between C and X

O
C
X

O has extra electron, therefore


negatively charged

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
replaced by other atoms or groups. This results in the formation of a
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

CH3 H

conc. KOH in ethanol


heat under reflux

Describe and explain the


elimination of water from
alcohols

H
C

H
C

H3C

+H

Cl

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:
CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

The H and OH are always


removed from adjacent C atoms.

conc. H2SO4

H
C

heat

+ H2O

With some alcohols more than one organic product is possible,


e.g. when 3-methylbutan-2-ol is dehydrated 3-methylbut-1-ene and
2-methylbut-2-ene are possible products (Figure G13).
When butan-2-ol is dehydrated but-1-ene and cis- and trans-but-2-ene
are all possible products.

See Higher Level section on


page 487 of Chapter 10 in the
Coursebook for an explanation of
cis and trans.

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

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
by the sulfuric acid or phosphoric acid. This creates a group that can more
readily leave than the OH group. In the third stage a pair of electrons
from the CH bond is used to form the second component of the C=C.
The H+ is used up in the first step but is regenerated in the last step.
So it is acting as a catalyst it is not used up in the reaction.

Elimination by this mechanism is


more likely with a tertiary alcohol
than with a primary alcohol as a
tertiary alcohol forms a more stable
carbocation.

H+ from either H2SO4 or H3PO4

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.

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G4 Additionelimination reactions

Learning objectives

The structure of 2,4-dinitrophenylhydrazine (2,4-DNPH) is shown in


Figure G14.
H
H

Write equations for the reaction


of 2,4-dinitrophenylhydrazine
with aldehydes and ketones

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.

2,4-dinitrophenylhydrazine reacts with aldehydes and ketones in an


additionelimination reaction. The reaction is so-called because the 2,4DNPH 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
shown in Figure G15.
H

H
C

H
H

H
H

N
N

N
N

NO2
+

C
C
H

NO2
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
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.

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

H
H

H
H

C
H

N
N
NO2

NO2
butanal 2,4-dinitrophenylhydrazone

Figure G17 The structure of the product


formed when butanal reacts with 2,4-DNPH.

Determination of the melting


point of hydrazone is quite an oldfashioned method of identifying
compounds and nowadays infrared/
nuclear magnetic resonance
spectroscopy would be used.

The structure of the product formed when butanal


(CH3CH2CH2CHO) reacts with 2,4-DNPH is shown in Figure G17.
The reaction with 2,4-DNPH is used as a test for the presence of
the carbonyl (C=O) group in aldehydes and ketones. A few drops of
the aldehyde or ketone is added to an acidified solution of 2,4-DNPH
in methanol (sometimes called Bradys reagent). The solution is orange
and when the aldehyde/ketone is added, a yellow-orange precipitate is
formed. The formation of the precipitate indicates the presence of an
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
2,4-dinitrophenylhydrazone.
If the melting point of these hydrazone crystals is determined and the
values compared with those in tables, exactly which aldehyde/ketone was
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.

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

Benzene and aromatic compounds

Explain the evidence for a


delocalised structure for benzene
Explain the relative rates of
substitution of halogens atoms
attached directly to a benzene
ring or in the side chain

Compounds that contain a benzene ring are called aromatic


compounds or arenes.

The structure of benzene

Figure G18 Kekul benzene.

Figure G19 Structure of benzene.

10

G FURTHER ORGANIC CHEMISTRY

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
Kekul and is usually called Kekul 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 cyclohexa1,3,5-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
atoms and one to an H atom) (Figure G20). The remaining electrons form
CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

a delocalised system of six electrons, which is represented by the circle in


the centre of this structure. These six electrons are not localised between
individual C atoms in double bonds but rather spread over the whole ring.
Delocalisation electrons shared between three or more atoms.

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).

Figure G21 Formation of the benzene delocalised system.

Evidence for the structure of benzene


Carboncarbon bond lengths
All CC bond lengths are equal in benzene and intermediate in length
between a CC single bond and a C=C double bond (Table G1).
If the structure of benzene were cyclohexa-1,3,5-triene (Kekul
benzene) then it would be expected that there would be three short
C=C bonds (approximately 0.133 nm) and three longer CC bonds
(approximately 0.154 nm).
Bond

Compound

C=C

ethene

0.133

CC

ethane

0.154

CC

benzene

0.139

CC bond lengths may be


determined by X-ray crystallography.

