Electrophilic Addition part 2

Addition to Unsymmetrical Alkenes

You must have the basic concepts in part 1 mastered before moving on to this stage.

In part 1, we looked at an example involving a symmetrical alkene. We will now look at an

unsymmetrical alkene (we have added a CH3 group to the alkene), which makes things a little more
difficult.

For example:

The mechanism is exactly the same as we did in part 1 BUT we now have a choice.

Do we add the H atom to the left or right hand carbon atom? This is important as two different products
are possible depending on where we add the H atom.

In the symmetrical alkene in part 1 it didn't matter, as it would be the same product no matter where the
H was added.

Major and Minor

The two possible products of the unsymmetrical alkene reaction are shown here:

So, which is the correct structure? The answer is both.

Number 1 is the major product and number 2 is the minor product. This question comes up almost all the
time in AS exams so you need an explanation.

A simple rule
This rule allows you to decide quickly which would be the major product without drawing mechanisms.
 Rule: add the H atom in step 1 to the carbon with the most hydrogens already present. This will give
you the major product.

Mechanism
The mechanism is exactly as we did in part 1.

In step 1, add the H on to the left hand carbon atom to give the carbocation shown below in number 1.

Then repeat the mechanism but this time add the H on to the right hand carbon, which gives the
carbocation shown in number 2:

The second step is also the same as in part 1. Just add the Cl- to the positively charged carbon.

The important part.the stability of the carbocations shown above, dictates which product is the major
one.

Carbocation intermediate
The major versus minor product thing comes down to which carbocation intermediate is the most stable.

the more stable carbocation gives the major product.

In this case, number 1 is the more stable intermediate.

Why is number 1 more stable than number 2?

It all comes down to primary versus secondary versus tertiary:

In our example, number 1 is a secondary carbocation (only 1 H attached to the carbon with the + charge)
intermediate whereas number 2 is a primary (2 hydrogens attached to the carbon with the + charge).
Why is the secondary more stable?

The aim is to try to stabilise the carbocation intermediate. And the way to do this is by donating electrons
to it.

The two CH3 groups attached to the carbon with the + charge have a slight electron donating effect,
which has a stabilising effect.

On the other hand, the primary intermediate (number 2) only has hydrogen atoms (no electron donating
effect) and only one CH3 group.

Therefore it doesnt have the same extent of electron donation and is not as stabilised. A more stable
carbocation means it hangs around a bit longer and has more chance of the Cl - reacting with it to form
the product.

These questions come down to being able to draw the carbocation intermediates and then deciding
which is the most stable.

Further alkene reactions

With these reactions you just need to know them, no mechanisms are required:

CH2=CH2 + KMnO4 CH2OH-CH2OH (a diol is formed)

CH2=CH2 + H2O (steam) CH3-CH2OH (H3PO4 catalyst)

CH2=CH2 + H2 CH3-CH3 (Ni catalyst)