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(l)
(m)
H
H
C
C
C
Benzene
C6H6
H
C
C
C
H
Methylbenzene
C7H8
+ Cl2
HCl
chlorobenzene
Similarly, bromine in the presence of the aluminium tribromide [or Iron(III)
bromide]:
C6H6 + Br2
AlBr3
C6H5Br + HBr
+ HNO3
H2O
nitrobenzene
Mechanism of Electrophilic Substitution: Nitration of Benzene:
The reaction occurs in several stages.
1. The Nitronium ion (NO2+) is generated:
H
H2SO4
H
NO2
HSO4-
NO2
H2O
+ O N O
nitronium ion
(electrophile)
O
H
O
H
NO2
NO2
H
+
NO2
NO2+
NO2
+
The positive charge is delocalised over three of the carbon atoms; the ion is
a resonance hybrid (mixture) of three structures above and this delocalisation
stabilizes the developing positive charge making benzenes and arenes
more reactive than alkanes. Remember the more spread out the positive
charge is around the ring and lower in energy! (The curly arrows represent a
movement of electrons).
H
NO2
positive charge spreads around the ring
NO2
NO2
+
HSO4-
H2SO4
Cl
AlCl3
AlCl4-
CH3CH2
Br
AlBr3
N:
N
..
N
..
Nitrogen of group V has two SP2 hybrid orbitals, one P orbital and one lone
pair of electrons. One electron from the P orbital is used in delocalised
bonding in the six-membered ring. In the diagram above the electron cloud
therefore becomes delocalised. It is the lone pair of electrons that make
pyridine basic in nature, but do not take part in the delocalised ring!