Bond length / nm

Table G1 Bond lengths in ethene, ethene and benzene.

The delocalised structure of benzene suggests a CC bond length


between that of a CC 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 CC.
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 mol1.

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

11

H = 120 kJ mol1

+ H2

cyclohexene

cyclohexane (C6H12)

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


benzene) contains three C=C. It would, therefore be expected that the
enthalpy change for the complete hydrogenation of cyclohexa-1,3,5-triene
(Kekul benzene) to cyclohexane would be 3 120, i.e. 360 kJ mol1.

H = 360 kJ mol1

+ 3H2

cyclohexa-1,3,5-triene

cyclohexane (C6H12)

The enthalpy change when benzene undergoes complete


hydrogenation to cyclohexane is, however, only 205 kJ mol1.

H = 205 kJ mol1

+ 3H2

benzene

cyclohexane (C6H12)

If an enthalpy level diagram is drawn for the hydrogenation reactions


of benzene and cyclohexa-1,3,5-triene (Kekul benzene) it is seen that
benzene is 155 kJ mol1 more stable than expected, i.e. 155 kJ mol1 more
stable than would be predicted if it had the structure with alternating
single and double carboncarbon 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 mol1.
This is reasonably close to 2 120 kJ mol1 and although there is some

Enthalpy

155 kJ mol1
H = 360 kJ mol1
H = 205 kJ mol1

cyclohexane

Figure G22 Comparative enthalpy changes for the hydrogenation reactions of


benzene and Kekul benzene.

12

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

delocalisation of electrons in this structure, it is not nearly as extensive as


in benzene.
H = 227 kJ mol1

+ 2H2

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 Kekul 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 CC single bond or a
C=C double bond.
Benzene

Cl

Kekul benzene

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 (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

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

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).

G FURTHER ORGANIC CHEMISTRY

13

Naming aromatic compounds/arenes


The names of some simple aromatic compounds are shown here.
O
CH3

OH

NO2

OH

C
Cl

methylbenzene

phenol

nitrobenzene

benzoic acid / benzene carboxylic acid

chlorobenzene

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 + OH

heat

H + Cl

Chlorobenzene does not undergo hydrolysis (nucleophilic substitution)


reactions with sodium hydroxide under normal conditions.
Cl

Halogen atom attached directly to


the ring.

+ NaOH

NO REACTION under normal conditions

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

Here the halogen atom is said to be


in the side-chain.

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

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

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

overlap of lone pair


with benzene system

lone pair on CI

This has two effects:


it strengthens the CCl bond, so that it is less easily broken (the
reaction involves breaking the CCl 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 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.

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

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

Describe the formation of


Grignard reagents
Write equations for reactions of
Grignard reagents

Organolithium compounds are also


commonly used.

Organometallic compounds are organic molecules which also contain a


metal atom. More precisely, they contain a bond between a carbon atom
and a metal atom. These are useful in organic synthesis.
The most commonly used organometallic reagents are Grignard
reagents. These may be formed when a halogenoalkane is reacted with
magnesium turnings using a dry ether (usually ethoxyethane, (C2H5)2O)
as the solvent.

Grignard is pronounced as
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:


The Grignard reagent cannot be
isolated from solution.

For example:
dry ethoxyethane

C2H5Br + Mg C2H5MgBr
Mg

Br

Figure G24 Grignard reagent structure.

This would, however, be rather a


waste of a Grignard reagent!

16

dry ethoxyethane

RX + Mg RMgX

G FURTHER ORGANIC CHEMISTRY

ethylmagnesium
bromide

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


covalent bond between the Mg and the C and between the Mg and the Br.
C is significantly more electronegative than Mg and the Grignard
reagent acts in reactions as R, that is, a negatively charged alkyl group.
The alkyl group is a nucleophile and will attack positive regions in a
molecule.
1 Reaction of Grignard reagents with water
An alkane is formed, e.g.
C2H5MgI + H2O C2H6 + Mg(OH)I
CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

2 Reaction of Grignard reagents with carbon dioxide


A carboxylic acid is produced. The salt of the carboxylic acid is first
formed and then the acid is generated by adding a dilute strong acid
such as sulfuric acid, e.g.
C3H7COOMgBr

C3H7MgBr + CO2
propylmagnesium
bromide

The conditions for the first


step must be completely free of
water pass dry CO2 through
the Grignard dissolved in dry
ethoxyethane.
Note that the length of the carbon
chain has increased by one C.

