AROMATIC CHEMISTRY

Course content:
 Aromaticity of compounds
 Structure of Benzene and its stability
 Nomenclature of aromatic compounds
 Eletrophilic substitution reactions
 Substituents and reactivity
 Aromatic diazonium salts: formation and reaction
 Aromatic aldehydes and ketones: methods of preparations and reactions.
 Nucleophilic aromatic substitution
 Polynuclear aromatic compounds

References:
- Organic chemistry by Morison and Boyd.
- Basic introduction to Organic chemistry by Norman.

INTRODUCTION
The term aromatic is derived from the greek word aroma meaning pleasant smell. Aromatic
compounds are compounds that are similar to Benzene in structure and chemical properties. The
fragrant odour of Benzene and related compounds led to it being classified aromatic. The term
aromaticity is now used to describe planar cyclically conjugated structures with (4n+2) π
electrons where n=0, 1, 2, 3, 4, 5, etc…,... The (4n+2) π electron rule is known as the Huckel’s
rule.
Conditions for Aromaticity (Basic requirements for aromaticity)
1- The compound must be cyclic
2- It must be planar (lie in one plane)
3- There must be conjugated.
4- The totality of the electron cloud in the cyclic system must conform to (4n+2)π
electrons

For example;

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Illustrations:

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3
4
Bonding and structure of benzene
Benzene is a flat six membered ring with the formula C6H6.

Kekule proposed a reasonable structure of benzene.

Which implied alternating single & double bonds (C-C = 1.47Å , C=C = 1.3 Å ),
Set backs; later spectroscopic analysis showed that all bond lengths to be equal &
intermediate between single & double bond length (1.39 Å).

Also if we accept the basic Kekule structure, we might expect the cyclohexatriene to have a heat
of hydrogenation about three times as large as cyclohexene i.e. about 85.8 k cal mol-1.

But the value for benzene is 49.8 kcal mol-1 i.e less 36k cal mol-1.

Actual for benzene = - 49.8 Kcal/mol

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Difference = - 36 Kcal/mol is known as resonance or stabilization energy and this illustrates the
extra stability that benzene has over the irregular cyclohexatriene molecule.

This stability also shows that addition reactions are not as easy as we would expected (c.f
alkanes).

i.e. Compounds which are unsaturated can undergo the following reactions:

 Addition of bromine water (Br2/H2O) to R-C=C-R, the brown color will be discharged.

Stability of benzene results from the following;

1. Resonance structures of the shared double bonds.ie

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2. Benzene is said to have a closed bonding shell of delocalised π electrons and this accounts in
part for its stability. i.e. it conserves energy by not restricting the electron movement as is the
case with the alkenes.

Nomenclature

Mono substituted- the substituent takes the lowest number.

Polysubstituted aromatic compounds

Older system of Nomenclature

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 OH
Br
NH2

Cl

NO2
COOH
o-chloroaminobenzene m-bromonitrobenzene
p-hydroxybenzoic acid (1-bromo-3-nitrobenzene)
(2-chloroaminobenzene) (4-hydroxybenzoic acid)

The older system of Nomenclature does not work for more than two substituents i.e.

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 CH3 Br
OCH3
OH
O2N NO2 Br
O2N
NO2

H3 C CH3
COOH
NO2
3,4-dibromobenzoic acid 1-methoxy-3,5-
2-methyl-1,3,5-trinitrobenzene NO2 dimethylbenzene

2,4,6-trinitrohydroxybenzene
(Picric acid)

When Benzene is named as a substituent, it is called a phenyl group e.g.

Removal of one hydrogen atom from toluene form a group known as benzyl

ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS

Because of the presence of electrons, benzene is expected to react more easily with elctrophiles
(E+) than nucleophiles (Nu-).

General mechanism for electrophilic aromatic substitution

1. Generation of Electrophile from the reagent

This is done by the catalyst i.e.

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 2. Electrophilic attack of aromatic ring

3. Regeneration of aromatic system

This is done through abstraction of a proton by a base (B:)

Common Electrophilic Substitution Reactions of benzene include;

1. Nitration

Mechanism

2. Halogenation

i) Halogenation using halogens

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The reactivity order for the halogen to react with benzene is as outlined below:-

F2 > Cl2 > Br2 > I2.

For practical consideration, F2 may be regarded far too reactive to be of practical use i.e
Florobenzenes cannot be prepared from the above methods. On the other hand I2 does not react
directly with benzene unless it has been oxidized into a fairly reactive electrophilic species (I+ )
using either CuCl2 or H2O2/H+ as oxidizing agents.

