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CH4
ethane
CH3CH3
propane
CH3CH2CH3
CH3
ethyl
CH3CH2
For example, ethanoic acid is CH3COOH and contains a methyl group. The carbon-hydrogen bonds in the methyl group behave just
like those in methane, and can be broken and replaced by something else in the same way.
A simple example of substitution is the reaction between methane and chlorine in the presence of UV light
(or sunlight).
CH4 + Cl2
+ HCl
CH3Cl
Notice that one of the hydrogen atoms in the methane has been replaced by a chlorine atom. That's substitution.
Cl
a methyl radical
CH3
Note: If you wanted to be fussy, the dot showing the electron really ought to be written next to the carbon atom in the methyl
radical, because that's the atom with the unpaired electron - in other words as CH3. This isn't normally done unless the radical gets
more complicated.
Note: These reactions are sometimes described as examples of photocatalysis - reactions catalysed by light. It is
better to use the term "photochemical" and keep the keep the word "catalysis" for reactions speeded up by actual
substances rather than light.
CH4 + Cl2
CH3Cl + HCl
The organic product is chloromethane. (or bromomethane if reaction occurs with bromine)
One of the hydrogen atoms in the methane has been replaced by a chlorine atom, so this is a substitution
reaction. However, the reaction doesn't stop there, and all the hydrogens in the methane can in turn be replaced by
chlorine atoms. [Multiple substitution]
The mechanism
The mechanism involves a chain reaction. During a chain reaction, for every reactive species you
start off with, a new one is generated at the end - and this keeps the process going.
Species: a useful word which is used in chemistry to mean any sort of particle you want it to mean. It
covers molecules, ions, atoms, or (in this case) free radicals.
The over-all process is known as free radical substitution, or as a free radical chain reaction.
Chain initiation: The chain is initiated (started) by UV light breaking a chlorine molecule into free
radicals.
Cl2
2Cl
Chain propagation reactions: These are the reactions which keep the chain going.
CH4 + Cl
+ HCl
CH3
CH3 + Cl2
+ Cl
CH3Cl
Chain termination reactions: These are reactions which remove free radicals from the system
without replacing them by new ones.
2Cl
Cl
CH3 + Cl
CH3Cl
CH3 + CH3
CH3CH3
methylbenzene and chlorine . . .
A Free Radical Substitution Reaction
Methylbenzene has a methyl group attached to a benzene ring. The hexagon with the circle inside is the
standard symbol for this ring. There is a carbon atom at each corner of the hexagon, and a hydrogen atom
on each carbon apart from the one with the methyl group attached.
The reaction we are going to explore happens between methylbenzene and chlorine in the presence of
ultraviolet light - typically sunlight. This is a good example of a photochemical reaction.
The organic product is (chloromethyl)benzene. The brackets in the name emphasise that the chlorine is part of the
attached methyl group, and isn't on the ring.
One of the hydrogen atoms in the methyl group has been replaced by a chlorine atom, so this is a substitution
reaction. However, the reaction doesn't stop there, and all three hydrogens in the methyl group can in turn be
replaced by chlorine atoms. [Multiple substitution]
Important! There is another reaction which happens between methylbenzene and chlorine in the absence of light and in the
presence of a number of possible catalysts. In that one, substitution happens in the benzene ring instead of in the methyl
group. You will find this reaction discussed under electrophilic substitution reactions.
The mechanism
The mechanism involves a chain reaction. During a chain reaction, for every reactive species you start
off with, a new one is generated at the end - and this keeps the process going.
The over-all process is known as free radical substitution, or as a free radical chain reaction.
Chain initiation: The chain is initiated (started) by UV light breaking a chlorine molecule into free
radicals.
Cl2
2Cl
Chain propagation reactions: These are the reactions which keep the chain going.
Chain termination reactions: These are reactions which remove free radicals from the system
without replacing them by new ones. If any two free radicals collide, they will join together
without producing any new radicals.
The simplest example of this is a collision between two chlorine radicals.
2Cl
Cl
Conditions
Temperature:
about 200C
Pressure:
Initiator:
Note: The oxygen is sometimes described as a catalyst for the reaction. That's not strictly true. A catalyst can be recovered
unchanged at the end of a reaction, but in this case the oxygen is used up. It gets incorporated into the polymer molecules - as you
will see shortly.
The mechanism
The over-all process is known as free radical addition.
Chain initiation: The chain is initiated by free radicals, Ra , produced by reaction between some of the
ethene and the oxygen initiator.
Chain propagation: Each time a free radical hits an ethene molecule a new longer free radical is formed.
Chain termination: Eventually two free radicals hit each other producing a final molecule. The
process stops here because no new free radicals are formed.
Because chain termination is a random process, poly(ethene) will be made up of chains of all sorts of
different lengths.
alkenes with hydrogen bromide . . .
The mechanism for the addition of hydrogen bromide to alkenes under free radical conditions. This
is often known as the "peroxide effect".
*Addition to symmetrical alkenes
A symmetrical alkene is one like ethene where the groups at both ends of the carbon-carbon double
bond are the same.
The reaction happens at room temperature in the presence of organic peroxides or some oxygen from the air. Alkenes
react very slowly with oxygen to produce traces of organic peroxides - so the two possible conditions are equivalent to
each other.
The reaction is a simple addition of the hydrogen bromide. For example, with ethene:
With a symmetrical alkene you get exactly the same product in the absence of the organic peroxides or
oxygen - but the mechanism is different.
The mechanism
Hydrogen halides (hydrogen chloride, hydrogen bromide and the rest) usually react with alkenes using an
electrophilic addition mechanism. However, in the presence of organic peroxides, hydrogen
bromide adds by a different mechanism.
With the organic peroxides present you get a free radical chain reaction.
Chain initiation: The chain is initiated by free radicals produced by an oxygen-oxygen bond in the
organic peroxide breaking.
These free radicals extract a hydrogen atom from a hydrogen bromide molecule to produce bromine
radicals.
Chain propagation: A bromine radical joins to the ethene using one of the electrons in the pi bond. That
creates a new radical with the single electron on the other carbon atom.
That radical reacts with another HBr molecule to produce bromoethane and another bromine
radical to continue the process.