H+

C3H7COOMgBr + H2O C3H7COOH + Mg(OH)Br


butanoic acid

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


the reagents for both steps on one arrow:

C3H7MgBr

(i) CO2

(ii) H+ / H2O

O
C
O

The reactions of Grignard reagents may be more easily understood and


remembered if we consider the first stage of the mechanism. The electrons
from the CMg bond are used to form a bond to a + C atom.
O

Examiners tip
The mechanism is not required
for the examination.

C +

O
Mg

Br

O
C

We could also show this more simply as a negatively charged alkyl


group attacking a + C.

C +

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
C2H5Mgl

(ii) H+ / H2O

H
H
H

H + Mg(OH)l

pentan-3-ol

Note the increase in the length of the carbon chain.

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

17

Aldehydes (with the exception of methanal) will form secondary


alcohols when reacted with a Grignard reagent. Methanal forms a
primary alcohol:
(i)

Br
Mg H
H

C
H

(ii) H+ / H2O

+ Mg(OH)Br

butan-1-ol

Ketones form tertiary alcohols when reacted with Grignard reagents:


(i)

Br
H

Mg H
H

H
H

(ii) H+ / H2O

H + Mg(OH)Br

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
+ C of the carbonyl group (Figure G25).
Some reactions of Grignard reagents are shown in Figures G26 and G27.

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

Figure G26 Some reactions of Grignard reagents.

18

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

H
O

R2

R2

R1

R1

H
H

conc. H3PO4 / heat

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

conc. H3PO4 / heat

H
H
R1

elimination mechanism

conc. H3PO4 / heat

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

10 a Name two aldehydes that could be reacted


with suitable Grignard reagents to produce
pentan-2-ol.
b True or false? 2-Methylpropan-2-ol can be
made by reacting propanal with a suitable
Grignard reagent.
c Give the structural formula of a Grignard
reagent that can be reacted with propanone
to form 2-methylhexan-2-ol.

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

19

G7 Reaction pathways

Learning objectives

We can use the reactions discussed in the previous section to design


reaction pathways.

Deduce reaction pathways using


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

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

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

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

The Grignard reagent must therefore be reacted with pentan-3-one.


H
Br
Br
H

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

12 Give reaction sequences for the following


transformations:
a 2-chloropropane to propane
b 2-chloropropane to 2-methylpropanoic acid
c propan-1-ol to 2-chloropropane

G8 Acids and bases

Learning objectives

Acidity

Carboxylic acids are weak acids that dissociate partially in aqueous


solution according to the equation:

O
R

C
O

H
+ H2O

C
O

+ H3O

Explain the relative acidities of


substituted carboxylic acids
Explain the relative acidities of
substituted phenols
Explain the relative basicities of
ammonia and amines

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
CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

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

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

ethanol

16

4-methylphenol

10.26

2,4,6-trinitrophenol

HL

The carboxylate ion actually has both CO distances equal and


between the length of a CO single bond and a C=O double bond.
It is, therefore, better described by the delocalised structure:

O
R

C
O

H
C

0.42

Cl
C
H

+ H+

Cl

ethanoate ion

Cl

ethanoic acid

The greater acidity of


chloroethanoic acid is sometimes
explained in terms of the stability
of the acid. The Cl atom is
electron-withdrawing and pulls
electron density from the COOH
group. This makes the H of the
COOH group more positive and
thus more likely to be lost as a
proton.

H
O

Table G2 pKa values.

C
O

+ H+

chloroethanoic acid

chloroethanoate ion

The difference in acidity can be explained by considering the stability


of the anion (conjugate base) formed. The Cl is a very electronegative
atom and, in the chloroethanoate ion, pulls electron density away from
the COO group (Figure G28). Since the COO group is less negative,
it attracts the H+ ion back less strongly. The conjugate base is, therefore,
more stable. A more stable conjugate base indicates a greater tendency to
dissociate and, therefore a stronger acid.

O
C

electron density withdrawn


from COO group

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.

Figure G28 The chloroethanoate ion.

Trichloroethanoic acid is a stronger acid than chloroethanoic


acid
Cl
Cl

Cl
O

Cl
trichloroethanoic acid

An electron-withdrawing effect
is sometimes called a negative
inductive effect.

