AROMATIC
COMPOUNDS
Aromatic
compounds are benzene
and compound that resemble
benzene in chemical behavior.
STRUCTURE OF BENZENE
Benzene is the parent substance of
aromatic hydrocarbons. It was first
isolated by Michael Faraday in 1825,
Its correct molecular formula, C6H6,
was established a few years later.
Properties of benzene was a very
difficult problem for chemists in the
mid-19th century
In 1826, August Kekule proposed
that carbon atoms in a benzene
molecule are arranged in a sixmembered ring with one hydrogen
atom bonded to each carbon atom
and with three carbon-carbon
double bonds. He further
suggested that the double bonds
are in rapid oscillation within the
molecule. Therefore he proposed
that the structure of benzene could
be represented in this fashion.
Or simply
Kekules formulas have one serious
shortcoming: they represent benzene and
related substances as highly unsaturated
compounds. Yet benzene does not react
like a typical alkene
Modern theory accounts for structure of
the benzene molecule in this way: the
orbital hybridization of the carbon atom is
sp2. a planar hexagonal ring is formed by
the overlapping of two sp2 orbitals on each
of six carbon atom. The other sp2 orbital on
each carbon atom overlaps an s orbital of
hydrogen atom, bonding the carbon atom,
overlap each other and form doughnutshaped pi electron clouds above an below
the plane ring.
Neither of two structures proposed
by kekule therefore represents
benzene. The real benzene
molecule is in fact a hybrid of the
two kekule structures and is
commonly represented by a
hexagon with a circle. The circle
represent the pi cloud of electron.
Or
NOMENCLATURE OF
AROMATIC COMPOUNDS
1.
Monosubstituted benzenes
A substituted benzene is by replacing one
or more hydrogen atoms of benzene by
another atom or group of atoms.
Named by adding the name of substituted
group as a prefix to the word benzene.
Cl
|
CH 2CH3
Chlorobenzene
ethylbenzene
NO2
nitrobenzene
Certain monosubstituted benzenes have
special names. These are used as parent
names for further substituted compounds so
they should be learned.
CH3
OH
COOH
CHO
NH 2
| |
|
|
|
Toluene
phenol
benzoic acid
benzaldehyde
anline
The C6H5- group is known as the phenyl group, and
the name phenyl is used to name compounds that
can not easily be named as benzene derivatives.
CH3
- CH 2|
- CHCHClCH2CH3
diphenylmethane
3-chloro-2-phenylpentane
2.
Disubstituted benzenes
When two substituted groups replace two
hydrogen atoms in a benzene molecule, three
different isomeric compounds are possible. The
prefix ortho-(o), meta-(m-), and para-(p-) are
used to name disubstituted benzens in one
nomenclature system. Ortho designates 1,2
disubstitution, meta reprsents 1,3 disubtitution,
and para designates 1,4 disubtitution.
Consider the dichlorobenzens, C 6H4Cl2
Cl
Cl
Cl
|
|
Cl
|
Cl
o-dichlorobenzene
Cl
m-dichlorobenzene
dichlorobenzene
(1,2-dichlorobenzene) (1,3-dichlorobenzene)
dicholorobenzene)
p( 1,4-
The dimethylbenzenes have special name
xylene
CH3
|
CH3
CH3
CH3
CH3
CH3
O-xylene
m-xylene
p-xylene
When the two susbstituents are different and
neither is part of a compound with a special
name. The names of the two substituent are
given in alphabetical order, followed by the
word benzene.
NO2
Cl
3. Polysubstituted benzenes
When there are more than two substituted
on beneze ring, the carbon atoms in the ring
are numbered starting of the substituted
groups.
Numbering may be either clockwise or
counterclockwise but musst be done in the
direction that gives the lowest posible numbers
to the substituted group.
Br Br
OH
Br
Cl
Br
1,2,4-tribromobenzene
5-bromo-2-chlorophenol
4. Polycyclic aromatic compounds
Polycyclic or fused aromatic ring system
structure consist of two or more rings
which two carbon atoms are common to
two rings. Three of the most common
hydrocarbons : Napthalene (C10H8),
anthracene (C14.H10), and phenanthrene
(C14H10). One hydrogen is attached to each
carbon atom except at the carbons that
are common to two rings.
Naphtalene
phenanthrene
anthracene
CHEMICAL REACTION OF
BENZENE AND
ALXYLBENZENES
Characteristically, the reagents
the react the aromatic ring of
benzene and its derivatives are
electrophiles.
general formula of Arene ArH,
where Ar - aryl group,
The electrophilic portion of the
reagent replaces one of the
hydrogens on the rings.
+
2. Halogenation of benzene
Bromine reacts with benzene in the
presence of Febr3 as a catalyst to give
bromobenzene. Chlorine reacts similarly in
the presence of FeCl3 to give
chlorobenzene.