Chain termination: Eventually two free radicals hit each other and produce a molecule of some sort. The
process stops here because no new free radicals are formed.
*Addition to unsymmetrical alkenes
An unsymmetrical alkene is one like propene where the groups at either end of the carbon-carbon
double bond are different.
The reaction happens under the same conditions as with a symmetrical alkene, but there is a complication because
the hydrogen and the bromine can add in two different ways. Which way they add depends on whether there are
organic peroxides (or oxygen) present or not.
Normally, when a molecule HX adds to a carbon-carbon double bond, the hydrogen becomes attached to
the carbon with the more hydrogens on already. This is known as Markovnikov's Rule.
Because the HBr adds on the "wrong way around" in the presence of organic peroxides, this is often known
as the peroxide effect or anti-Markovnikov addition.
In the absence of peroxides, hydrogen bromide adds to propene via an electrophilic addition
mechanism. That gives the product predicted by Markovnikov's Rule.
The free radical mechanism
Chain initiation:This is exactly the same as in the ethene case above.
Chain propagation: When the bromine radical joins to the propene, it attaches so that a secondary
radical is formed. This is more stable (and so easier to form) than the primary radical which would be
formed if it attached to the other carbon atom.
That radical reacts with another HBr molecule to produce 1-bromopropane and another bromine
radical to continue the process.
Chain termination
Eventually two free radicals hit each other and produce a molecule of some sort. The process stops here
because no new free radicals are formed.
Why don't the other hydrogen halides behave in the same way?
The reason that hydrogen bromide adds in an anti-Markovnikov fashion in the presence of organic
peroxides is simply a question of reaction rates. The free radical mechanism is much faster than the
alternative electrophilic addition mechanism.
Both mechanisms happen, but most of the product is the one from the free radical mechanism because
that is working faster.
With the other hydrogen halides, the opposite is true.
Hydrogen fluoride
The hydrogen-fluorine bond is so strong that fluorine radicals aren't formed in the initiation step.
Hydrogen chloride
With hydrogen chloride, the second half of the propagation stage is very slow. If you do a bond enthalpy
sum, you will find that the following reaction is endothermic.
In the case of hydrogen bromide, both steps of the propagation stage are exothermic.
Note: This diagram shows a side view of an ethene molecule. The dotted lines to two of the hydrogens show bonds going back into
the screen or paper away from you. The wedge shapes show bonds coming out towards you.
The pi electrons are not as fully under the control of the carbon nuclei as the electrons in the sigma bond
and, because they lie exposed above and below the rest of the molecule, they are relatively open to attack
by other things.
Electrophiles
An electrophile is something which is attracted to electron-rich regions in other molecules or
ions. Because it is attracted to a negative region, an electrophile must be something which carries either
a full positive charge, or has a slight positive charge on it somewhere.
Note: The ending ". . phile" means a liking for.
Ethene and the other alkenes are attacked by electrophiles. The electrophile is normally the slightly
positive ( +) end of a molecule like hydrogen bromide, HBr.
Electrophiles are strongly attracted to the exposed electrons in the pi bond and reactions happen
because of that initial attraction.
You might wonder why fully positive ions like sodium, Na+, don't react with ethene. Although these
ions may well be attracted to the pi bond, there is no possibility of the process going any further to form
bonds between sodium and carbon, because sodium forms ionic bonds, whereas carbon normally forms
covalent ones.
Addition reactions
In a sense, the pi bond is an unnecessary bond. The structure would hold together perfectly well with a
single bond rather than a double bond. The pi bond often breaks and the electrons in it are used to join
other atoms (or groups of atoms) onto the ethene molecule. In other words, ethene undergoes addition
reactions.
For example, using a general molecule X-Y . . .
You are now much more likely to find the electrons in the half of the pi bond nearest the XY. As the process
continues, the two electrons in the pi bond move even further towards the X until a covalent bond is made.
The electrons in the X-Y bond are pushed entirely onto the Y to give a negative Y- ion.
Help! Why does the carbon atom have a positive charge? The pi bond was originally made using an
electron from each carbon atom, but both of these electrons have now been used to make a bond to the X
atom. This leaves the right-hand carbon atom an electron short - hence positively charged.
Note also that we are only showing one of the pairs of electrons around the Y - ion. There will be other lone
pairs as well, but we are only actually interested in the one we've drawn.
In the final stage of the reaction the electrons in the lone pair on the Y- ion are
strongly attracted towards the positive carbon atom. They move towards it and form a co-ordinate
(dative covalent) bond between the Y and the carbon.
Help! A co-ordinate (dative covalent) bond is simply a covalent bond in which both shared electrons originate from the same atom.
The bond formed between the X and the other carbon atom was also a co-ordinate bond. Once a co-ordinate bond has been formed
there is no difference whatsoever between it and any other covalent bond.
The structures of the cyclohexene and the bromocyclohexane are often simplified:
The mechanisms
The reactions are examples of electrophilic addition.
With ethene and HBr:
The only difference is in how fast the reactions happen with the different hydrogen halides. The rate of
reaction increases as you go from HF to HCl to HBr to HI.
HF
slowest
reaction
HCl
HBr
HI
fastest
reaction
The reason for this is that as the halogen atoms get bigger, the strength of the hydrogen-halogen
bond falls.
As you have seen in the HBr case, in the first step of the mechanism the hydrogen-halogen bond gets
broken. If the bond is weaker, it will break more readily and so the reaction is more likely to happen.
The mechanisms
The reactions are still examples of electrophilic addition.
With ethene and HCl, for example:
This is exactly the same as the mechanism for the reaction between ethene and HBr, except that we've
replaced Br by Cl.
All the other mechanisms for symmetrical alkenes and the hydrogen halides would be done in the same
way.
The reaction with sulphuric acid . . .
The mechanism for the reaction between ethene (and cyclohexene) and sulphuric acid.
The structure of the product molecule is sometimes written as CH3CH2HSO4, but the version
in the equation is better because it shows how all the atoms are linked up. You may also find
it written as CH3CH2OSO3H.
All you need to do is to learn the structure of sulphuric acid, and after that the mechanism is exactly the same as the
one with hydrogen bromide. As you will find out, the formula of the product follows from the mechanism in an
inevitable way.