22

G FURTHER ORGANIC CHEMISTRY

Cl

O
C

+ H+

Cl
trichloroethanoate ion

Again, we will consider the stability of the anion/conjugate base


formed. Three very electronegative Cl atoms have a greater electronwithdrawing effect than just one. More electron density is thus pulled
away from the COO group making it less negative and less likely
CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

to attract back the H+ (Figure G29). The trichloroethanoate ion


is thus relatively more stable than the chloroethanoate ion and so
trichloroethanoic acid dissociates more.

Cl
Cl

Cl

Chloroethanoic acid is a stronger acid than iodoethanoic acid


I
C

O
C

H
O

O
C

more electron density


withdrawn from COO group

Figure G29 The trichloroethanoate ion.


+ 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
H

O
C
O

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


Ethanoic acid has an electron-releasing group attached to the
COOgroup in the anion. This increases the electron density on the
COO group and therefore the H+ is attracted back more strongly (Figure
G30). This means that the conjugate base is less stable for ethanoic acid
and, it is, therefore a weaker acid.
O
H

H
O

methanoic acid

H
H

O
C

electron density donated


to COO group

Figure G30 The ethanoate ion.

+ H+

H
O

ethanoic acid

methanoate ion

O
C
O

+ H+

H
ethanoate ion

The electron-releasing effect of an alkyl group is often called a


positive inductive effect.

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

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.

The effect of distance of the Cl group from the COOH group on


acid strength
2-Chlorobutanoic acid is a stronger acid than 4-chlorobutanoic acid.
The further the Cl is from the COO group in the anion, the smaller
the electron-withdrawing effect it has on it.

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

Phenol reacts with blue litmus and


forms salts with sodium hydroxide.
It is still however a weaker
acid than carboxylic acids.
Phenol may be distinguished from
carboxylic acids by the fact that it
will not liberate CO2 from sodium
hydrogencarbonate solutions, i.e. it
is a weaker acid than carbonic acid.

Phenol is a signicantly stronger acid than aliphatic alcohols


such as ethanol
The dissociation of phenol may be shown as:
C6H5OH

C6H5O + H+

or, showing structures:


H
O

+ H+

Phenol is more soluble in sodium


hydroxide solution than in water. It
reacts with the sodium hydroxide
to form an ionic salt (C6H5ONa+)
and therefore there are stronger
interactions with water molecules.

phenol

phenoxide ion

The dissociation of ethanol is:

ethanol

O+ H+

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 electrondonating alkyl group.
24

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

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 electrondonating 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
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

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

25

O
N

O
+

Figure G32 Lewis structure for (a) the NO2


group attached to a benzene ring and (b)
showing the charges.

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.
The NO2 group is electron-withdrawing because it consists of three
very electronegative atoms and there is no lone pair on the N that could
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
is often shown with a positive charge (as it is has essentially given one
electron to the O) (Figure G32b).

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

Table G3 The formula and pKb of various bases.

26

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

In all of these compounds the N is the most electronegative atom and


will have a small negative charge.

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

Figure G35 Hydrogen bonding of the H


atoms in the (a) dimethylammonium ion
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 signicantly weaker base than ammonia


C6H5NH2 + H2O
phenylamine

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

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

Amines are more soluble in


hydrochloric acid than in water
due to the formation of the
ionic salt and, therefore, stronger
interactions with water molecules.

G FURTHER ORGANIC CHEMISTRY

27

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 BrnstedLowry acid. NaOH
is a stronger base than the amine
and therefore can take the proton
away from it.

This can be shown as an ionic equation:


CH3NH3+ + OH CH3NH2 + H2O

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

Describe the reactions of acyl


chlorides with nucleophiles
Explain the mechanism for the
reaction of acyl chlorides with
nucleophiles
Describe the reactions of acid
anhydrides with nucleophiles

HL

G9 Additionelimination reactions
Acyl chlorides (acid chlorides)
The basic structure of an acyl chloride is:
O
R

C
Cl

Acyl chlorides may be prepared by reacting carboxylic acids with


SOCl2 or PCl5.
They are named as alkanoyl chloride, e.g.
H
H

O
C

Cl

O
H

CH3 H

O
C

Cl

H
ethanoyl chloride

butanoyl chloride

Cl
3-methylbutanoyl chloride

These are extremely reactive and react to add an acyl group to


nucleophiles with the elimination of HCl.
O
R

acyl group

1 Reaction with water


Acyl chlorides react violently with water to from carboxylic acids.
H
H

+
Cl

28

G FURTHER ORGANIC CHEMISTRY

O
H

O
H

O
C

ethanoyl chloride

ethanoic acid

+ H

Cl

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

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

acyl group added to O

Cl H
HCl eliminated

Figure G36 Reaction of an acyl chloride with


water.