C6H6 + Cl2
FeCl
C6H5NO2 + HCl
3
3. Nitration of benzene
Warning benzene with a mixture of
concentrated nitric acid and concentrated
sulfuric acid gives nitrobenzene. In this
reaction a nitro group (-NO2) replaces a
hydrogen atom of benzene.
C6H6 + HO - NO2
H SO 60c
C6H5NO2 +
2
4.
Friedel-crafts alkylation of benzene
Alkyl halides react with benzene in the
presence of AlCl3 to yield alkyl benzenes
C6H6 + CH3CH2Br
H2 O
ArCl3
C6H5SO3H +
5. Friedel-crafts alkylation of benzene
An analogous reaction occurs when acyl
halides react with benzene in the
presence of AlCl3. The products are
acylbenzenes.
C H
+ CH COCl
AlCl
C H COCH
6. Oxidation of alkylbenzenes
An alkyl side chain on a benzene ring is
oxidized on being heated with a mixture of
aqueous Na2Cr2O7 and H2SO4. the alkyl
groups, regardless of their chain leght, are
converted to carboxyl groups; thus, the
product is benzoic acid or a substituted
derivative of benzoic acid. The other
carbon atoms of the side chain are
converted to CO2.
- CH3 + (O)
O2N+ CO2
-CH2CH3 + (O)
- COOH
O2N-
-COOH
7. Halogenation of alkylbenzenes
Side-chain halogenation of toluene can
yield successively the mono-, di-, and trihalo compounds.
CH3
CH2Cl
CHCl2
CCl3
|
|
Cl2
uv
|
Cl2
uv
Toluene benzyl cholride
benzotichloride
|
Cl2
uv
benzal chloride
RATE AND ORIENTATION IN
ELECTROPHILIC AROMATIC
SUBSTITUTION
Substituents already present on an
aromtic ring have two effects:
1. It effects the rate of electrophilic aromatic
ring have two effects:
2. It effects the regioselectivity (orietation)
of electrophillic aromatic substitution
CH3
CF 3
|
Toluene
benzene triflouromethylbenzene
Most reactive
least reactive
EFFECT ON
RATE
Very strongly
activating
Strongly
activating
Activating
SUBSTITUENT
-NH2
Amano
-NHR
Alkylamino
-NH2
dialkylami
no
-OH
hydroxyl
-NHCOR Acylamino
-OR
Alkoxyl
-R
Alkyl
EFFECT ON
ORIENTATION
ortho-para
directing
Ortho-para
directing
Ortho-para
directing
Deactivating
-X
Halogen
Ortho-para
directing
Strongly
deactivating
-CHO
Formyl
Meta directing
-COR
Acyl
-COOH Carboxyl
-COOR Ester
Very strongly
deactivating
-COCl
Acyl
choloride
-CN
Cyano
-SO3H
Sulfuric acid
-CF3
Triflouromet
hyl
-NO2
nitro
Meta directing
MULTIPLE SUBSTITUENT
EFFECTS
When a benzene ring bears two or more
substituents, noth its reactivity and
orientation of further substitution can, in
most cases, be predicted from the
cumulative effects of its substituents.
CH3
CH3
|
O O
| COCH3
+ CH3COCCH3
AlCl
3
CH3
P-xylene
CH3
2,5-dimethylacetophenone
In cases inwhiich the directing effects of
individual substituents oppose each other, it is
the more activating substituent that controls the
regioselectively of electrophilic aromatic
substitution. Thus, bromination occurs ortho to
the N-methylamino group in 4-Chloro-Nmethylaniline because this group is a very
powerful activating substituent whilt the
chlorine is weakly deactivating.
NHCH3
|
NHCH3
|
+ Br2
Br
HAr
Cl
4-chloro-N-methylaniline
methylaniline
Cl
2 bromo-4chloro-N-
When two positions are comparably
activated by alkyl groups, substitution
usually occurs at the methyl group in
presence to those ortho to the larger
tert-butyl group. This is an example of
steric effect.
CH3
CH3
|
|
+ HO NO2
|
C(CH3)3
P-tert-butyltouluene
NO2
H2SO4
|
C(CH3)3
4-tert-butyl-2-nitrotoluene
Nitration of m-xylene is directed ortho to
one methyl group and para to other.
CH3
CH3
|
|
+ HO NO2
CH3
H2SO4
| CH3
NO2
m-xylene
2,4-dimethyl-1-nitrobenzene
The ortho position between the two methyl groups
is less reactive because it is more sterically
hindred.
AROMATIc
COMPOUNDS
SUBMITTED BY : SHERLENE A.
GESIM
SUBMITTED TO: MRS.
ELIZABETH VIVAR