The mechanism for the reaction between ethene and sulphuric acid
Sulphuric acid as an electrophile
The hydrogen atoms are attached to very electronegative oxygen atoms which means that the
hydrogens will have a slight positive charge while the oxygens will be slightly negative. In the
mechanism, we just focus on one of the hydrogen to oxygen bonds, because the other one is too far from
the carbon-carbon double bond to be involved in any way.
The mechanism
Look carefully at the structure of the product so that you can see how it relates to the various formulae
given earlier (CH3CH2OSO2OH etc).
The electrophilic addition reaction between cyclohexene and sulphuric acid
This time we are going straight for the mechanism without producing an initial equation. This is to show
that you can work out the structure of obscure products provided you can write the mechanism.
The mechanism for the reaction between cyclohexene and sulphuric acid
Having worked out the structure of the product, you could then write a simple equation for the reaction if
you wanted to.
This decolourisation of bromine is often used as a test for a carbon-carbon double bond. If an
aqueous solution of bromine is used ("bromine water"), you get a mixture of products. The presence of the
water complicates the mechanism.
The other halogens, apart from fluorine, behave similarly. (Fluorine reacts explosively with all
hydrocarbons - including alkenes - to give carbon and hydrogen fluoride.)
The mechanism for the reaction between ethene and bromine
The reaction is an example of electrophilic addition.
Bromine as an electrophile
The bromine is a very "polarisable" molecule and the approaching pi bond in the ethene induces
a dipole in the bromine molecule. If you draw this mechanism in an exam, write the words "induced
dipole" next to the bromine molecule .
The simplified version of the mechanism
The bromonium ion is then attacked from the back by a bromide ion formed in a nearby reaction.
The bromonium ion is then attacked from the back by a bromide ion formed in a nearby reaction.
Notice that it doesn't matter how complicated the attached alkyl group is. All you are doing is
counting the number of bonds from the positive carbon to other carbon atoms. In all the above
cases there is only one such link.
Using the symbol R for an alkyl group, a primary carbocation would be written
box.
as in the
Secondary carbocations
In a secondary (2) carbocation, the carbon with the positive charge is attached to two other
alkyl groups, which may be the same or different.
Examples:
A secondary carbocation has the general formula shown in the box. R and R' represent
alkyl groups which may be the same or different.
Tertiary carbocations
In a tertiary (3) carbocation, the positive carbon atom is attached to three alkyl groups, which may be any
combination of same or different.
A tertiary carbocation has the general formula shown in the box. R, R' and R" are alkyl
groups and may be the same or different.
The arrow shows the electrons being "pushed" away from the CH 3 group. The plus sign on the left-hand end of it shows that the CH 3
group is becoming positive. The symbols + and - simply reinforce that idea.
You will see that the electron pushing effect of the CH3 group is placing more and more negative charge on
the positive carbon as you go from primary to secondary to tertiary carbocations. The effect of this, of
course, is to cut down that positive charge.
At the same time, the region around the various CH3 groups is becoming somewhat positive. The net
effect, then, is that the positive charge is being spread out over more and more atoms as you go from
primary to secondary to tertiary ions.
The more you can spread the charge around, the more stable the ion becomes.
Order of stability of
carbocations
primary < secondary <
tertiary
With these unsymmetrical alkenes, it is possible to get two different products during some addition
reactions.
During the addition of a molecule HX to propene, you could in principle get either this reaction:
or this one:
It depends on which way around you add the HX across the double bond.
In fact, in most cases, it's mainly the second reaction which happens. The hydrogen atom becomes
attached to the right-hand carbon atom as we've drawn it.
Markovnikov's Rule
When a compound HX is added to an unsymmetrical alkene, the hydrogen becomes attached
to the carbon with the most hydrogens attached to it already.
Remember that the HX has to attach itself to the carbon atoms which were originally part
of the double bond. So in this case, adding HX to CH3CH=CH2, the hydrogen is attached to
the CH2 group, because the CH2 group has more hydrogens than the CH group.
Notice that only the hydrogens directly attached count. The ones in the CH 3 group are totally irrelevant.
The Mechanism
HX as an electrophile
In each of the cases we are interested in, X is more electronegative than hydrogen. That means that the
bonding pair of electrons will be dragged towards the X end of the bond, and so the hydrogen becomes
slightly positively charged.
The slightly positive hydrogen is the electrophile, and is attracted to the pi bond in the propene.
What happens next determines which way around the HX adds across the double bond.
The two possible mechanisms
In both possibilities, the pi bond breaks and the electron pair swings down to form a bond with the
hydrogen atom. At the same time, the electrons in the H-X bond are repelled right down on to the X to give
an X- ion.
The difference lies in which way the electron pair in the pi bond swings.
First possibility
The electron pair moves to form a bond between the hydrogen and the left-hand carbon.
When the second stage of the mechanism happens, and the lone pair on X- forms a bond with the positive
carbon atom, the product of this mechanism is not the one which Markovnikov's Rule predicts.
Second possibility
The electron pair moves to form a bond between the hydrogen and the right-hand carbon.
In the slow mechanism which produces hardly any product, you get a primary carbocation formed instead.
It is much easier to form the secondary carbocation because it is more energetically stable. The activation
energy for the reaction will be less, and so most of the reaction happens via that mechanism.
If you are asked why the HX adds this way round, look at the carbocation formed as an intermediate and decide whether it is
secondary or tertiary. Here it is a secondary ion. Then think about what sort of ion would be formed if the HX added the other way
around. In this case that would be a primary ion.
The addition is this way around because the intermediate carbocation (previously called a carbonium ion)
formed is secondary. This is more stable (and so is easier to form) than the primary carbocation which
would be produced if the hydrogen became attached to the centre carbon atom and the bromine to the
end one.
Electrophilic addition reactions involving the other hydrogen halides
Hydrogen fluoride, hydrogen chloride and hydrogen iodide all add on in exactly the same way as hydrogen
bromide.
The only differences lie in the rates of reaction:
HF
slowest
reaction
HCl
HBr
HI
fastest
reaction
This is because the hydrogen-halogen bond gets weaker as the halogen atom gets bigger. If the bond is
weaker, it breaks more easily and so the reaction is faster.
