Chapter 4

Aromatic Compounds
 Teaching Objectives and Requirements
 Understand: Substituted Benzene, Polycy
clic and Heterocyclic Aromatic Compound
s.
 Grasp: Aromaticity, Hückel’s Rule, Nomen
clature, Electrophilic Aromatic Substitution
,
 Interpretation of Rate Effects and Directin
g Effects, Reactions of Side Chains: Free-
Radical, Halogenation and Oxidation.
 Key points and Areas of Difficulty
 Hückel’s Rule, Nomenclature, Electrophili
c Aromatic Substitution, Interpretation of R
ate Effects and Directing Effects
 Reactions of Side Chains: Free-Radical H
alogenation and Oxidation.
 4.1 Substituted Benzene
Compounds
 Aromatic means “fragrant”
 Some fragrant compounds contain benzene
ring
 In early time, that’s how the name of
aromatic compound comes from
OH O
C CH3
O

oil of wintergreen
 4.1 Substituted Benzene
Compounds
 Many benzene compounds are not fragrant
 Six-membered benzene ring is the character

HO O
C
O CH3
C
O
aspirin
 4.2 Aromaticity
 C6H6 is highly unsaturated compared with
hexane C6H12
 It does not undergo addition reactions.
 Benzene reacts with bromine, in the prese
nce of iron bromide as a catalyst, to give a
single monosubstituted product, C6H5Br.
H Br
FeBr3
+ Br2 + HBr
 4.2 Aromaticity
 Kekule’s Concept of Benzene
 In 1865,a German chemist,August Kekule
 Benzene is a ring of six carbon atoms linked by
alternating single and double bonds.
 Two structures differing only in the arrangemen
t of single and double bonds
H H

H C H H C H
C C C C
or
C C C C
C H H C H
H
H H
 4.2 Aromaticity
 Oscillate around the ring
 Rapid oscillation of single and double
bonds around the ring makes all six
carbon atoms, and therefore all six
hydrogen atoms, equivalent.
 A single structure is observed
 Resonance Theory and Benzene
 A planar molecule ,same C-C bonds
 4.2 Aromaticity
 The bond angles of the ring are all 120 de
gree.
 sp2-hybridized carbon atoms
 Three σbonds
 4.2 Aromaticity
 The fourth electron is in a 2p orbital perpend
icular to the plane of the benzene ring.
 A set of six 2p orbitals overlap to share their
six electrons in a πsystem that extends
 4.2 Aromaticity
 Over the entire ring of carbon atoms.
 The sharing of electrons over many atoms
is called delocalization.
 The Huckel Rule
 Three general criteria must be met if a mol
ecule is to be aromatic.
 First, the molecule must be cyclic and pla
nar.
 4.2 Aromaticity
 Second, the ring must contain only sp2-hy
bridized atoms containing 2p orbitals that
can form a delocalized system of πelectro
ns.
 Third, the number of πelectrons must be e
qual to 4n+2, where n is an integer.

benzene cyclobetadiene cyclooctatetraene

 4.3 Polycyclic and Heterocyclic
Aromatic Compounds
 Polycyclic aromatic hydrocarbons equal to
“fused” contain two or more rings.
3
4 2
8 1 8 9 1 5
1
7 2 7 2 6

6 3 6 3 7 10
5 4 5 10 4 8 9
naphthalene anthracene phenanthrene
 4.3 Polycyclic and Heterocyclic
Aromatic Compounds
 Cyclic compounds that have one or more at
oms other than carbon within the ring are sa
id to be heterocyclic compounds.
 Heterocyclic aromatic compounds:4n+2π el
ectrons.

