Benzene Chemistry part 1

Structure
Benzene comes under a category called aromatic compounds.

It is often called an aromatic or benzene ring which consists of 6 carbons and 6 hydrogens (1 hydrogen
on every carbon) with formula C6H6.

The benzene ring was initially thought to contain three alternating double and single bonds, which is
known as the Kekule model shown here:

H C H
C C
C C
H C H
H

X-ray diffraction studies are used to measure bond lengths (and bond angles). It showed that the bonds
in benzene are all the same length and somewhere inbetween double and single bonds. Therefore, the
Kekule model is incorrect.

This leads to the commonly used circle representation when drawing benzene, which shows that the
bonds are the same length:

Benzene is flat or planar. All planar molecules have bond angles of 120.

Reactivity

Benzene is very unreactive. Its stability is due to a delocalised system of 6 electrons in 6 x p orbitals.

H
H
C C
H C C H

C C
H H
Each carbon has an empty p orbital that can overlap with another p orbital on an adjacent carbon
allowing the electrons to move between carbon atoms i.e. not fixed to one carbon. It is this
delocalisation that accounts for the stability.

Enthalpy Experiments
The stability of benzene has been shown by two enthalpy experiments. These experiments also showed
that the Kekule model was incorrect.

The first experiment was the hydrogenation (addition of hydrogen) of cyclohexene (an alkene) to form
cyclohexane, which gave an enthalpy value of -120 kJmol-1 (only one double bond being hydrogenated).

The other experiment was to hydrogenate benzene to form the same cyclohexane product. The Kekule
model implies that it is three double bonds that are being hydrogenated. If this was the case then we
would expect an enthalpy value of -360 kJmol-1 i.e. 3 x -120.

But the value found for benzene was only -208 kJmol-1. This implies that benzene is much more stable
than cyclohexene and that it is not simply three double and single bonds.

The correct way to draw benzene. The circle is there to show the
delocalised ring.

The proposed Kekule structure and the circle representation are compared. The Kekule structure is there
to represent the hypothetical three double and single bond structure.

The diagram below shows the different enthalpies for the Kekule and the correct structure. The difference
in energy between the two structures is sometimes referred to as the extra stabilisation energy of
benzene, which is approximately -152 KJ mol-1.
The final product, cyclohexane, is the same for both reactions (and therefore at the same energy). This
means that the different enthalpy change values seen for the hydrogenation reactions, the starting
structures must be at different energies to begin with.

As the value for the benzene reaction is only -208 kJmol -1, it therefore must be at a lower energy to begin
with than the Kekule structure (-360 kJmol-1). And a lower energy means more stable/less reactive.

Electrophilic Substitution

the main reaction of benzene chemistry is electrophilic substitution

at no other point will you see electrophilic substitution. So, as soon as you see benzene or another
similar molecule, the words electrophilic substitution must be in your head!

The mechanism is very similar, but not identical, to the electrophilic addition to alkenes in AS.

The way to tackle this section is to learn and understand the basic mechanism, which is the same for all
benzene reactions.

E+ represents any electrophile:

Step 1: draw an arrow from the benzene ring to the electrophile. A new bond is formed between a
carbon atom on the benzene and the electrophile.

remember the arrow goes from the area of high electron density to the electron deficient
electrophile.

Step 2: the structure drawn here is the carbocation intermediate. As we have used a pair of electrons to
form the bond, the benzene ring has been broken.

draw the intermediate as a broken circle with a + in the middle that covers at least 3 carbon atoms.

Step 3: As was mentioned above, the key point about benzene is that it is unreactive in comparison to
alkenes due to delocalization of electrons. So in step 3 we need to substitute a hydrogen atom to
regenerate the benzene ring for stability reasons.