If the halogen is given the symbol X, the equation for the reaction with propene is:
Again, the intermediate carbocation formed is secondary. This is more stable than the primary carbocation
ion which would be formed if the hydrogen attached to the centre carbon atom and the X to the end one. If
it is more stable it will be easier to make.
The reaction with sulphuric acid . . .
The electrophilic addition reaction between propene and sulphuric acid
Alkenes react with concentrated sulphuric acid in the cold to produce alkyl hydrogensulphates. In the case
of propene, the equation is:
In this case, the hydrogen becomes attached to the CH2 group, because the CH2 group has more
hydrogens than the CH group.
Notice that only the hydrogens directly attached to the carbon atoms at either end of the double bond
count. The ones in the CH3 group are totally irrelevant.
The mechanism
This is an example of electrophilic addition.
The addition is this way around because it is easier to produce the secondary carbocation (carbonium ion)
than the primary one which would be formed if the hydrogen became attached to the centre carbon atom
and the rest of the sulphuric acid to the end one.
The reaction with bromine . . .
An unsymmetrical alkene is one like propene in which the groups or atoms attached to either end of the
carbon-carbon double bond are different.
For example, in propene there are a hydrogen and a methyl group at one end, but two hydrogen atoms at
the other end of the double bond. But-1-ene is another unsymmetrical alkene.
The other halogens, apart from fluorine, behave similarly. (Fluorine reacts explosively with all
hydrocarbons - including alkenes - to give carbon and hydrogen fluoride.)
The mechanism for the reaction between propene and bromine
The reaction is an example of electrophilic addition.
The simplified version of the mechanism
In the first stage of the reaction, one of the bromine atoms becomes attached to both carbon atoms, with
the positive charge being found on the bromine atom. A bromonium ion is formed.
The bromonium ion is then attacked from the back by a bromide ion formed in a nearby reaction.
Benzene, C6H6, is a planar molecule containing a ring of six carbon atoms each with a hydrogen
atom attached.
There are delocalised electrons above and below the plane of the ring.
Benzene resists addition reactions because that would involve breaking the delocalisation and
losing that stability.
Benzene is represented by this symbol, where the circle represents the delocalised electrons, and
each corner of the hexagon has a carbon atom with a hydrogen
attached.
If benzene underwent addition reactions in the same way as ethene, it would need to use some of the
delocalised electrons to form bonds with the new atoms or groups. This would break the delocalisation and this costs energy.
Instead, it can maintain the delocalisation if it replaces a hydrogen atom by something else - a substitution
reaction. The hydrogen atoms aren't involved in any way with the delocalised electrons.
In most of benzene's reactions, the electrophile is a positive ion, and these reactions all follow a general
pattern.
The general mechanism
The first stage
Suppose the electrophile is a positive ion X+.
Two of the electrons in the delocalised system are attracted towards the X + and form a bond with it. This
has the effect of breaking the delocalisation, although not completely.
The ion formed in this step isn't the final product. It immediately goes on to react with something else. It
is just an intermediate.
There is still delocalisation in the intermediate formed, but it only covers part of the ion. When you
write one of these mechanisms, draw the partial delocalisation to take in all the carbon atoms apart from
the one that the X has become attached to.
The intermediate ion carries a positive charge because you are joining together a neutral molecule and a
positive ion. This positive charge is spread over the delocalised part of the ring. Simply draw the "+" in the
middle of the ring.
The hydrogen at the top isn't new - it's the hydrogen that was already attached to that carbon. We need to
show that it is there for the next stage.
The second stage
Here we've introduced a new ion, Y-. Where did this come from? You have to remember that it is
impossible to get a positive ion on its own in a chemical system - so Y- is simply the negative ion that
was originally associated with X+.
A lone pair of electrons on Y- forms a bond with the hydrogen atom at the top of the ring. That
means that the pair of electrons joining the hydrogen onto the ring aren't needed any more.
These then move down to plug the gap in the delocalised electrons, so restoring the delocalised ring
of electrons which originally gave the benzene its special stability.
Electrophilic substitution reactions not involving positive ions
Halogenation and sulphonation
In these reactions, the electrophiles are polar molecules rather than fully positive ions.
These mechanisms are different from what's gone before (and from each other).
The nitration of benzene . . .
The mechanism for the formation of nitrobenzene from benzene.
The electrophilic substitution reaction between benzene and nitric acid
Benzene is treated with a mixture of concentrated nitric acid and concentrated sulphuric acid at a
temperature not exceeding 50C. As temperature increases there is a greater chance of getting more than
one nitro group, -NO2, substituted onto the ring.
Nitrobenzene is formed.
or:
Stage two
or better:
The aluminium chloride isn't written into these equations because it is acting as a catalyst. If you wanted to include it, you could
write AlCl3 over the top of the arrow.
Stage two
The hydrogen is removed by the AlCl4- ion which was formed at the same time as the CH3CO+ electrophile.
The aluminium chloride catalyst is re-generated in this second stage.
The Friedel-Crafts alkylation of benzene . . .
The mechanism for the substitution of an alkyl group such as CH3 into benzene.
The electrophilic substitution reaction between benzene and chloromethane
What is alkylation?
Alkylation means substituting an alkyl group into something - in this case into a benzene ring. A
hydrogen on the ring is replaced by a group like methyl or ethyl and so on.
Benzene is treated with a chloroalkane (for example, chloromethane or chloroethane) in the presence of
aluminium chloride as a catalyst. Any other alkyl group could be used in the same way.
Substituting a methyl group gives methylbenzene - once known as toluene.
or better:
The aluminium chloride isn't written into these equations because it is acting as a catalyst. If you wanted
to include it, you could write AlCl3 over the top of the arrow.
Note: The methylbenzene formed is more reactive than the original benzene, and so the reaction doesn't stop there. You get further
methyl groups substituted around the ring.
Stage two
The hydrogen is removed by the AlCl4- ion which was formed at the same time as the CH3+ electrophile.
The aluminium chloride catalyst is re-generated in this second stage.
An industrial alkylation of benzene . . .
The mechanism for the substitution of an alkyl group such as CH3CH2 into benzene, by a reaction
involving an alkene such as ethene.
Note: The process described below is one of several ways of making alkylbenzenes like ethylbenzene
from benzene and alkenes, using a variety of different catalysts and conditions.