N N O S
H
pyridine pyrrole furan thiophene
 4.4 Nomenclature of Benzene
Compounds
 Uses the names of the substituents as prefix
es to benzene.
NO2 CH2CH3 Br

nitrobenzene ethylbenzene bromobenzene

 Ortho isomer has two groups on adjacent ca

rbon atoms, in a 1,2 relationship.
 Meta isomer:1,3 relationship
 Para isomer:1,4 relationship
 4.4 Nomenclature of Benzene
Compounds
Cl
Cl Cl
Cl

Cl Cl
o-dichlorobenzene m-dichlorobenzene p-dichlorobenzene
1,2-dichlorobenzene 1,3-dichlorobenzene 1,4-dichlorobenzene

 Numbering the benzene ring to give the low

est possible numbers to the carbon atoms b
earing the substituents.
 4.4 Nomenclature of Benzene
Compounds
Cl 6 Cl
Cl 6 5 1
1 5
4 2
2 3
Cl 4 Cl
3 Cl
1,2,4-trichlorobenzene 1,3,5-trichlorobenzene
 Common name of a monosubstituted arom
atic compounds as the parent
 The position of the substituent of the paren
t is automatically designated 1.
 But the number is not used in the name.
 4.4 Nomenclature of Benzene
Compounds
 In alphabetical order to the parent name alo
ng with numbers indicating their locations.
OCH3
CH3CH2 F 1 CH3

1 NH2 CH2CH3
 Aromatic hydrocarbons
4-ethyl-2-fluoroaniline belong to a general
3-ethyl-2-methylanisole
class called arenes.
 4.4 Nomenclature of Benzene
Compounds
An aromatic ring residue is an aryl group, sy
mbolized as Ar
 Two groups phenyl and benzyl are often co
nfused.

CH2

phenyl group benzyl group

4.5 Electrophilic Aromatic Substitutio
n
 An electrophile(E+) substitutes for H+
H E
+ E Nu + H Nu

 Mechanism of electrophilic aromatic substiti

on
 The electrophile accepts an electron pair fro
m the aromatic ring.
H
H E
-
+ E Nu + + Nu
4.5 Electrophilic Aromatic Substit
ution
 The proton bonded to the same carbon atom as the
newly arrived electrophile is lost.
 The aromatic πsystem restored.
E
H E
+ -
+ Nu + H Nu

 Typical electrophilic substitution reactions

 Bromination and chlorination:Br2 and Cl2,Lewis acid
,FeBr3 and FeCl3
4.5 Electrophilic Aromatic Substitutio
n
Br
FeBr3
+ Br2

 In nitration, a nitro group, － NO2, is introduc

ed onto an aromatic ring using nitric acid, H
NO3, with sulfuric acid as the catalyst.
NO2
H2SO4
+ HNO3
4.5 Electrophilic Aromatic Substitutio
n
 Sulfonation: A sulfonic acid group, － SO3H can
be introduced onto an aromatic ring by electrophi
lic aromatic substitution.
SO3H
+ H2SO4

benzensulfonic acid
 Friedel-Crafts alkylation: an alkyl group can be s
ubstituted for a hydrogen atom of an aromatic rin
g.
4.5 Electrophilic Aromatic Substitutio
n
 Alkyl bromides or alkyl chlorides, Lewis acid
AlCl3 does not occur on aromatic rings:
 that have one of the groups NO2, SO3H, CN
, or any carbonyl-containing group (aldehyd
es, carboxylic acids, and esters ) bonded dir
ectly to the aromatic ring.
CH(CH3)2 CH2CH2CH3
+ CH3CH2CH2Cl +
isopropylbenzene propylbenzene
major product minor product
4.5 Electrophilic Aromatic Substitutio
n
 Isomerization of carbocation by a hydride shift, by
the trend to form more stable carbocation.
H H
+
+
CH3 CH CH2 CH3 CH CH2
 Friedel-Crafts acylation: an acyl group can replac
e hydrogen in an aromatic ring.
O
O C
AlCl3 CH2CH3
+ CH3CH2C Cl

propanoyl chloride propiophenone

4.5 Electrophilic Aromatic Substitutio
n
 The same limitation as F-C alkylation
 Reduction of phenone result to alkyl substit
ued benzene without rearrangement.
 Clemmensen reduction: react in the presen
ce of zinc/mercury amalgam and HCl
O
C Zn/Hg
CH2CH3
HCl

