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ELECTROPHILIC ADDITION

Background
Electrophilic addition happens in many of the reactions of compounds containing carboncarbon double bonds - the alkenes.
The structure of ethene
We are going to start by looking at ethene, because it is the simplest molecule containing
a carbon-carbon double bond. What is true of C=C in ethene will be equally true of C=C in
more complicated alkenes.
Ethene, C2H4, is often modelled as shown on the right. The double bond between the
carbon atoms is, of course, two pairs of shared electrons. What the diagram doesn't show
is that the two pairs aren't the same as each other.
One of the pairs of electrons is held on the line between the two
carbon nuclei as you would expect, but the other is held in a
molecular orbital above and below the plane of the molecule. A
molecular orbital is a region of space within the molecule where
there is a high probability of finding a particular pair of electrons.
In this diagram, the line between the two carbon atoms represents a normal bond - the
pair of shared electrons lies in a molecular orbital on the line
between the two nuclei where you would expect them to be.
This sort of bond is called a sigma bond.
The other pair of electrons is found somewhere in the shaded
part above and below the plane of the molecule. This bond is
called a pi bond. The electrons in the pi bond are free to
move around anywhere in this shaded region and can move
freely from one half to the other.
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.
Note: Check your syllabus to see if you need to know how a pi bond is formed.
Haven't got a syllabus? If you are working towards a UK-based exam, find out
how to get one by following this link.
If you do need to know about the bonding in ethene in detail, follow this link as
well.

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. For example, a francophile is
someone who likes the French; an anglophile is someone who likes the English.

Ethene and the other alkenes are attacked by electrophiles. The


electrophile is normally the slightly positive ( +) end of a molecule
like hydrogen bromide, HBr.
Note: If you aren't sure about why some bonds are polar, read the page
on electronegativity.
Use the BACK button on your browser to return to this page.

Electrophiles are strongly attracted to the exposed electrons in the pi bond and reactions
happen because of that initial attraction - as you will see shortly.
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 . . .

Summary: electrophilic addition reactions


An addition reaction is a reaction in which two molecules join together to make a bigger
one. Nothing is lost in the process. All the atoms in the original molecules are found in the
bigger one.
An electrophilic addition reaction is an addition reaction which happens because what we
think of as the "important" molecule is attacked by an electrophile. The "important"
molecule has a region of high electron density which is attacked by something carrying
some degree of positive charge.
Note: When we talk about reactions of alkenes like ethene, we think of the
ethene as being attacked by other molecules such as hydrogen bromide.
Because ethene is the molecule we are focusing on, we quite arbitrarily think of it
as the central molecule and hydrogen bromide as its attacker.
There's no real justification for this, of course, apart from the fact that it helps to
put things in some sort of logical pattern. In reality, the molecules just collide and
may react if they have enough energy and if they are lined up correctly.

THE REACTION BETWEEN SYMMETRICAL ALKENES


AND THE HYDROGEN HALIDES

This page gives you the facts and a simple, uncluttered mechanism for the electrophilic
addition reactions between the hydrogen halides and alkenes like ethene and
cyclohexene. Hydrogen halides include hydrogen chloride and hydrogen bromide. If you
want the mechanisms explained to you in detail, there is a link at the bottom of the page.

Electrophilic addition reactions involving hydrogen bromide


The facts
Alkenes react with hydrogen bromide in the cold. The double bond breaks and a hydrogen
atom ends up attached to one of the carbons and a bromine atom to the other.
In the case of ethene, bromoethane is formed.
Note: Be careful when you write the names of the addition products that you
change the ene ending in the original alkene (showing the C=C) into
an ane ending (showing that it has been replaced by C-C).

With cyclohexene you get bromocyclohexane.

The structures of the cyclohexene and the bromocyclohexane are often simplified:

Note: Each corner in one of these diagrams represents a carbon atom.


Each carbon atom has enough hydrogens attached to make the total number
of bonds up to 4.
In the case of the bromocyclohexane, it isn't necessary to write the new
hydrogen into the diagram, but it is helpful to put it there to emphasise that
addition has happened.

Be sure that you understand the relationship between these simplified diagrams and the
full structures.
The mechanisms
The reactions are examples of electrophilic addition.
With ethene and HBr:

and with cyclohexene:

Electrophilic addition reactions involving the other hydrogen halides


The facts
Hydrogen chloride and the other hydrogen halides add on in exactly the same way. For
example, hydrogen chloride adds to ethene to make chloroethane:

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 hydrogenhalogen bond falls. Bond strengths (measured in kilojoules per mole) are:

H-F

568

H-Cl

432

H-Br

366

H-I

298

Note: You may find slightly different values depending on which data source
you use. It doesn't matter - the differences are minor and the pattern is
always the same.