H + H

Cl

Cl
H

butanoyl chloride

ethyl butanoate

An alkaline solution of phenol reacts with benzoyl chloride to form


phenyl benzoate:

This reaction is usually carried out


in the presence of a base such as
pyridine (C5H5N).

O
O

OH

Cl

+ 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

O
C
Cl

+
H

H
H

O
C

+ H

Cl

NH2

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

O
C

+
Cl

H
H

+ H

Cl

ethylamine

N-ethylpropanamide

Again, the balanced equation should, more correctly, be written as:


CH3CH2COCl + 2CH3CH2NH2
CH3CH2CONHCH2CH3 + CH3CH2NH3Cl

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

29

HL

The additionelimination 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:

C +

H
Cl

Cl

+ Cl
X

The nucleophile attacks the + C of the C=O group. The


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 CCl bond breaks.
Now, if we look at the reaction with water:

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+

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.

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

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

This can be regarded as being formed from two molecules of carboxylic HL


acid with water removed (Figure G37).
Acid anhydrides are named according to the carboxylic acid from
which they are derived, e.g.

H
H

O
C

H
O
H3C

CH3CH2

H3C

ethanoic anhydride

O
H3C

O
H

Figure G37 Formation of an acid anhydride.

O
C

propanoic anhydride

C
O +

C
H

Acid anhydrides are actually made


by the reaction between an acyl
chloride and the sodium salt of a
carboxylic acid.

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

Note that acid anhydrides are less


reactive than acyl chlorides.

ethanoic acid

2 Reaction with alcohols


Acid anhydrides react when heated with alcohols to form esters:
O
CH3CH2

CH3CH2

O + O

H + H

ethyl propanoate

propanoic anhydride

O
O
H3C
H3C

C
O +

propanoic acid

Ethanoic anhydride can be heated with 2-hydroxybenzoic acid to make


aspirin:
H

O
C

Aspirin contains an ester linkage.

C
O

C
O

C
H

H
+H

O
C

ethanoic 2-hydroxybenzoic acid


anhydride

O O

aspirin

ethanoic acid

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

The systematic name of aspirin is


2-ethanoyloxybenzenecarboxylic
acid!

G FURTHER ORGANIC CHEMISTRY

31

HL 3 Reactions with ammonia

When excess concentrated aqueous ammonia solution is reacted with


an acid anhydride a primary amide is formed:
O

CH3CH2

CH3CH2

O +
H
O

H
H

O
C
NH2

+ H

propanamide

propanoic anhydride

O
C
O

propanoic acid

4 Reactions with amines


When acid anhydrides are reacted with amines N-substituted amides
are formed:
O
CH3CH2

CH3CH2

O +
H
O

propanoic anhydride

ethylamine
ethanamine

+ H

N-ethylpropanamide

O
C
O

propanoic acid

Ethanoic anhydride reacts with 4-aminophenol at room temperature to


form paracetamol:
OH
H3C
H3C
NH2
4-aminophenol

C
O

The systematic name


of paracetamol is N-(4hydroxyphenyl)ethanamide!

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

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G10 Electrophilic substitution reactions


Benzene reacts with electrophiles via an electrophilic substitution reaction.
The general mechanism is:

X+

X + H+

HL

Learning objectives

electrophile

In the first step a pair of electrons from the benzene delocalised


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
of the delocalised system. The delocalised system can then only extend
over the other five C atoms (Figure G38). This is shown by the partial
ring. There were originally six electrons in the delocalised system (one
from each C atom) but two are now used to form the CX bond, which
leaves only four electrons shared over five C atoms; the ring thus has a
positive charge.

Describe the chlorination,


alkylation, acylation and
nitration reactions of benzene
Explain the mechanism for
electrophilic substitution
Describe the chlorination,
alkylation, acylation and
nitration reactions of
methylbenzene
Explain the relative rate of
electrophilic substitution in
benzene and substituted benzene
rings
Explain the position of
substitution in substituted
benzene rings

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.

