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7.1 Introduction
Discovery of Benzene
Isolated in 1825 by Michael Faraday who determined
C:H ratio to be 1:1.
Synthesized in 1834 by Eilhard Mitscherlich who
determined molecular formula to be C6H6.
Other related compounds with low C:H ratios had a
pleasant smell, so they were classified as aromatic.

=>

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 Unusual Reactions

Alkene + KMnO4  diol (addition)

Benzene + KMnO4  no reaction.
Alkene + Br2/CCl4  dibromide (addition)
Benzene + Br2/CCl4  no reaction.
With FeCl3 catalyst, Br2 reacts with benzene to form
bromobenzene + HBr
(substitution!). Double bonds remain.
=>

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 Unusual Stability
Hydrogenation of just one double
bond in benzene is endothermic!

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 Benzene is a planar molecule. Each of its six carbon
atoms is hybridized, with bond angles of 120°. A p
orbital of each carbon overlaps the p orbitals of both
adjacent carbons.
 The six electrons are shared by all six carbons.
Compounds such as benzene that are unusually stable
because of large delocalization energies are called
aromatic compounds.
Resonance Energy

Benzene is 152 kJ or 36 kcal / mol more stable than the hypothetical system.
This is the resonance energy for benzene.

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 Common Names of Benzene Derivatives
OH CH3 NH2 OCH3

phenol toluene aniline anisole

H O O O
C CH2 C C C
CH3 H OH

styrene acetophenone benzaldehyde benzoic acid

=>
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Disubstituted Benzenes
The prefixes ortho-, meta-, and para- are commonly used for th
1,2-, 1,3-, and 1,4-positions, respectively.
Br NO2

Br HO
o-dibromobenzene or p-nitrophenol or
1,2-dibromobenzene 4-nitrophenol

=>
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 7.2 Aromaticity
 criteria to be aromatic compound.
 It must be cyclic compound
 It is planar.
 In general presence of sp2 hybridized carbon imparts
planarity.
 It is conjugated.
 It exhibits continous delocalization of π (continous
delocalization is possible if p orbitals are available on each
carbon for overlap)
 It should follow Huckel’s rule, only those compounds
possessing (4n+2) π electrons, where n =1, 2, 3, etc, is

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 Aromatic Ions

Cyclobutadiene
Benzene Cyclooctatetrene
is aromatic as n=1 not aromatic ,since n=1/2 not aromatic ,since n=3/2
and saisfies Huckel's does not satify does not satify
Huckel's rule Huckel's rule

Aromatic Ions

Cycloheptatrienyl cation(tropilium ion), cycloheptatriene

is aromatic as n=1&satisfies Huckele's rule not aromatic,since it is not completely conjugated

Cyclopentadienyl cation cyclopedienyl anion

non-aromatic aromatic

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 Non aromatic why?

Heterocyclic Aromatic Compounds

Those heterocyclic compounds that possess aromatic stability are called heterocyclic
aromatic compounds.

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 7.3 Aromatic electrophilic substitution

E
E
H E
H :base
+ H-base

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 EAS Reactions of Benzene
NO 2

CHO Cl

O
CR Br

R I

SO 3H

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 7.4 Application of electrophilic substitutions

7.4.1 Halogenation
Bromination / Chlorination
H Br
Br2, FeBr3
+ HBr

H Cl
Cl2, FeCl3
+ HCl

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 Bromination Mechanism

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 Reaction Profile

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 7.4.2 Sulfonation
Sulfonation is Reversible
fuming sulfuric acid
H SO3H
SO3, H2SO4

O
S
O O H OSO3H

SO3H
OSO3H
H
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 Desulfonation

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 7.4.3 Nitration

NO2
HNO3, H2SO4
+ H 2O

Formation of electrophile
+ -
HNO3 + H2SO4 NO2 + H2O + HSO4

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 Nitration Mechanism

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 Nitration of Toluene

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 7.4.4 Friedel-CraftsAlkylation

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 Limitation of Friedel-Crafts alkylation
•Remember the cause for rearrangement reaction is due to stability
preference, i.e30carbocation >20 carbocation> 10 carbocation
When the carbocation can rearrange in a Friedel–Crafts alkylation reaction, the major
product will be the product with the rearranged alkyl group on the benzene ring.
Examples:

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 Carbocation Generated From Alkene

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 7.4.5 Friedel-Crafts Acylation

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 Friedel-Crafts Acylation

O
O C
RCCl, AlCl3 R
+ HCl

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27
 1st, Formaton of Electrophile

O
O
+ -
C   C
Cl AlCl3 R C O AlCl4
R R
acylium ion

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 Acylation Mechanism
O
O
C
C R
H Cl AlCl3
R

O
C
R + HCl

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 Intermediate is
Resonance-Stabilized

O O O
C C C
R R R
H H H

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 An Acylation

CH3 CH3 O
O
CH3CH2CH2CH2CCl CCH2CH2CH2CH3

TiCl 4 in CH2Cl2 + HCl

CH3 CH3

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 7.5 Directing effects
So far we have looked at the electrophilic aromatic substitution of benzene itself.
Of course substituted benzenes can undergo further substitution to give poly-
substituted systems:

Two questions arise based on this general scheme...

