25.

1 Benzene and its

compounds
The benzene ring
A benzene ring is a hexagon made of 6 carbon atoms bonded together in a particular
way. they are found in man y compounds that are commercially important, e.g.,
medicines, dyes, and plastics.

💡 Benzene is highly toxic, and is a carcinogen. It is particularly hazardous as

it can be absorbed through the skin.

Compounds based on benzene are widely found in nature, such as vanillin in vanilla.
Organic hydrocarbons containing one or more benzene rings are called arenes.
Generally, compounds of benzene are called aryl compounds or aromatic
compounds, e.g. chlorobenzene.
The benzene molecule is planar, and perfectly symmetrical.
It does not react like regular alkenes; for example, ethene decolourises bromine
water at rtp., whereas benzene needs much harsher conditions.

Structure of benzene
Each of the 6 carbon atoms in benzene is sp² hybridised, sharing:

1 pair of e¯ s with one of its neighbouring carbon atoms

1 pair of e¯ s with its other neighbouring carbon atom

1 pair of e¯ s with a hydrogen atom

That’s 3 δ bonds. This leaves one e¯ spare on each of the 6 carbon atoms in
benzene. Each carbon atom contributes that 1 spare e¯ to a π bond.
However, these π bonds are not the same as the π bonds found in alkenes.
In alkenes, a π bond helps to bond one pair of carbon atoms to each other, but in
benzene the 6 spare p-orbital e¯ s are spread over all 6 carbon atoms in the ring.
These e¯ s are said to be delocalised.

25.1 Benzene and its compounds 1

 These π bonds are formed from the overlap of the carbon atoms’ unhybridised p-
orbital. So to achieve maximum overlap, the benzene molecule must be planar. The
lobes of the p-orbitals overlap side-by-side to form a ring of delocalised electrons
above and below the plane of carbon atoms.

Reactions of arenes
Most reactions of benzene and other arenes maintain the highly stable ring of π
bonding electrons intact.
This occurs by substituting an atom/group of atoms, for one or more hydrogen atoms
attached to the benzene ring.
Addition reactions into the benzene ring would disrupt the ‘aromatic stabilisation’
achieved by the complete delocalisation in the ring.
The initial attack is usually by an electrophile, which is attracted to the high electron
density around the ring.

About electron-donating and electron-withdrawing groups

When halogenating methylbenzene or other alkylarenes, the halogen atom
substitutes into the benzene ring at positions 2 or 4. These positions are ‘activated’
by any electron-donating groups bonded directly to the benzene ring.

So when methylbenzene is reacted with Cl₂, using an anhydrous AlCl₃ catalyst, two
products can be made: 2-chloromethylbenzene and 4-chloromethylbenzene.

If excess Cl₂ gas is bubbled through, we can form 2,4-dichloromethylbenzene,

2,6-dichloromethylbenzene and 2,4,6-dichloromethylbenzene.
The carbon-halogen bond in halogenoarenes is stronger than the equivalent bond in
a halogenoalkane, making halogenoarenes much less reactive. this is because the
lone pairs on the halogen atom overlap slightly with the π bonding system in the
benzene ring. this gives the carbon-halogen bond in a halogenoalkane a partial
double-bond character.

25.1 Benzene and its compounds 2

 💡 Note:
The methyl side chain off the benzene ring is not affected under the
conditions used in the previous reaction. However, Cl₂ will react with
alkanes in the presence of UV light or strong sunlight (free-radical
substitution). So if the Cl₂ is passed through boiling methylbenzene in the
presence of UV light, a Cl will substitute an H in the side chain, giving
chloromethylbenzene.

Note that there is no substitution into the benzene ring under these
conditions.

In excess Cl₂, eventually all 3 hydrogen atoms on the methyl side chain
will be replaced by chlorine atoms.

In the case of nitration, in order to predict the products of further substitution into the
benzene ring of the nitrobenzene formed, we must consider the ‘directing effect’ of
the nitro group.
Further nitration produces 1,3-dinitrobenzene and 1,3,5-trinitrobenzene.

The —NO₂ group is electron-withdrawing. This type of group deactivates the 2 and 4
positions in the benzene ring, thus when there is a nitro group bonded to the
benzene ring, further substitutions are directed to the 3 and 5 positions.

Electron-donating groups Electron-withdrawing groups (deactivate

(activate 2,4,6 positions) 2,4,6 positions, so 3,5 left)

—NH₂ —NO₂

—OH —COR

—R —CHO

—Cl —COOH

25.1 Benzene and its compounds 3