Another way of thinking about this


is that the initial reaction involved
a neutral species reacting with a
positively charged species, therefore
the intermediate must also have a
positive charge.

The nitration of benzene


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

+ HNO3

NO2

conc. HNO3
conc. H2SO4
heat under reflux
60C

C6H6 + HNO3

+ H2O
nitrobenzene

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

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

33

HL

The mechanism is basically the same as shown in the general


mechanism on page 33:
NO2+

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.

All reactions involving AlCl3 must


be carried out in the absence of
water as AlCl3 reacts with this.
Examiners tip
This is the equation you need
for the examination.

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.

Formation of the electrophile


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:
Cl2 + AlCl3 [AlCl4] + Cl+
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
Cl

34

G FURTHER ORGANIC CHEMISTRY

Cl

Al

Cl
Cl

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

The mechanism is basically the same as the general mechanism given


on page 33:
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

The first stage in this mechanism


can be regarded as a Lewis acid
base reaction: the benzene ring
is the Lewis base (electron pair
donor) and the Cl+ the Lewis acid
(elecron pair acceptor).

Cl + HCl + AlCl3
catalyst re-formed

Cl

Cl

Al

Cl
Cl

Alkylation (also known as FriedelCrafts 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

CH3

CH3
C

+ H3C

CH3

AlCl3
5 C

+ HCl

Cl
(1,1-dimethylethyl)benzene

Formation of the electrophile


(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
+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

CH3 + HCl + AlCl3


catalyst re-formed

Cl
Cl

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

35

HL

Acylation (also known as FriedelCrafts 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
H

The benzene ring here is named as


a phenyl substituent.

H
H
+H

AlCl3
50
C
Cl

O
C

H
+ HCl
phenylethanone

Formation of the electrophile


This is a similar reaction to that already seen on pages 3435 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

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

Some of the electrophilic substitution reactions of methylbenzene are


shown in Figure G39.

36

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

CH3

O
C

HL

CH3
CH3

H
H3C

O
C

H
O

Cl

H
AlCl3

CH3

CH3

CH3

conc. HNO3
conc. H2SO4

NO2

heat under reflux

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

If methylbenzene is reacted with chlorine in the presence of UV


light then side-chain substitution occurs where a hydrogen atom in
the methyl group is substituted by a Cl atom. This involves a free radical
substitution mechanism as for alkanes.
H
H

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

RCH3 + Cl RCH2 + HCl


RCH2 + Cl2 RCH2Cl + Cl
plus a termination step.

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

37

HL

Multiple substitution can occur to form (dichloromethyl)benzene and


(trichloromethyl)benzene.
H
H

H
H

Cl
H

Cl

Cl
Cl

Cl

Cl2

Cl2

Cl2

UV

UV

UV

(chloromethyl)
benzene

(dichloromethyl)
benzene

Cl

(trichloromethyl)
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

Cl

Cl

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

OH

CH3
CH3

NO2

Cl

IUPAC name 1-chloro-2-methylbenzene 1-methyl-2-nitrobenzene


Alternative
names

2-chloromethylbenzene

2-nitromethylbenzene

2-methylchlorobenzene

2-methylnitrobenzene

4-chlorophenol

Table G4 Naming multi-substituted benzene rings.

38

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

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
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

CH3
and other alkyl
group

CH3

OH

OH

CH3

Rate of substitution
relative to benzene

Nature of effect on electrophilic


substitution

faster

activating and 2,4-directing

faster

activating and 2,4-directing

slower

deactivating and 3-directing

Cl

Cl
OH
Cl

OH
Cl

Cl

NO2

CH3

NO2

Cl

Cl

Cl
Table G5 Reactions of substituted benzene rings.

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

39

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?


lone pair

C
C

C
C

O
donation
into ring

Figure G40 Activation of the benzene 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.

Reaction of phenol with chlorine

Phenol is also made more reactive


in water since it is acidic and
produces the phenoxide ion
C6H5O. The negative charge
on the O means withdrawal
is reduced and donation is
increased, therefore the ring is
more attractive to electrophiles.

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
2,4,6-trichlorophenol (no halogen carrier required):
OH

OH
Cl

Cl

+ 3Cl2

+ 3HCl
Cl
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 electrons from the ring onto the NO2 group.