N.B. The flurobenzene compounds are prepared usually via diazonium salts.

ii) Halogenation using hypohalous compounds (HOX) - Few drops of mineral acid
catalyse the reaction

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FRIEDEL –CRAFT’S REACTIONS

1. Alkylation

2. Acylation

Alkylation

This requires treatment of an aromatic nucleus with an alkyl halide in the presence of a catalyst
i..e

Large excess of catalyst leads to isomerisation of 1,2 and 1,4 substitution products.

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If benzene is in large excess,

If it’s a long chain alkyl halide,

Mechanism

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Catalysts

These include FeX3, SbCl5, BF3, AlX3 and SnCl4. SnCl4 is far more superior to AlCl3, but AlCl3
is cheaper therefore easily available.

Alkylation using aliphatic alcohols and alkenes require catalysts like conc. H2SO4, H3PO4, HF,
and HF- BF3.

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Alkylation using Alcohols

Important things to note when looking at Friedel- Craft’s alkylation reactions

There are limitations and also some setbacks associated with Friedel- Craft’s alkylation reaction.

1. Friedel – Craft’s reaction is not possible on the electron withdrawing group.

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 Because nitrobenzene is unreactive in Friedel – Craft’s reactions, its normally used as a solvent
in acylation reactions.

2. Active side groups on the benzene ring do not allow alkylation of the ring i.e. in presence

Instead;

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Benzene rings with side chains that may react with Lewis acids without giving carbocations as
electrophiles cannot be alkylated. These include; amino groups –NH2 and its derivatives -NHR

3. In Friedel- Craft’s reactions, polyalkylation cannot be avoided. This may be improved by

using a very large excess of the aromatic compound.
4. Side chains or alkyl groups with carbon atoms greater than 2 normally undergo
rearrangement to give branched chains rather than straight chains.

FRIEDEL-CRAFT’S ACYLATION

The acyl functionality is the electrophile i.e

OR

NOTE:

 Yields of carbonyl compounds are much better in acylation than alkylation.

 There is no isomerisation in case of acylation as is the case of alkylation.
 C-side chains which are straight are possible to form. (This is the solution to the
limitation in alkylation of straight chains)

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SULPHONATION

Conc. H2SO4 or fuming H2SO4 which is a mixture of sulphuric acid and SO3 reactions with
aromatic hydrocarbons. The reactive electrophiles can either be HSO3+ or SO3.

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Sulphonation mechanism

OR

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THE INFLUENCE OF SUBSTITUENT ON REACTIVITY AND ORIENTATION IN
ELECTROPHILIC AROMATIC SUBSTITUTION.

Generally there are two types of substituents

Activating substituents

Substituents that are capable of increasing electron density on benzene. These groups increase
the electrophilic aromatic subsitution reaction rate.

Deactivating substituents

Substituents that are capable of decreasing electron density on benzene. These groups decrease
the electrophilic aromatic substitution reaction rate.

The donation or removal of electron density from benzene ring can be achieved via

 Induction (removal or donation through a sigma bond due to electronegativity or

polarity of bonds) e..g.

 Resonance (Conjugation of substituents with the aromatic ring) e.g.

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From above, CH3 functionality activate the ring towards further eletrophilic substitution.
The Nitro functionality slows down the attack by eletrophiles to the benzene.

Also the nature of the substituent influences product ratio during electrophilic aromatic
substitution .i.e.

X- gives two types of products, ortho and para attachments to the benzene ring. Therefore X is
ortho and para directing.

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Y- gives only one type of product. The product given is a meta product. Therefore Y is meta
directing.
The following are activating substituents with respect to the ring and they always activate ortho
and para positions much more than the meta positions. Therefore they are said to direct the
incoming electrophile into the ortho and para positions with activation. Such groups include
among others;
- OH with all its derivatives e.g. –OR, O- etc.
- NH2 and its derivatives (NHR, RNR, -NHCOR). - Alkyl groups (R),

CH CH2, .

Orientation and reactivity effects of ring substituents

Activating substituents Deactivating substituents Deactivating substituents

Ortho and para directing Meta directing Ortho and para directing
Strong activators Strong deactivators
NH2, NHR, NR2, OH NO2, -R3N+, -CF3, F
-O-, -OR -CCl, +NH3, +NHR2 Cl
NH2R, CN, SO3H Br
Moderate activators Moderate deactivators I
-NH-CO-R -COH, -COR, -COOR, - CH2-Cl
-O-CO-R -COCl, COOH CH=CHNO2
Weak activators
-R
-Ar
CH=CHR

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If Y stabilizes then it is activating the ring. There are two categories of groups of Y.
a) Y that has lone electron pairs by resonance.
e.g

b) That with Inductive effect.

