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Arenes

Arenes are aromatic hydrocarbons containing one or more benzene rings.


A benzene derivative is formed when one of the hydrogen atoms on the benzene ring by an atom or group.

Structure of Benzene
Evidence against Kekules model of Benzene:

Discovered that all bond lengths are equal and all bond angles are 120.
Enthalpy change of hydrogenation of Kekules benzene much higher than experimental value.
Does not undergo electrophilic addition reactions such as bromination, as normal alkenes would.

The Delocalised model of Benzene:

Each carbon atom has 4 valence electrons, 3 of which are used in bonding (-bonds).
One valence electron occupies the p-orbital above and below the plane of the carbon atoms.
The electron in the p-orbital of one atom overlaps with electrons in the p-orbitals of adjacent
carbon atoms, resulting in a ring of electron density above and below the carbon atoms.
This overlap produces a system of -bonds spread over all six of the carbon atoms.
The
electrons are said to
be
delocalised

Reactions of Benzene - Electrophilic Substitution:


Benzene takes place in substitution reactions to preserve the stability of the benzene ring.

The electron-dense ring attracts electrophiles


The electrophile accepts a pair of electrons from the delocalised ring, forming a covalent bond.
An intermediate forms containing both the electrophile and the hydrogen to be substituted.
As the delocalised ring structure is disrupted, the intermediate is less stable than benzene.
The unstable intermediate rapidly loses the hydrogen atom as H+, with the two electrons from the
covalent bond reforming the benzene ring, increasing the stability of the molecule.

Nitration:
50C (for mononitration), Nitrating mixture of HNO3 and Conc. H2SO4
The sulphuric acid acts as a catalyst. It is needed to generate the nitronium ion, NO2+ from the nitric acid
HNO3 + H2SO4 NO2+ + H2SO4- + H2O

The H2SO4 is then reformed:


H+ + HSO4- H2SO4
Halogenation:
Benzene is too stable to react with halogens. It will however react in the presence of a halogen carrier, used
to generate a positively charged halonium ion (e.g bromonium, Br+) which is a more powerful electrophile
than a halogen (e.g Br2)
Br2 + FeBr3 Br+ + FeBr4-

The FeBr3 is then reformed and HBr is also produced:


H+ + FeBr4- FeBr3 + HBr

Halogen Carriers:
Bromination Fe, FeBr3, AlBr3
Chlorination Fe, AlCl3, FeCl3

Reactivity of Alkenes and Benzene

Benzene has delocalised electrons spread over all 6 carbon atoms.


Alkenes have localised electrons above and below the two carbon atoms in the double bond.
Benzene therefore has a lower electron density than alkenes.
Non-polar molecules such as bromine can therefore not be polarised by benzene and no reaction
can occur, without the use of a halogen carrier.

The greater positive charge from the more powerful electrophile, X+, means the halonium ion is
able to attract a pair of electrons from the benzene ring so that a reaction can take place.