SN1

versus SN2 (Edexcel)

Most of the A2 nucleophilic chemistry involves carbonyl groups (see carbonyl chemistry section).
However, we are going to revisit the haloalkanes here.

From AS, the basic mechanism is as follows. We are now going to take this one stage further.

SN1 and SN2
You will have briefly looked at SN1 and SN2 at AS. The 1 and the 2 normally causes confusion at AS but
now you are going to unravel this great mystery! Although this is an organic chemistry reaction, it also
involves rates, so it could appear in either section.

SN1 stands for Substitution Nucelophilic Unimolecular and SN2 stands for Substitution Nucleophilic
Bimolecular.

Both are simple nucleophilic substitutions but the mechanisms differ slightly depending on the starting
haloalkane.

The 1 (unimoecular) tells you that there is only one reactant in the rate equation:

Rate = k[A]

The 2 (bimolecular) tells you that there are two reactants in the rate equation:

Rate = k[A][B]

SN1
Tertiary haloalkanes do SN1 reactions and the reaction occurs in 2 steps.

Most people initially assume that the 1 means one step, so please avoid this mistake. As was said above,
the 1 is from from the rate equation.

The key point here is that it is a tertiary haloalkane.

The CH3 groups are bulky and take up a lot of space and act like a shield or barrier. The nucelophile is
blocked by the electron clouds from the methyl groups.

This means that the nucleophile cannot attack the carbon with the + as normal (shown below) and
instead requires a two step mechanism.

Therefore, the first step in the mechanism is for the bromide ion to leave before the nucleophile is added
(see mechanism at bottom of previous page). Or as students normally say, the Br group just magically
falls off!.

Why does the bromo group just fall off? This doesnt matter, you will never be asked this.

The structure that is formed with the + on the carbon is a carbocation intermediate:

The nucleophile can then attack from the front as shown in step 2 above.

Note: the product from an SN1 reaction could be a racemic mixture. A chiral centre could be formed if
there are four different groups attached to the carbon. In the mechanism above, this is not the case.

The reason for the racemic mixture is the same as when talking about it in the carbonyl topic. The second
step of the mechanism is the attack of the nucleophile from above or below the planar C+, both of which
have a 50% chance of happening.

SN2
Primary haloalkanes do SN2 reactions that occur in 1 step.

Remember that the 2 refers to bimolecular and is to do with the number of reactants in the rate
equation.

The mechanism is one step but it does go through a transition state, which is the middle structure shown
below:

A transition state is a theoretical state of high energy (very unstable) where the bonds arent completely
broken or formed.its as the name suggests, in a state of transition.

Only one product is formed but the stereochemistry is reversed. If you had one enantiomer to begin with,
you end up with the opposite one in the product.

By looking at the mechanism above, they sometimes refer to a blowing an umbrella inside out effect.
Look at the starting compound and the product and it kind of looks like it is inside out!

Note: secondary haloalkanes can do be SN1 or SN2. You cant tell without some help from the question.


This whole SN1 and SN2 thing is simply looking at a specific reaction in more detail and it is unnecessary to
mention it unless specifically asked about. When doing normal organic questions just draw the simple
substitution and forget this stuff.