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 The positive charge is broken down to neutrality. The ring is stabilized by activation.

The above Ortho-para products depend on the position of the attack.

i.e.
Ortho attack

CH3 CH3 CH3

CH3
H H
H
E E

+ E+ E

Para attack
CH3 CH3
CH3

H E H E
H E
Meta attack

CH3 CH3 CH3

H H
H

E E
E

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Because of the electron pushing nature of the methyl functionality, the ortho and para
intermediates both have a carbo cation that is directly attached on the methyl functionality. This
means that the carbo cation has the lowest energy.

On the other hand, meta attack gives 3 intermediates with medium or lower energy and without a
carbocation which is directly on the same carbon atom as the electron donating methyl group.
Hence the ortho–para route has lower energy of activation than the meta route. The methyl group
is therefore said to activate the ring because it pushes electrons into the carbocation and it directs
the incoming electrophiles into the ortho-para position.

i.e. The ortho-para product ration decreases as the size of the substituent on the ring increases.

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Try to synthesise the following from Benzene:

Other useful reactions

(i) Hydrogenation of benzene (where it behaves like a normal hexatriene)

(ii) Halogenation

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(iii) Oxidation

a) Benzene ring

b) Oxidation of the side chain (Benzylic hydrogen)

Applied in synthesis of many compounds e.g synthesize

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DIAZONIUM SALTS

These are aromatic compounds which are essential in the dye industry.

Preparation

When primary amines react with nitrous acid in the presence of a few drops of mineral acid, a
diazonium salt, RN2+X- is formed. If R is alkyl, it easily decomposes, if it is aromatic, it can
easily be isolated and the temperatures suitable for the stability are around 0 – 5oC. The process
through which a primary amine is reacted with nitrous acid using dil HCl and NaNO2 is known
as diazotization.

HNO2 H+
RNH2 RN2 +

Nitrous acid reacts in situ and reacts as it is formed.

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Mechanism

Reactions of Diazonium salts

There are 2 main reactions that are characteristic of benzene diazonium salts. These are;
1. Reactions during which a molecule of nitrogen is eliminated from the compound
(Replacement reactions).
2. Reactions during which nitrogen molecule is retained in the compound (Coupling reactions).

Reactions where the nitrogen molecule is eliminated

Reactions of this type are normally characteristic of ionic intermediates and the reactions that
take place are SN1 (Unimolecular Electrophillic Substitution Reaction). They include;

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Fusion of a nitrile salt with benzene sulphonic acid can introduce a nitrile group on to the
benzene i.e.

Mechanisms

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Other reactions include;
Methyl-de-diazoniation
This requires that the diazonium salt is treated with tetramethyl tin [Sn(CH3)4] in presence of
palladium ethanoate as a catalyst

Coupling reactions to form azodyes

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Benzynes
Any derivative of benzene formally produced by obstruction of two hydrogen atoms from
neighboring atoms to produce a formal triple bond

Benzynes are unstable & very reactive intermediates.

Methods of generating Benzynes

1. Dehydrohalogenation of halobenzene using strong base i.e.

e.g.

2. Elimination from organolithium or organomagnesium precursors e.g. loss of fluoride ion from
the reagent of 1- bromo-2-fluorobenzene.ie

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3. Loss o f neutral leaving groups.

4. Photolytic methods

Reactions of benzyne

1. Addition of nucleophiles e.g

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Mechanism

2. Addition of electrophiles

3. Cyclo addition reactions

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Nucleophilic Aromatic Substitution (NAS)

Though electrophilic substitution reactions is by far the most common mode of substitutions in
aromatic systems, nucleophilic substitution is indeed possible and a useful tool in certain cases.
In this case a nucleophile displaces a good leaving group eg a halide.

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e.g. Industrial preparation of Phenol

Other examples of NAS include some reactions of benzyne and diazonium salts

NOTE:

1. SN1 and SN2 is not favoured in nucleophilic aromatic substitution. The phenyl cation is less
stable than 1o cation (SN1). Conjugation does not favour backside attack (SN2).

There are two mechanisms which are possible and they are:

a) Addition-Elimination Mechanism
b) Elimination-Addition Mechanism (like in benzynes)

2. NAS is enhanced by electron withdrawing substituents like –NO2, –CN, -CO.

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Nucleophilic aromatic substitution is enhanced by electron withdrawing substances e.g.

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All the above reactions can be adequately explained by addition-Elimination mechanism.

Other studies suggests Initial elimination of HX by the strong base like in Benzynes

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POLYNUCLEAR AROMATIC HYDROCARBON

Polynuclear Aromatic hydrocarbon that contains two or more benzene rings with each pair of
rings sharing two adjacent carbon atoms e.g.

