Documente Academic
Documente Profesional
Documente Cultură
Aromatic Hydrocarbon
Prepared by:
Arbanah Muhammad
arbanah@micet.unikl.edu.my
TOPICS
Benzene
Naming benzene derivatives
Mono Substituted Benzene
Di substituted Benzene
Three Or More Substituents
Phenyl
Preparation of Benzene
Reaction of Benzene
P/S: IF more than one Lewis structure can be drawn, the molecule or ion
is said to have resonance
Kekule structure
Kekule suggested that the carbon atoms of
benzene ring are in the ring, bonded to each
other by alternating single and double bonds.
H
H
OR
H
Kekule
Structure
H
H
However,
benzene
reaction.
Resonance Structure
In 1930s , Linus Pauling introduced the concept
of hybrid orbital and resonance.
The real structure of benzene is the resonance
hybrid from two Kekul structure as shown below:
Hybrid resonance
structure
AROMATIC COMPOUNDS
Nomenclature of benzene
and its derivatives
EXAMPLE:
CH3
Common: toluene
IUPAC:
methylbenzene
fluorobenzene
Br
chlorobenzene
NO2
nitrobenzene
bromobenzene
CH2CH3
ethylbenzene
OH
Toluene
NH2
phenol
COOH
benzoic acid
aniline
CHO
benzaldehyde
DISUBSTITUTED BENZENE
Two Same Substituents
Br
Br
2
3
1,2dibromobenzene
or
odibromobenzene
2
3
4
Br
1,3dibromobenzene
or
mdibromobenzene
Br
1,4dibromobenzene
or
pdibromobenzene
NO2
NO2
NO2
2
3
1,2dinitrobenzene
or
odinitrobenzene
1,3dinitrobenzene
or
mdinitrobenzene
NO2
NO2
2
3
4
NO2
1,4dinitrobenzene
or
pdinitrobenzene
DISUBSTITUTED BENZENE
Two Different Substituents
1
NO2
3
NO2
2nitrobenzoic acid
or
onitrobenzoic acid
COOH
3nitrobenzoic acid
or
mnitrobenzoic acid
NO2
4nitrobenzoic acid
or
pnitrobenzoic acid
Br
2 Br
3
4
Br
1,2,4tribromobenzene
Br
I
2bromo1chloro3iodobenzene
COOH
2 NO2
6
3
HO
NO2
OH
3,5dihydroxybenzoic acid
2,4dinitrophenol
Br
CH3
CH3
4bromo1,2dimethylbenzene
Keep in mind!
Br
CH3
CH3
4bromo1,2dimethylbenzene
correct
4bromoodimethylbenzene
PHENYL GROUP
Benzene ring as substituent.
If alkyl substituent is larger than the ring
(more than 6 C), the compound is named as
phenyl-substituted alkane.
1 CH2
2
CHCH2CH2CH2CH2CH3
2phenylheptane
Phenyl = C6H5 = Ph
CH2C
3 4
CCH3
1phenyl2butene
CH2CH2OH
2phenylethanol
BENZYL GROUP
CH2
phenyl group
benzyl group
CH2Br
CH2OH
benzyl bromide
benzyl alcohol
PROPERTIES OF BENZENE
Physical Properties
Benzene is a colourless, volatile, highly flammable and
non-polar liquid.
Its physical properties include:
Molecular
weight
Melting point
Boiling point
Solubility
78.11
5C
80.1C
Slightly soluble in water
Very soluble in organic
solvents and oil
Preparation of Benzene
Reaction of Benzene
1.HALOGENATION, X2
2.NITRATION, NO3
3.FRIEDAL CRAFT AKYLATION,
RCl
4.FRIEDAL CRAFT ACYLATION,
RC=0Cl
X2, FeX3
(X = Cl Br)
HNO3
X
+ HX
NO2
H2SO4
RCl , AlCl3
+ H2O
nitration
+ HCl
Friedel-Crafts
Alkylation
(R can rearrange)
O
RCCl , AlCl3
halogenation
O
CR
+ HCl
Friedel-Crafts
Acylation
1. Halogenation
The reaction occurs in the presence of Lewis acid
catalyst such as Fe, FeX3,AlX3 ( X is Cl or Br)
The catalyst polarized the halogen molecule & acts as
an electrophile
X
+ X2
Fe or FeX3
+ Br2
FeBr3
+ HBr + FeBr3
2. Nitration
Reagents used for nitration of benzene are conc.
nitric acid and conc. sulphuric acid as catalyst.
The rxn mixture is heated to yield nitrobenzene.
+ HNO3
H2SO4 (conc.)
Heat (50-55C)
NO2
+ H2O
3. Friedel-Crafts Alkylation
This rxn used Lewis acid as a catalystsuch as AlCl 3.
R
+
Benzene
RX
AlX3
+ HX
Alkyl halides
Alkylbenzene
EXAMPLE:
CH2CH3
+ CH3CH2Cl
Benzene
Chloroetane
AlCl3
+ HCl
Ethylbenzene
4. Friedel-Crafts Acylation
Introducing acyl group R
O
Two common acyl groups are the acetyl group and the
benzoyl group
O
CH3C
acetyl group
(ethanoyl group)
O
C
Benzoyl group
For example:
CH3C Cl
acetyl chloride
AlCl 3
80C
C CH3
ketone
HCl
2. Deactivating group
is the electron withdrawing group
that cause the ring to be less
reactive than benzene.
2. Meta director
The group that directs an electrophile to
the meta position
increasing reactivity
ortho/para directors
meta directors
Groups
Activating
Ortho-para
director
-NH2, -NHR,
-NR2,
-OH,
-OR,
C6H5-, R-
Deactivating Halogen
Meta director
-NO2,
-COOH, -CN,
-COOR, -SO3H,
-CHO, -COR
EXAMPLE:
What is the products of the rxn if these given
Compound goes nitration process?
CH3
CH3
NHO3 / H2SO4
methylbenzene
Ortho-para director
NO2
heat
CH3
and
NO2
NO2
NO2
nitrobenzene
meta director
NHO3 / H2SO4
heat
NO2
ADDITIONAL PROBLEMS
1. Write structural formulas for each of the following;
CH3
Br
OH
Br
O 2N
3,5-dinitrophenol
o-dibromobenzene
Br
NO2
p-bromotuluene
H3C
CH2Br
Benzyl bromide
CH3
CH3
tert-buthylbenzene