Position of substitution in arenes

Figure G41 Resonance structures of


benzene.

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 Kekul 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
resonance hybrid of these two structures not one or the other but
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.
40

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

The structure of nitrobenzene showing the bonds involved is shown in HL


Figure G42. The nitrogen forms a dative covalent bond to one of the O
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.
some resonance forms of the intermediate

substitution
at position 2

X
H

O
+

Figure G42 The structure of nitrobenzene


showing charge on N.

X+

N
X
H

X
H

2 positive charges
next to each other
curly arrows represent delocalisation of electrons

A similar situation occurs if substitution occurs at position 4.

+
+
X+

2 positive charges
next to each other

substitution
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.

X+

N
+

X
H

N
+

X
H

X
H

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.
some resonance forms of the intermediate

O+

X+

substitution
at position 2

X
H

X
H

intermediate stabilised
by donation of lone pair
into ring

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

41

HL

The same stabilisation is possible when substitution occurs at position 4.


some resonance forms of the intermediate

O+

+
X+

substitution
at position 4

intermediate stabilised
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

X
H

substitution
at position 3

C
C

donation
into ring

H
H

C
C

Figure G43 The electron-releasing effect of


the methyl group.

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

G FURTHER ORGANIC CHEMISTRY

delocalisation not possible


as C has 4 bonds

Position of substitution in methyl benzene


The methyl group has an electron-releasing effect and this also stabilises
the intermediate when substitution occurs at positions 2 and 4.
The electron-releasing effect of the methyl group comes from the
overlap of the electron density in the CH bond with a p orbital on an
adjacent atom (Figure G43).
The stabilising effect of the methyl group on the intermediate can be
shown as:
H

C
X+

substitution
at position 2

X
H

intermediate stabilised by
donation of electrons into ring

As for phenol, this stabilisation is only possible when substitution


occurs at positions 2 or 4.

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

An alternative way of explaining the directing


effect of substituent groups (not for examinations)
is in terms of the charge distribution in the initial
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
6 and, therefore, there is more electron density at
positions 3 and 5 and an electrophile is attracted to
these positions.
electron-releasing
group

This can also be shown using resonance forms.


H
O

O+

O
N

electron density increased


at position 2

electron density reduced


at position 2

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

16 The molecule in Question 15a can react with


chlorine under suitable conditions to form five
possible monochlorinated products. Draw the
structures of the possible products and suggest
which is least likely to be formed when the
molecule reacts with chlorine.

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

43

HL

Learning objectives

Deduce reaction pathways using


the reactions in the sections
above.

G11 Reaction pathways


Reaction pathways
Some reactions of aromatic compounds and acyl chlorides are summarised
in Figure G44.
CH2OH

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

heat under reflux

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

Figure G44 Summary of reactions of aromatic compounds and acyl chlorides.

44

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

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

heat under reflux

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

heat under reflux

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

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

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]

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.
ii Write a balanced equation for the reaction that occurs when the organic product of this reaction
is boiled with aqueous acid.
3 a Draw the isomers of C6H4Cl2 and explain how the number of isomers provides evidence for a
delocalised structure of benzene.
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.
ii Draw the structure of one isomer which will not react with aqueous sodium hydroxide and explain
why it does not react.
4 a Explain why chloroethanoic acid is a stronger acid than ethanoic acid.
b

i Write an equation for the dissociation of phenol in aqueous solution.


ii Predict and explain the relative acidities of 2-methylphenol and phenol.

c Explain why dimethylamine is a stronger base than methylamine.

[4]
[2]

[4]

[1]
[3]
[2]
[2]
[3]
[2]

5 2-chloropropane can form a Grignard reagent.

46

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]

G FURTHER ORGANIC CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

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.

i Draw the structure of ethanoyl chloride.


ii Write an equation showing full structural formulas for the reaction between ethanoyl chloride
and propan-2-ol.
iii To what class of compounds does the organic product in part ii belong?
iv Draw out the mechanism for the reaction between ethanoyl chloride and water.

[1]

i Draw the structure of propanoic anhydride.


ii Draw the full structural formulas of both organic products of the reaction between
propanoic anhydride and ammonia.

[1]

[2]
[1]
[4]

[2]

7 a The compound shown can be formed from benzene in a single step.

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

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

G FURTHER ORGANIC CHEMISTRY

47

You might also like