As you have seen in the HBr case, in the first step of the mechanism the hydrogenhalogen 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.
Suggestion: Find out if your syllabus mentions a particular hydrogen
halide, and learn that mechanism. You can simply swap the halogen atom if
a different hydrogen halide comes up in an exam.
Haven't got a syllabus? If you are working towards a UK-based exam, follow
this link to find out how to get one.

THE REACTION BETWEEN SYMMETRICAL ALKENES


AND SULPHURIC ACID

This page gives you the facts and a simple, uncluttered mechanism for the electrophilic
addition reactions between sulphuric acid and alkenes like ethene and cyclohexene. If you
want the mechanisms explained to you in detail, there is a link at the bottom of the page.

The electrophilic addition reaction between ethene and sulphuric acid


The facts
Alkenes react with concentrated sulphuric acid in the cold to produce alkyl
hydrogensulphates. Ethene reacts to give ethyl hydrogensulphate.

The structure of the product molecule is sometimes written as CH 3CH2HSO4, 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.
Confused by all this? Don't be!
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.
Important! Learn this structure for sulphuric acid. Sketch it over and over
again until you can't possibly get it wrong.

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.

THE REACTION BETWEEN SYMMETRICAL ALKENES


AND BROMINE

This page gives you the facts and a simple, uncluttered mechanism for the electrophilic
addition reactions between bromine (and the other halogens) and alkenes like ethene and
cyclohexene. If you want the mechanisms explained to you in detail, there is a link at the
bottom of the page.

The electrophilic addition of bromine to ethene


The facts
Alkenes react in the cold with pure liquid bromine, or with a solution of bromine in an
organic solvent like tetrachloromethane. The double bond breaks, and a bromine atom
becomes attached to each carbon. The bromine loses its original red-brown colour to give
a colourless liquid. In the case of the reaction with ethene, 1,2-dibromoethane is formed.

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 beyond what is required by current
UK A level (or equivalent) syllabuses.
The other halogens, apart from fluorine, behave similarly. (Fluorine reacts explosively with
all hydrocarbons - including alkenes - to give carbon and hydrogen fluoride.)
If you are interested in the reaction with, say, chlorine, all you have to do is to replace Br
by Cl in all the equations on this page.
The mechanism for the reaction between ethene and bromine
The reaction is an example of electrophilic addition.
Warning! There are two versions of the ethene / bromine mechanism in common use,

and you must know which your examiners will accept.


One version is simplified to bring it into line with the other alkene electrophilic addition
mechanisms. You will probablyfind that your examiners will accept this one, but you must
find out to be sure.
You almost certainly won't be able to tell this from your syllabus. You need to refer to
recent mark schemes, or to any support material that your examiners provide. If you still
aren't sure, contact your examiners direct. If you are working towards a UK-based exam,
you can find out how to do this by using the link to your Board's web site on
the syllabusespage.
The person you need to contact will probably have the titleSubject Officer for Chemistry or
something similar. Ask whether they want the mechanism for the reaction between
bromine and alkenes which proceeds via a carbocation or via a bromonium ion
intermediate.

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 - to show that you understand
what's going on.
The simplified version of the mechanism
Note: Use this version unless your examiners insist on the more accurate one.

The more accurate version of the mechanism


Note: Don't learn this unless you have to. There is a real risk of getting confused. If your
examiners are happy to accept the simple version, there's no point in making life difficult
for yourself.

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.

The electrophilic addition of bromine to cyclohexene


The facts
Cyclohexene reacts with bromine in the same way and under the same conditions as any
other alkene. 1,2-dibromocyclohexane is formed.

The mechanism for the reaction between cyclohexene and bromine


The reaction is an example of electrophilic addition.
Warning! Again, there are two versions of this mechanism in common use, and
you must know which your examiners will accept.

Bromine as an electrophile
Again, the bromine is polarised by the approaching pi bond in the cyclohexene. Don't
forget to write the words "induced dipole" next to the bromine molecule.
The simplified version of the mechanism
Note: Use this version unless your examiners insist on the more accurate one.

The alternative version of the mechanism


Note: Don't learn this unless you have to. If your examiners are happy to accept the
simple version, there's no point in making life difficult for yourself.

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.