The electrophilic substitution reaction between benzene and ethene
Industrially, alkyl groups can be substituted into a benzene ring using a variant on Friedel-Crafts alkylation.
One possibility is that instead of using a chloroalkane with an aluminium chloride catalyst, they use an
alkene and a mixture of aluminium chloride and hydrogen chloride as the catalyst.
This is a cheaper method because it saves having to make the chloroalkane first.
To put an ethyl group on the ring (to make ethylbenzene), benzene is treated with a mixture of ethene, HCl
and aluminium chloride.
or better:
The aluminium chloride and HCl aren't written into these equations because they are acting as catalysts. If
you wanted to include them, you could write AlCl3 and HCl over the top of the arrow.
The formation of the electrophile
The electrophile is CH3CH2+. It is formed by reaction between the ethene and the HCl - exactly as if you
were beginning to add the HCl to the ethene.
The chloride ion is immediately picked up by the aluminium chloride to form an AlCl 4- ion. That prevents
the chloride ion from reacting with the CH3CH2+ ion to form chloroethane.
Note: It wouldn't matter if it did react, because chloroethane will react with benzene using a simple
Friedel-Crafts alkylation reaction to give the product you want anyway.
Stage two
The hydrogen is removed by the AlCl4- ion which was formed at the same time as the CH3CH2+ electrophile.
The aluminium chloride and hydrogen chloride catalysts are re-generated in this second stage.
The electrophilic substitution reaction between benzene and propene
The problem with more complicated alkenes like propene is that you have to be careful about the structure
of the product. In each case, you can only really be sure of that structure if you work through the
mechanism first.
For example, the propyl group becomes attached to the ring via its middle carbon atom - and not its end
one.
You still need a mixture of aluminium chloride and hydrogen chloride as catalysts.
The formation of the electrophile
When the propene reacts with the HCl, the hydrogen becomes attached to the end carbon atom. A
secondary carbocation (carbonium ion) is formed because it is more stable than the primary one which
would have been formed if the addition was the other way round.
Because the positive charge is on the centre carbon atom, that is the one which will become attached to
the ring.
Stage two
Again, the hydrogen is removed by the AlCl4- ion. The aluminium chloride and hydrogen chloride catalysts
are re-generated in this second stage.
The halogenation of benzene . . .
The mechanism for the substitution of atoms like chlorine and bromine into benzene rings.
The electrophilic substitution reaction between benzene and chlorine or bromine
Benzene reacts with chlorine or bromine in an electrophilic substitution reaction, but only in the
presence of a catalyst. The catalyst is either aluminium chloride (or aluminium bromide if you are
reacting benzene with bromine) or iron.
Strictly speaking iron isn't a catalyst, because it gets permanently changed during the reaction. It reacts
with some of the chlorine or bromine to form iron(III) chloride, FeCl 3, or iron(III) bromide, FeBr3.
These compounds act as the catalyst and behave exactly like aluminium chloride in these reactions.
The reaction with chlorine
The reaction between benzene and chlorine in the presence of either aluminium chloride or iron gives
chlorobenzene.
or:
or:
As a chlorine molecule approaches the benzene ring, the delocalised electrons in the ring repel electrons
in the chlorine-chlorine bond.
It is the slightly positive end of the chlorine molecule which acts as the electrophile. The presence of the
aluminium chloride helps this polarisation.
The electrophilic substitution mechanism
Stage one
Stage two
The hydrogen is removed by the AlCl4- ion which was formed in the first stage. The aluminium chloride
catalyst is re-generated in this second stage.
The sulphonation of benzene . . .
The mechanism for reaction between benzene and concentrated sulphuric acid to produce
benzenesulphonic acid
The electrophilic substitution reaction between benzene and sulphuric acid
There are two equivalent ways of sulphonating benzene:
Heat benzene under reflux with concentrated sulphuric acid for several hours.
Warm benzene under reflux at 40C with fuming sulphuric acid for 20 to 30 minutes.
Or:
Note: Which version of this equation you use will depend on what question you are being asked. If the
question refers to the reaction with sulphuric acid, then you must use that one. If the question refers to
SO3 as the electrophile, then you could use this one.
Fuming sulphuric acid, H2S2O7, can be thought of as a solution of SO3 in sulphuric acid - and so is a much
richer source of the SO3.
Sulphur trioxide is an electrophile because it is a highly polar molecule with a fair amount of positive
charge on the sulphur atom. It is this which is attracted to the ring electrons.
The electrophilic substitution mechanism
Stage one
Stage two
The second stage of the reaction involves a transfer of the hydrogen from the ring to the negative oxygen.
Some substitution reactions of methylbenzene . . .
Illustrates how to cope with the problem of substituting things into rings which already have
something else attached.
There are two problems you might come across:
Whereabouts in the ring does the substitution happen? Does this make a difference to
how you draw the mechanisms?
Can the group already attached to the ring get involved in any way?
The carbon with the methyl group attached is thought of as the number 1 carbon, and the ring is
then numbered around from 1 to 6. You number in a direction (in this case, clockwise) which produces the
smaller number in the name - hence 2-nitromethylbenzene rather than 6-nitromethylbenzene.
In the case of methylbenzene, whatever you attach to the ring, you always get a mixture consisting mainly
of the 2- and 4- isomers. The methyl group is said to be 2,4-directing, in the sense that it seems to
"push" incoming groups into those positions.
Isomers: Molecules which have the same molecular formula (i.e. contain exactly the same number and type of atoms), but with a
different spatial arrangement of those atoms.
Some other groups which might already be on the ring (for example, the -NO 2 group in nitrobenzene)
"push" incoming groups into the 3- position. We'll have a quick look at this later on this page.
How to write the mechanism for the nitration of methylbenzene
Reacting methylbenzene with a mixture of concentrated nitric and sulphuric acids gives both 2nitromethylbenzene and 4-nitromethylbenzene. The mechanism is exactly the same as the nitration
of benzene. You just have to be careful about the way that you draw the structure of the intermediate
ion.
Making 2-nitromethylbenzene (the first step)
This just shows the first step of the electrophilic substitution reaction. Notice that the partial delocalisation
in the intermediate ion covers all the carbon atoms in the ring except for the one that the -NO 2 group gets
attached to.
