Electrophilic Addition part 1

This main reaction of alkenes at AS level is electrophilic addition. There are other alkene reactions but
this will get you the most marks.

Electrophiles

an electrophile is an electron deficient species.

An electrophile must have a full positive charge + or a + charge.

Note: the + symbol means that it has a partial charge i.e. it is not as strong as a full positive charge.

The main electrophiles that you will be using are simply: H+, Br+, Cl+. However, you have to recognise
these from the reagents.

For example, H+ is likely to come from H-Br, H-Cl, H2O or HCN. Br+ would come from Br2.

Electrophilic Addition Reactions

If you see an alkene you should be thinking of electrophiles immediately.

All we are going to do is add something like H-Br to a double bond, in an electrophilic addition reaction:

CH2=CH2 + H-Br CH3-CH2Br

The H from the HBr is added to one of the carbons, the Br is added to the other carbon and the double
bond of the alkene is broken to leave a single bond. With addition reactions there is only one product,
therefore, has an atom economy of 100%.

Reaction Mechanisms
A chemical equation simply shows us the reactants used and the products that are formed, but it doesnt
tell us how we go from reactants to products. A reaction mechanism looks at the how part.

Drawing mechanisms are very easy marks but you need to get them spot on. There are many places
where examiners take off marks.

I am going to walk you through this mechanism step by step and explain exactly what is going on.

Step 1

We have an electron-rich alkene and we are going to add H-Cl to it as shown below.

Notice the partial charges on the H-Cl due to the differences in electronegativity. We need to firstly make
a bond between a carbon in the alkene and the H in the H-Cl:
When drawing reaction mechanisms we need to show the movement of electrons. This is done by the
use of curly arrows:

Remember that one bond = 2 electrons and that the curly arrows show the movement of 2
electrons.

Also, remember the golden rule of negative goes towards positive. This means that an arrow
must come from the double bond (electron rich) towards the + on the hydrogen:

First arrow: comes from the double bond and goes to the atom with the + charge. Students often draw
the arrow going towards the double bond, which is just wrong, so dont do it!

Second arrow: if we didnt have this arrow, then there would be too many electrons around the
hydrogen (should only form one bond) so we need to move these electrons on to the Cl.

Quite often you will hear the phrase "electrophilic attack" or the "electrophile attacks the double bond".
This is correct terminology but it misleads people into drawing the arrow from the electrophile, which is
incorrect.

The result of step 1 is shown below:

Carbocation
intermediate
We have made a new bond between the left hand carbon atom and the hydrogen and we have broken
the double bond of the alkene.

The carbon on the right now only has 3 bonds and 6 electrons around it, so we need the positive charge
to show that it is missing 2 electrons.

This structure is called a carbocation intermediate.remember this phrase!

Step 2

The chloro atom now has a negative charge to show that it has picked up an extra electron.

All we have to do is join the Cl- to the carbon atom to make a new bond (again negative going towards
positive). This part should be easy:

And thats it. Once you can do one example, you can do them all. It just takes a bit of practise.

The good news is that a lot of the rules for electrophilic reactions also apply to nucleophilic chemistry and
even benzene chemistry in A2.
So it is very important to grasp these concepts and rules as soon as you can. You will use them for as long
as you do chemistry.