propiophenone propylbenzene
4.6 Structure Effects in Electrophilic
Aromatic Substitution
 Activating groups: make the aromatic ring
more reactive compared to benzene, such
as hydoxyl, methyl groups.
 Deactivating groups: make the aromatic ri
ng less reactive, such as chloro and nitro
groups.
 Orientation effects of substituents
 Ortho,para director: directs or orients the
substituent into position ortho, and para
4.6 Structure Effects in Electrophilic
Aromatic Substitution
 All activating groups are ortho, para director
. Halogens, which are weakly deactivating,
are also ortho, para directors.
 Meta directors: include nitro, trifluoro-methyl
, cyano, sulfonic acid, and all carbonyl-cont
aining groups.
CH3 CH3 CH3 CF3 CF3
NO2
HNO3 HNO3
+ H2SO4
H2SO4
NO2
NO2
4.7 Interpretation of Rate Effects
 The ability of the substituents to either donate or withdr
aw electrons from the aromatic ring.
EDG EWG

If the group is electron donating If the group is electron withdrawing

(EDG), the ring gains electron (EWG), the ring loses electron
density and is more reactive. density and is less reactive.
 Substituents can donate or withdraw electrons density
by inductive or resonance efects or a combination of th
ese effects.
4.7 Interpretation of Rate Effects
 Inductive effects of substituents
 Related to the electronegativity
 Alkyl groups are electron donating, stabiliz
e carbocations
 Transfer electron density through the σ bo
nds to sp2 –hybridized carbon atom
 Donate electron density to the benzene rin
g by an inductive effect
4.7 Interpretation of Rate Effects
 The trifluoromethyl group, whose fluorine at
oms pull electron density away from the car
bon atoms to which they are bonded.
 An inductively electron withdrawing
CH3 CF3

methyl group activates trifluoromethyl group

the aromatic ring deactivates the aromatic ring
4.7 Interpretation of Rate Effects
 The halogens directly bonded to an aromati
c ring withdraw electron density and deactiv
ate the compound toward electrophilic arom
atic substitution.
 The other groups have the same rule.
 Conjugating effects

O H
4.7 Interpretation of Rate Effects
 Orbitals overlap each other, the lone pair
electrons in the p orbital of oxygen atom c
an be donated to aromatic ring by this way
.
 If the atom bonded directly to aromatic rin
g is attached with lone pair electrons, the
substituent can activate the aromatic com
pound.
4.8 Interpretation of Directing Effects

 Attack at either the ortho or the para positio

n results in one resonance structure with a
positive charge on the ring carbon atom bon
ded to the methyl group.
 The carbocation is close mostly to the electr
on donating group, and is most stable.
CH3 CH3 CH3 CH3
H H H
+
ortho NO2 NO2 NO2
NO2+ + +

most stable
resonance form
4.8 Interpretation of Directing Effects
CH3 CH3 CH3 CH3

para +

NO2+ + +

H NO2 H NO2 H NO2

most stable
resonance form
 Further more the carbocation is tertiary carbon.
 Attack at either the meta position results only
secondary carbocation resonance structure.
CH3 CH3 CH3 CH3

meta + +
H H H
NO2+ +
NO2 NO2 NO2
4.8 Interpretation of Directing Effects

 Substituent with unshared pair of electrons

can make the carbocation stable by sharing
the lone pair electrons.
OH OH + OH OH OH
H H H H
+ +
ortho Br
Br Br Br
Br+ + +

most stable
resonance form
OH OH OH + OH OH

+ +
para
Br+ + +

H Br H Br H Br H Br
most stable
resonance form
 OH OH OH OH

meta + +
H H H
Br+ +

-Br
Br Br
- O - -
O + O O + O + O O + O
N N N N
H H H
+
ortho NO2 NO2 NO2
NO2+ + +

least stable
resonance form
O + O- O + O- O + O- O + O-
N N N N

para +

NO2+ + +

H NO2 H NO2 H NO2

least stable
resonance form
4.8 Interpretation of Directing Effects

 Meta substitution is favored by avoiding the

positive charge of carbocation near to the ni
tro group.
O + O- O + O- O + O- O + O-
N N N N

meta + +
H H H
NO2+ +
NO2 NO2 NO2
 The halogen substituents are weakly deacti
vating but yet are ortho, paro directors.
4.8 Interpretation of Directing Effects