That is the only point of interest in this example - everything else is just the same as with the nitration of
benzene. The hydrogen atom is then removed by an HSO4- ion - exactly as in the benzene case.
Making 4-nitromethylbenzene (the first step)
Once again, the only point of interest is in the way the partial delocalisation in the intermediate ion is
drawn - again, it covers all the carbon atoms in the ring apart from the one with the -NO 2 group attached.
The electrophilic substitution reaction between methylbenzene and chlorine
This is a good example of a case where what is already attached to the ring can also get involved in the
reaction.
It is possible to get two quite different substitution reactions between methylbenzene and chlorine
depending on the conditions used. The chlorine can substitute into the ring or into the methyl group.
Here we are only interested in substitution into the ring. This happens in the presence of aluminium
chloride or iron, and in the absence of UV light.
Substituting into the ring gives a mixture of 2-chloromethylbenzene and 4-chloromethylbenzene.
The mechanisms are exactly the same as the substitution of chlorine into benzene - although you
would have to be careful about the way you draw the intermediate ion.
For example, the complete mechanism for substitution into the 4- position is:
Stage one
Stage two
The mechanism is exactly the same as the nitration of benzene or of methylbenzene - you just have to be
careful in drawing the intermediate ion. Draw the partial delocalisation to include all the carbons except
for the one the new -NO2 group gets attached to.
In the second stage, the hydrogen atom is then removed by an HSO 4- ion - exactly as in the benzene case.
This isn't shown because there's nothing new.
Everything else present (including anything formed in the alternative substitution reaction) will be trapped
in the flask.
The mechanism
In elimination reactions, the hydroxide ion acts as a base - removing a hydrogen as a hydrogen ion
from the carbon atom next door to the one holding the bromine.
The resulting re-arrangement of the electrons expels the bromine as a bromide ion and
produces propene.
The hydroxide ion removes a hydrogen from one of the carbon atoms next door to the carbon-bromine
bond, and the various electron shifts then lead to the formation of the alkene - in this case, propene.
With an unsymmetric halogenoalkane like 2-bromobutane, there are several hydrogens which might
possibly get removed. You need to think about each of these possibilities.
Where does the hydrogen get removed from?
The hydrogen has to be removed from a carbon atom adjacent to the carbon-bromine bond. If
an OH- ion hit one of the hydrogens on the right-hand CH3 group in the 2-bromobutane (as we've drawn it),
there's nowhere for the reaction to go.
To make room for the electron pair to form a double bond between the carbons, you would have to expel a
hydrogen from the CH2 group as a hydride ion, H-. That is energetically much too difficult, and so this
reaction doesn't happen.
That still leaves the possibility of removing a hydrogen either from the left-hand CH 3 or from the CH2
group.
If it was removed from the CH3 group:
but-1-ene
Elimination v. substitution . . .
The reaction between a halogenoalkane and hydroxide ions can lead to either an
elimination reaction or nucleophilic substitution.
The reactions
Both reactions involve heating the halogenoalkane under reflux with sodium or potassium hydroxide
solution.
Nucleophilic substitution
The hydroxide ions present are good nucleophiles, and one possibility is a replacement of the
halogen atom by an -OH group to give an alcohol via a nucleophilic substitution reaction.
substitution or
elimination?
primary
mainly substitution
secondary
tertiary
mainly elimination
For example, whatever you do with tertiary halogenoalkanes, you will tend to get mainly the elimination
reaction, whereas with primary ones you will tend to get mainly substitution. However, you can influence
things to some extent by changing the conditions.
The solvent
The proportion of water to ethanol in the solvent matters.
The temperature
Higher temperatures encourage elimination.
Concentration of the sodium or potassium hydroxide solution
Higher concentrations favour elimination.
In summary
For a given halogenoalkane, to favour elimination rather than substitution, use:
heat
The acids aren't written into the equation because they serve as catalysts. If you like, you could write, for
example, "conc H2SO4" over the top of the arrow.
The mechanism - the full version
We are going to discuss the mechanism using sulphuric acid. Afterwards, we'll describe how you can use a
simplified version which will work for any acid, including phosphoric(V) acid.
In the first stage, one of the lone pairs of electrons on the oxygen picks up a hydrogen ion from the
sulphuric acid. The alcohol is said to be protonated.
The protonated ethanol loses a water molecule to give a carbocation (a carbonium ion).
Finally, a hydrogensulphate ion (from the sulphuric acid) pulls off a hydrogen ion from the carbocation.
An advantage of this (apart from the fact that it doesn't require you to draw the structure of sulphuric acid)
is that it can be used for any acid catalyst without changing it at all. For example, if you use this version,
you wouldn't need to worry about the structure of phosphoric(V) acid.
Note: Although most people probably write the mechanism in this form, it is actually quite misleading
because it suggests the possibility of a free hydrogen ion in a chemical system. A free hydrogen ion is a
raw proton and this is always attached to something else during a chemical reaction.
The dehydration of more complicated alcohols . . .
You have to be wary with more complicated alcohols in case there is the possibility of more than one
alkene being formed. Butan-2-ol is a good example of this, with no less than three different alkenes
being formed when it is dehydrated.
Butan-2-ol is just an example to illustrate the problems
The basic facts and mechanisms for these reactions are exactly the same as with a simple alcohol like
ethanol. This page only deals with the extra problems created by the possibility of more than one
dehydration product.
Background
To make the diagrams less cluttered, we'll use the simplified version of the mechanism showing gain and
loss of H+.
Remember that the mechanism takes place in three stages:
The protonated alcohol loses a water molecule to give a carbocation (carbonium ion).
The carbocation formed loses a hydrogen ion and forms a double bond.
In the second stage, the positive ion then sheds a water molecule and produces a carbocation.
The complication arises in the next step. When the carbocation loses a hydrogen ion, where is it going to
come from?
Where does the hydrogen get removed from?
So that a double bond can form, it will have to come from one of the carbons next door to the one with the
positive charge.
If a hydrogen ion is lost from the CH3 group
But-1-ene is formed.
but-1-ene
Note: When you are naming these compounds, don't forget that the longest carbon chain has to include
the carbon in the -CN group. In both of the above examples, the longest carbon chain is 3 carbons - hence
the "prop" in both names. The carbon with the nitrogen attached is always counted as the number 1
carbon in the chain.