•How easy is the second substitution reaction compared to the first?
•Is it faster or slower or the same rate?
•Where does E2 substitute relative to E1?  There are 3 possibilities:

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 Here are some general pointers for recognizing the substituent
effects:
The H atom is the standard and is

regarded as having no effect.
EDG / activating groups
Activating groups increase the rate
 direct ortho / para
Deactivating groups decrease the rate
 EWG / deactivating groups

EDG = electron donating group
direct meta

EDG can be recognised by lone pairs
on the atom adjacent to the π system,
except halogens (-X) which
eg: -OCH3 are deactivating BUT direct

except -R, -Ar or -vinyl ortho / para
(hyperconjugation, π electrons) EDG add electron density to
EWG = electron withdrawing group


EWG can be recognised either by the
the π system making it more
atom adjacent to the π system having nucleophilic
several bonds to more electronegative EWG remove electron
atoms, or, having a formal +ve or δ
+ve charge, eg: -CO2R, -NO2
density from the π system
making it less nucleophilic.
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Examples

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 7.6 Diazotization of Amines
The process of forming diazonium compounds is called "diazotation",
"diazoniation", or "diazotization".

Reaction mechanism:
Generation of nitric oxide cation

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Replacement reactions
It is synthetically useful transformations involving aryl diazonium ions are shown below:

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 Take note

H2 O
Ar-OH
HBF4 Schiemann
Ar-F
reaction
HCl, CuCl Ar-Cl
HNO2 + (-N ) Sandmeyer
Ar-NH2 Ar-N2 2 HBr, CuBr Ar-Br
0-5°C reaction
KCN, CuCN Ar-CN
KI Ar-I
H3 PO2
Ar-H

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Coupling Reactions of Diazonium Ions

•Coupling reaction with phenol.

N N Cl- + H OH N N OH + HCl

benzene phenol diazo product

diazonium chloride
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 slow H
N N+H OH N N OH

benzene phenol
diazonium ion fast

N N OH

diazo product
•Coupling reaction with aniline.

N N Cl- + H NH2 N N NH2 + HCl

benzene aniline
diazo product
diazonium chloride

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 1. Side-Chain Halogenation

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7.7 Reactions of aromatic side chains

1) Reduction of Aromatic Ketones

(will also reduce alkenes and alkynes)

H2, Pd/C
in ethanol

Alternatively, use Zn(Hg), dil. HCl to avoid reduction of

alkenes and alkynes). Clemmensen reduction
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•The Clemmensen reduction is a way to convert acylbenzenes to
alkylbenzenes by treatment with aqueous HCl and amalgamated zinc.

Wolff-Kishner Reduction

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 Straight-chain Alkylation can be Accomplished in 2 steps:
Acylation, then Reduction

CH2CH2CH3 CH(CH3)2
CH3CH2CH2Cl
AlCl3 minor + major

H2, Pd/C
O O
CH3CH2CCl CCH2CH3
AlCl3

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 2) Oxidation of Alkyl Substituents
O
CH3 COH
KMnO4, H2O

CO2H
KMnO4
H2O

CH3 CO2H
KMnO4, H2O

CH(CH3)2 CO 2H
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 Cont….

Aromatic compounds with benzilic hydrogens are also susceptible to oxidative

degradation: Potassium permanganate (KMnO4) decomposes these to the
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benzoic acid (caution - you loose the WHOLE side-chain on this one!):
 3) Benzylic Bromination with NBS
benzylic hydrogen
H Br

NBS, CCl4, h

NBS NBr

O
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 4) Alkali Fusion of Sulfonic Acids

SO3H OH
o
1) NaOH, 300 C
+
2) H3O
phenol

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 5) Reduction of Nitro Groups

NO2 1) SnCl2, HCl NH2

2) NaOH
or H2 on Pt

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 Excercises
1.Write the structure of the principal organic product: 0.5 point each
obtained on Sulfonation of each of the following:
A. p-Methylbenzoic acid B. m-Dinitrobenzene
C. p-Methylanisole D. 2, 6-Dibromoanisole

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60 compiled by Gezu Feleke (MSc.) DEC.2011 12/04/2022
 Provide the Reagents
NH2

C(CH3)3
Br

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 Additional exercises
Unexpected Product?
CH2CH2CH2CH3
CH3CH2CH2CH2Cl, AlCl 3 minor product

CH3
CHCH2CH3
major product

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 Provide the Reagents
NH2

C(CH3)3
Br

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 Must Acylate First
NH2

O
ClCCH2CH2CH2CH3
AlCl3 H2, Pt/C
NO2

HNO3
H2SO4

O meta director O
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 Give the Reagents

CO2H

CH3
Cl
O

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 Provide the Reagents

CH2CH3

Br OH

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 O CH2CH3
1) ClCCH3, AlCl 3
2) SO3, H2SO4
3) Br2, FeBr3 Br OH
1) 4) H2 Pd/C
o
5) NaOH, 300 C 5,6)
+
6) H3O
O O O

2) 3) 4)

SO3H Br SO3H Br SO3H

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 Provide the Reagents

HO2C

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 Cl

1) AlCl3 HO2C

2) Cl

O AlCl3 6) workup w/
+
3) KMnO4, H2O HO 2C H3O

1) 4) H2, Pd/C
5) NBS, h
6) NaOCH3 in CH3OH, heat
(E2 elim of HBr) HO 2C Br
5)

HO2C 4)
2) 3)

69 O O
 Benzyne intermediate has 2 reactive
sites

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 Mixture of Regioisomers

Br NH2
H2N
NaNH2, NH3
+

OCH3 OCH3 OCH3

minor major
+ NaBr

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 N K
H A
T U!
72 YO
compiled by Gezu Feleke (MSc.) DEC.2011 12/04/2022