Chapter 4
Chapter 4
Chapter 4
AROMATIC HYDROCARBON
Aromatic Compounds
Benzene is
• An aromatic compound.
• a ring of 6 C atoms and 6 H atoms.
• a flat ring structure drawn with three double
bonds.
Benzene
• Kekule suggested two structural formulas for benzene:
Parent name
CH32 CH3
CH CH2 CH3
CHCl CH=CHCHCH
CH2-CH
CH33 CH=CHC
3 2 3 2 2
methylbenzene
Eth ylb enzene Eth ylbeenzene
chlorobenzene
Toluen Toluen
Eth ylb
e enzene Styrene
ethylbenzene
Styrene Tolu
Two commonly encountered substituent groups that
incorporate a benzene ring are phenyl, and benzyl.
m-nitrotoluene
R ipso NO2
ortho
o- 1-methyl-3-nitro-benzene
meta Cl
m-
p- para p-dichlorobenzene
Cl
1,4-dichlorobenzene
WWU -- Chemistry
Naming Multisubstituted Benzene Compounds
• When there are 2 or more substituents, they are numbered to
give the lowest numbers (alphabetical if same both ways)
• Disubsituted benzenes are also named by the common prefixes
ortho, meta and para
Examples:
Br CH3
Cl
Br
meta-dibromobenzene ortho-chlorotoluene
(1,3-dibromobenzene) (1-chloro-2-methylbenzene)
OH NH2
Br
para-ethylphenol 4-bromo-2-fluoroanaline
(1-hydroxy-4-ethylbenzene) (1-amino-4-bromo-2-fluorobenzene)
Electrophilic Aromatic Substitution
H E
+ E+ + H+
Mechanism of Bromonation of Benzene
• First, a Br+ is transferred from Br2 to benzene, forming a
carbocation and a chloride ion
• Next, the chloride ion removes an H+ from the carbocation
to form chlorobenzene and HBr
Br
H
FeBr3
+ Br Br + Br
Br
H Br
+ Br + H Br
Halogenation
• In halogenation, benzene reacts with Cl2 or Br2 in the presence
of a Lewis acid catalyst, such as FeCl3 or FeBr3, to give the aryl
halides chlorobenzene or bromobenzene respectively.
• Analogous reactions with I2 and F2 are not synthetically useful
because I2 is too unreactive and F2 reacts too violently.
Halogenation of Benzene
H X
FeX3
+ X2 + H X
X2 + FeX3 X FeX4
a "stable" complex
•X+ is a halonium ion:
•Cl+ = chloronium ion
•Br+ = bromonium ion
•The halonium ion is the electrophile in this reaction.
Addition reaction
Halogenation
Cl
Cl Cl
u.v.
+ 3Cl2
Cl Cl
Cl
(i) Halogenation
ArH reacts with halogen (X2), in the presence of a Lewis acid
catalyst (AlX3 or FeX3).
(ii) Nitration
ArH reacts with concentrated nitric acid (HNO3), in the presence
of concentrated sulphuric acid (H2SO4) as a catalyst, to form
nitrobenzene (ArNO2).
(iv) Friedel-Craft alkylation
ArH reacts with haloalkanes (RX), in the presence of
Lewis acid catalyst (AlX3 or FeX3), to form alkylarene (Ar-
R). The electrophile is alkylcarbocation (R+).
H C R
AlCl3
+
+
O
H X
R C Cl
H2
Pt/Ni/Pd
CHARACTERIZATION TEST
Nitration of benzene
Reagent: concentrated HNO3
Condition: concentrated H2SO4, 55°C
Equation:
+ conc HNO3 H2SO4
+ HO
2
55 C
NO2