The reaction isn't normally done using hydrogen cyanide itself, because this is an extremely poisonous
gas. Instead, the aldehyde or ketone is mixed with a solution of sodium or potassium cyanide in water to
which a little sulphuric acid has been added. The pH of the solution is adjusted to about 4 - 5, because this
gives the fastest reaction.
The solution will contain hydrogen cyanide (from the reaction between the sodium or potassium cyanide
and the sulphuric acid), but still contains some free cyanide ions. This is important for the mechanism.
Note: If the reaction is done using hydrogen cyanide itself, a little sodium hydroxide solution is added to
produce some cyanide ions from the weakly acidic HCN. Again the pH of the solution is adjusted to around
pH 5 - in other words, the sodium hydroxide is not added to excess. The rate of the reaction falls if the pH
is any higher.
Whichever set of reagents you use, the reaction contains the same mixture of hydrogen cyanide and
cyanide ions.
The mechanisms
These are examples of nucleophilic addition.
The carbon-oxygen double bond is highly polar, and the slightly positive carbon atom is attacked by the
cyanide ion acting as a nucleophile.
Nucleophile: A species (molecule or ion) which attacks a positive site in something else. Nucleophiles are either fully
negative ions or contain a fairly negative region somewhere in a molecule. All nucleophiles have at least one active
lone pair of electrons. When you write mechanisms for reactions involving nucleophiles, you must show that lone pair.
In the first stage, there is a nucleophilic attack by the cyanide ion on the slightly positive carbon atom.
The negative ion formed then picks up a hydrogen ion from somewhere - for example, from a hydrogen
cyanide molecule.
The hydrogen ion could also come from the water or the H3O+ ions present in the slightly acidic solution.
You don't need to remember all of these. One equation is perfectly adequate.
Note: The product molecule here has been drawn differently from the one in the equation further up this page. It has been rotated
through 90. There is no reason why you can't do that if it makes the appearance of the mechanism easier to follow.
It is completed by the addition of a hydrogen ion from, for example, a hydrogen cyanide molecule.
Note: Again, the product molecule looks different from the one in the equation further up this page. The central carbon atom still
has the same four groups attached, but to make the mechanism easier to follow, they are simply arranged differently. That's not a
problem - we're still talking about the same substance.
Attack from one side will lead to one of the two isomers, and attack from the other side will lead to the
other.
All aldehydes will form a racemic mixture in this way. Unsymmetrical ketones will as well. (A
ketone can be unsymmetrical in the sense that there is a different alkyl group either side of the carbonyl
group.) What matters is that the product molecule must have four different groups attached to the carbon
which was originally part of the carbon-oxygen double bond.
The reduction of aldehydes and ketones . . .
The reduction of aldehydes and ketones by sodium tetrahydridoborate
Sodium tetrahydridoborate (previously known as sodium borohydride) has the formula NaBH4, and
contains the BH4- ion. That ion acts as the reducing agent.
There are several quite different ways of carrying out this reaction. Two possible variants (there are
several others!) are:
The reaction is carried out in solution in water to which some sodium hydroxide has been added
to make it alkaline. The reaction produces an intermediate which is converted into the final
product by addition of a dilute acid like sulphuric acid.
The reaction is carried out in solution in an alcohol like methanol, ethanol or propan-2-ol. This
produces an intermediate which can be converted into the final product by boiling it with
water.
In each case, reduction essentially involves the addition of a hydrogen atom to each end of the
carbon-oxygen double bond to form an alcohol. Reduction of aldehydes and ketones lead to
two different sorts of alcohol.
The reduction of an aldehyde
For example, with ethanal you get ethanol:
Notice that this is a simplified equation - perfectly acceptable to examiners. The H in square brackets
means "hydrogen from a reducing agent".
In general terms, reduction of an aldehyde leads to a primary alcohol. A primary alcohol is one which
only has one alkyl group attached to the carbon with the -OH group on it. They all contain the grouping
-CH2OH.
Note: There is one exception to this. Methanol CH3OH is also a primary alcohol. Think of this as H-CH2OH.
Reduction of a ketone leads to a secondary alcohol. A secondary alcohol is one which has two alkyl
groups attached to the carbon with the -OH group on it. They all contain the grouping -CHOH.
The simplified mechanisms
The BH4- ion is essentially a source of hydride ions, H-. The simplification used is to write H- instead of BH4-.
Doing this not only makes the initial attack easier to write, but avoids you getting involved with some
quite complicated boron compounds that are formed as intermediates.
The reduction is an example of nucleophilic addition.
The carbon-oxygen double bond is highly polar, and the slightly positive carbon atom is attacked by the
hydride ion acting as a nucleophile. A hydride ion is a hydrogen atom with an extra electron - hence the
lone pair.
The mechanism for the reduction of ethanal
In the first stage, there is a nucleophilic attack by the hydride ion on the slightly positive carbon atom. The
lone pair of electrons on the hydride ion forms a bond with the carbon, and the electrons in one of the
carbon-oxygen bonds are repelled entirely onto the oxygen, giving it a negative charge.
What happens now depends on whether you add an acid or water to complete the reaction.
Adding an acid:
When the acid is added, the negative ion formed picks up a hydrogen ion to give an alcohol.
Note: You may find that other sources write the hydrogen ion simply as H+. That's not good practice,
because it suggests a free hydrogen ion. The hydrogen ion is actually attached to a water molecule as
H3O+. Writing that makes the equation look more complicated. H+(aq) is a happy compromise.
Adding water:
This time, the negative ion takes a hydrogen ion from a water molecule.
Again, what happens next depends on whether you add an acid or water to complete the reaction.
Adding an acid:
The negative ion reacts with a hydrogen ion from the acid added in the second stage of the reaction.
Adding water:
This time, the negative ion takes a hydrogen ion from a water molecule.
If you remove the -OH group and replace it by a -Cl, you have produced an acyl chloride.
This molecule is known as ethanoyl chloride and for the rest of this topic will be taken as typical of acyl
chlorides in general.
Acyl chlorides are extremely reactive. They are open to attack by nucleophiles - with the overall
result being a replacement of the chlorine by something else.
Nucleophiles
A nucleophile is a species (an ion or a molecule) which is strongly attracted to a region of positive charge
in something else.
