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The structure of benzene

Aromatic Compounds

unsaturated cyclic hydrocarbons


organic compounds had an aroma or
odour
contain single rings or groups of rings
simplest aromatic compound is benzene
aromatic compounds include benzene or
are benzene based and have benzene-
like structures and properties.
Physical Properties of Benzene
MPbenzene = 5.5C, BPbenzene=80.1C

non-polar Molecule

insoluble in water

less dense than water


This new hydrocarbon isolated by Michael Faraday in 1825
presented a huge problem.
.
The % of carbon was 92% Carbon (C= 12) . Its
relative molecular mass was 78.
Calculate the molecular formula
The molecular formula is C6H6 suggesting that the molecule
contained a large number of double bonds.

Benzene did not, it was surprisingly unreactive

All the chemistry they knew suggested that any substance


with a double or triple bond would be very reactive and react
readily with HBr in the dark.
In 1865 after a dream about a snake biting its own tale, Kekul
suggested the following structure for benzene.

This did not explain why the structure was so unreactive, the
chemists of the time were convinced that it should react with
bromine in the dark at room temperature. This does not happen
with benzene.
This does not fit with Kekuls idea of alternating double and single bonds.
Another problem was the energy of hydrogenation (addition of hydrogen).
The hydrogenation of cyclohexane is well known.
So if three double bonds are present as in benzene, then the
comparable reaction should liberate 3 times that of cyclohexane.
-(3 120) = - 360 kJ mol-1

But the actual value for benzene was found to be different. -208kJ
mol-1

So benzene is (360-208) = 152 kJ mol-1 more stable than


otherwise expected, or if it contained 3 ordinary C=C bonds.
E

-360kJ/mol (3
X 120)

-208kJ/mol

progress
This is a better all round model than the Kekul
structure which shows 2 extremes of the same
thing. The circle in the middle shows the
delocalisation of the aromatic system.
The bond length of C-C bonds in benzene are found
someway between that of an alkane and an alkene.

Bond Lengths /nm

C-C 0.154
cyclohexane
C=C 0.134
cyclohexane
C-C in benzene 0.140
Evidence for delocalisation in benzene

Hydrogenation energies are lower than expected

Delocalised systems are highly saturated, but their


reactions are of substitution rather than addition..

Carbon-Carbon bond lengths are equal in the delocalised system.


Benzene is a flat
molecule, with all atoms
in the same plane,( bond
angle 120)

When the benzene ring is


attached to an aliphatic
Any compound skeleton, it is called the
where the ratio of phenyl group. The formula
C:H is about 1:1 is of a phenyl group id C6H5.
likely to contain a
benzene ring.
There are several methods of displaying the formula of
benzene, the standard A2 method is:

This represents the delocalised electrons, and is


probably the best way of representing the delocalisation
during mechanisms
Benzene is a flat molecule with 6 carbons bonded in a
Planar ring
Each carbon is covalently joined to two other carbons
and one hydrogen. A total of three covalent bonds
The remaining outer electron of each carbon is shared
with the other carbons in the ring. The six electrons are
delocalised around the ring system, giving stability
All bond lengths are the same.
Never draw benzene as a
simple hexagon. This would
be a molecule of cyclohexane
this has no delocalised
electrons, and is not flat like
benzene.

Also unless drawing


mechanisms, never include
the hydrogens attached
directly to the benzene ring.
This is bad chemistry.
Nomenclature
A. Single group
OCH3 O H O OH

methoxybenzene benzenecarbaldehyde acid


benzenecarboxylic
(anisole) (benzaldehyde) (benzoic acid)
NH2 SO3H

benzenamine benzenesulfonic acid


(aniline) 16
B. Two groups
X X X
Y

ortho Y
(or 1,2) meta
(or 1,3) para (or 1,4)
NO2

Br

NO2

17
Naming benzene molecules

1.2-dimethyl benzene
(ortho-dimethyl benzene) 1,4-dimethyl benzene
(para-dimethyl benzene)

1,3-dimethylbenzene
(meta-dimethyl benzene)
Common Names of Subs. Benzenes
CH3 OH NH2

toluene phenol H aniline


OCH3 C
CH2

O anisole O O
styrene
C C C
H OH CH3

CH3
benzaldehyde benzoic acid acetophenone
C N CHCH3

benzonitrile cumene
Fused ring systems