 Because the halogens have lone pair electr

ons, they can donate electrons to the carbo
cation intermediate.
+ +
Cl Cl Cl

- -
 4.9 Reactions of Side Chains

 Carbon atoms directly bonded to the arom

atic ring are influenced by the ring.
 Benzyl carbocation has a postively charge
d carbon atom attached to a benzene ring.
 More stable than primary and secondary c
arbocations and of comparable stability to
a tertiary carbocation.
 Also the same for benzyl radical
 4.9 Reactions of Side Chains
H H
H H
H Br + H
H + H or
H
less stable intermediate more stable intermediate
indene
(a secondary carbocation) (a benzylic secondary carbocation)
Br
+
+ Br2

only product
Br
CH2CH3 CHCH3

+ Br2

only product
 4.9 Reactions of Side Chains

 Oxidation of side chain: in spite of the side

chain length, the product is benzoic acid.
KMnO4
Br CH2CH2CH3 + Br COOH
H3O

KMnO4
Br CH3 + Br COOH
H3O
4.10 Functional Group Modification

 Only a few functional groups can be placed

directly on an aromatic ring by electrophilic
aromatic substitution.
 Oxidation of methyl to carboxylic acid
O
C Zn/Hg
CH2CH3
HCl

 Reduction of acyl to alkyl with amalgam

KMnO4
O2N CH3 + O 2N COOH
H3O
p-nitrotoluene p-nitrobenzoic acid
4.10 Functional Group Modification

 A diazonium ion, is made by treating an aniline

with nitrous acid,HNO2, prepared by reaction of
sodium nitrite with sulfuric acid: diazotization.

NaNO2
Ar NH2 Ar N2+ diazonium ion
 AromaticHdiazonium
2SO4 ions are extremely reactive.
They react with nucleophiles, replacing the diaz
onium group and liberating nitrogen gas.
4.10 Functional Group Modification
Ar N2+ + Nu- Ar Nu + N2
 Sandmeyer reaction: In 1884, the German c
hemist T. Sandmeyer found that diazonium
ions react with nucleophiles supplied in the f
orm of a Cu(Ⅰ) salt.
NH2 N 2+ Br
CH3 CH3 CH3
NaNO2 Cu2Br2
H2SO4
4.10 Functional Group Modification

 Cuprous salts of the cyanide ion result in the form

ation of aryl nitriles.
Br NH2 Br N 2+ Br CN
NaNO2 Cu2(CN)2
H2SO4

 Phenols can be synthesized by reaction of the ary

ldiazoniun compound with hot aqueous acid.
NH2 N 2+ OH

NaNO2 H3O+
H2SO4

CH(CH3)2 CH(CH3)2 CH(CH3)2

4.10 Functional Group Modification

 A diazonium group can also be replaced by

hydrogen using hypophosphorous acid.
 This process removes the amino substituen
t from the aromatic ring after its role as dire
cting group in a series of synthetic steps is
concluded.
NH2 N 2+ H

NaNO2 H3PO2
H2SO4
Br Br Br Br Br Br
 4.11 Synthesis of Substituted
Aromatic Compounds
 Benzene derivatives with two or more subs
tituents.
 An analysis of the ortho, para- or meta-direc
ting characteristics of substituents.
Cl Cl Cl
NO2
Cl2 HNO3
FeCl3 H2SO4 +

NO2
NO2 NO2

HNO3 Cl2
H2SO4 FeCl3
Cl
 4.11 Synthesis of Substituted
Aromatic Compounds
 Synthesis of m-dibromobenzene
 The bromo groups are meta to each other, but br
omine is an ortho, para director.
Br Br Br
Br
Br2 Br2
FeBr3 FeBr3 +

Br
 However, the nitro group is a meta director.
 So nitration to form nitrobenzene followed by bro
mination gives m-bromobenzene.
 4.11 Synthesis of Substituted
Aromatic Compounds
NO2 NO2

HNO3 Br2
H2SO4 FeBr3
Br
 A nitro group can be converted to a bromo
group by (1) reducing the nitro group to an
amino group, (2) converting the amino grou
p to a diazonium group, and (3) treating dia
zonium compound with copper(Ⅰ) bromide.
4.11 Synthesis of Substituted
Aromatic Compounds

NO2 NH2 N 2+ Br

Sn/HCl NaNO2 Cu2Br2

H2SO4
Br Br Br Br