Nucleophiles are either fully negative ions, or else have a strongly - charge somewhere on a molecule.
The nucleophiles that we shall be looking at all depend on lone pairs on either an oxygen atom or a
nitrogen atom.
Nucleophiles based on oxygen atoms
We shall be talking about water and alcohols, taking ethanol as a typical alcohol.
Notice how similar these two molecules are around the oxygen atom. That's what turns out to be
important.
Nucleophiles based on nitrogen atoms
We shall be considering ammonia and primary amines, taking ethylamine as a typical primary amine. A
primary amine contains the -NH2 group attached to either an alkyl group (as it is here) or a benzene ring.
As far as these reactions are concerned, the nature of any hydrocarbon attached to the nitrogen makes no
difference. The nitrogen atom is the important bit.
Again, notice how similar these two molecules are around the nitrogen atom - and also how similar they
are to the previous ones containing oxygen. Both types of molecule have an active lone pair of electrons
attached to one of the most electronegative elements. All of these molecules also have at least one
hydrogen atom attached to the oxygen or nitrogen.
Why are acyl chlorides attacked by nucleophiles?
The carbon atom in the -COCl group has both an oxygen atom and a chlorine atom attached to it. Both
of these are very electronegative. They both pull electrons towards themselves, leaving the carbon atom
quite positively charged.
In each case, the net effect is that you replace the -Cl by -Nu, and hydrogen chloride is formed as well.
Since the initial attack is by a nucleophile, and the overall result is substitution, it would seem
reasonable to describe the reaction as nucleophilic substitution. However, the reaction happens in two
distinct stages. The first involves an addition reaction, which is followed by an elimination reaction
where HCl is produced. So the mechanism is also known as nucleophilic addition / elimination.
The general mechanism
The addition stage of the mechanism
As the lone pair on the nucleophile approaches the fairly positive carbon in the acyl chloride, it moves to
form a bond with it. In the process, the two electrons in one of the carbon-oxygen bonds are repelled
entirely onto the oxygen, leaving that oxygen negatively charged.
Notice the positive charge that forms on the nucleophile. Just accept this for the moment. It's much easier
to explain why that charge must be there if you have a real example in front of you. This is fully explained
in the pages on the reactions involving water, ammonia and so on.
The elimination stage of the mechanism
This happens in two steps. In the first step, the carbon-oxygen double bond reforms. To make room for it,
the electrons in the carbon-chlorine bond are repelled until they are entirely on the chlorine atom - forming
a chloride ion.
Finally, the chloride ion plucks the hydrogen off the original nucleophile. It removes it as a hydrogen ion,
leaving the pair of electrons behind on the oxygen or nitrogen atom in that nucleophile. That cancels the
positive charge.
The mechanism
The first stage (the addition stage of the reaction) involves a nucleophilic attack on the fairly positive
carbon atom by one of the lone pairs on the oxygen of a water molecule.
Note: Only one of the two lone pairs on the oxygen in water is shown. This is to avoid cluttering an already complicated diagram
with things that aren't relevant.
The second stage (the elimination stage) happens in two steps. In the first, the carbon-oxygen double
bond reforms and a chloride ion is pushed off.
That is followed by removal of a hydrogen ion by the chloride ion to give ethanoic acid and hydrogen
chloride.
The mechanism
The first stage (the addition stage of the reaction) involves a nucleophilic attack on the fairly positive
carbon atom by one of the lone pairs on the oxygen of an ethanol molecule.
Note: Only one of the two lone pairs on the oxygen in the ethanol is shown. This is to avoid cluttering an already complicated
diagram with things that aren't relevant.
The second stage (the elimination stage) happens in two steps. In the first, the carbon-oxygen double
bond reforms and a chloride ion is pushed off.
That is followed by removal of a hydrogen ion by the chloride ion to give ethyl ethanoate and hydrogen
chloride.
Notice that, unlike the reactions between ethanoyl chloride and water or ethanol, hydrogen chloride isn't
produced - at least, not in any quantity. Any hydrogen chloride formed would immediately react with
excess ammonia to give ammonium chloride.
The mechanism
The first stage (the addition stage of the reaction) involves a nucleophilic attack on the fairly positive
carbon atom by the lone pair on the nitrogen atom in the ammonia.
The second stage (the elimination stage) happens in two steps. In the first, the carbon-oxygen double
bond reforms and a chloride ion is pushed off.
That is followed by removal of a hydrogen ion from the nitrogen. This might happen in one of two ways:
It might be removed by a chloride ion, producing HCl (which would immediately react with excess
ammonia to give ammonium chloride as above) . . .
and
The ammonium ion, together with the chloride ion already there, makes up the ammonium chloride
formed in the reaction.
The reaction of acyl chlorides with primary amines . . .
Ethanoyl chloride is taken as a typical acyl chloride. Any other acyl chloride will behave in the same way.
Simply replace the CH3 group in what follows by anything else you want.
Similarly, ethylamine is taken as a typical amine. Any other amine will behave in the same way. Replacing
the CH3CH2 group by any other hydrocarbon group won't affect the mechanism in any way.
The reaction between ethanoyl chloride and ethylamine
Ethanoyl chloride reacts violently with a cold concentrated solution of ethylamine. A white solid product is
formed which is a mixture of N-ethylethanamide (an N-substituted amide) and ethylammonium chloride.
Notice that, unlike the reactions between ethanoyl chloride and water or ethanol, hydrogen chloride isn't
produced - at least, not in any quantity. Any hydrogen chloride formed would immediately react with
excess ethylamine to give ethylammonium chloride.
The mechanism
The first stage (the addition stage of the reaction) involves a nucleophilic attack on the fairly positive
carbon atom by the lone pair on the nitrogen atom in the ethylamine.
The second stage (the elimination stage) happens in two steps. In the first, the carbon-oxygen double
bond reforms and a chloride ion is pushed off.
That is followed by removal of a hydrogen ion from the nitrogen. This might happen in one of two ways:
It might be removed by a chloride ion, producing HCl (which would immediately react with excess
ethylamine to give ethylammonium chloride as above) . . .
and
The ethylammonium ion, together with the chloride ion already there, makes up the ethylammonium
chloride formed in the reaction.