Since fused rings must share a pair of electrons, the aromaticity and the delocalisation energy per
ring is less than that of benzene itself.

As the number of fused rings increases, the delocalisation energy per ring continues to decrease
in absolute value, compounds become more reactive, especially towards addition.

Naming

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REACTIONS

BUCHERER REACTION

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Reversible conversion of Naphthol to naphthylamine in presence of ammonia and sodium
bisulfate.

mechanism

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AROMATIC ALDEHYDES AND KETONES

These are intermediates in synthesis of pharmaceutical agents, biological pathways, numerous

industrial processes. The compounds occur widely in nature as intermediates in metabolism and
biosynthesis

AROMATIC ALDEHYDES

Preparation:
1. Gatterman-Koch reaction: Formylation of hydrocarbons
Requirements:- An aromatic hydrocarbon, Carbon monoxide, Hydrogen chloride gas (HCl) in
presence of a Lewis acid e.g. AlCl3 ornCu2Cl2, Room temp, the reaction must be under high
pressure.

Mechanism

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2. Using hydroxyl aromatic compounds or hydroxyl aromatic ethers in the presence of HCN and
AlCl3 (Lewis acid)- Gatterman reaction

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N.B. The predominant carbonyl is the para ratio than the ortho because of the steric hinderance
and the molecule carrying the carbo cation is quite bulky. In case of;

3. Treatment of hydroxyaromatic compound using trihalomethane/ Alkoxide of a strong base

like KOH.

Mechnanism

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 O O
O

Br
:CBr2 H
-
OH
CHBr
CBr2
-
OH

OH O O
H H
H

CHO C O C OH

Br

For a para compound

:CBr2

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4. From Acid chlorides
Aromatic acid chloride, hydrogen gas and a catalyst such as palladium poisoned with sulphur are
required.

5. From Halogenation product of methyl side chain of benzene

6. From Benzenenitrile

Mechanism

7. Using Aromatic ethers and methanamide

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Mechanism

47
REACTIONS OF AROMATIC ALDEHYDES

1.Oximes, phenylhydrazones, semicarbazones are all formed with benzaldehyde. However,

reduction of Fehlings solution and polymerization are not observed.
2. Cannizzaro reaction
Here the -OH acts as a base due to lack of alpha hydrogens

NaOH (aq)
Ph-CHO PhCOO-Na+ + PHCH2OH

O O O O
-H+
Ph-C H Ph C H Ph C H C-Ph
:OH OH OH H

PhCOO- + PhCH2OH

3. Benzoic condensation

O
OH
CH C
CN- (aq)
Ph-CHO

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 O
OH
CH C
CN- (aq)
Ph-CHO

O O OH O OH O
Ph C H Ph C H Ph C- C Ph Ph C C Ph
CN CN CN H CN H

O OH O OH

Ph C C Ph Ph C C Ph
H CN H

4. Clasein-Schmidt reaction
Used to prepare α,β unsaturated carbonyl compounds and esters. Because of the absenc of α
hydrogen in aromatic aldehydes, there is no elimination of α-hydrogens to form a double bond

CHO CH=CHCOCH3

10% NaOH
+ CH3COCH3

Mechanism

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AROMATIC KETONES

PREPARATION:

COCH3

1) + (CH3CO)CO
or CH3 COCl + CH3COOH

COCl
COCH3
2)
(CH3)2CuLi
Lithiumdimethylcopper)

NO2
NO2 an

N.B Organic copper compounds are less reactive than Grignard compounds and Organolithium

COCl CO

3) +

4) CO
PhCOO
Ca Heat
+ CaCO3
very strongly
PhCOO

COCl
CO
5)
+ + HCl

NO2
NO2

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REACTIONS OF AROMATIC KETONES

1. Mannich Reaction

An Aromatic Ketone reacts with methanal and an amine or in ammonia to give a Keto amine and
can undergo some other reactions to give a variety of products. These keto aminocompounds are
known as mannich bases
O
O
C CH
3 C CH CH -NR
2 2 2

+ HCHO + HNR2 1) H2O / H+

or RNH2 2) HO- / H2O (Mannich base)
or NH3
Mechanism
O OH
OH
H C H + H + H
H C H H C N R2

H H

R2NH
H+ shift

H -H2O OH2
C=NR2
H H C N R2

H
O
O C CH2
C CH2

OH

O
C CH2CH2NR2

H
O
C=NR2
C CH2 H
Mannich base

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REACTION OF Mannich bases

O C CH=CH2

C heat
CH2CH2-NR2 + R2N
strongly
O

C CH2 CH3
[H]
H2 /Ni

(CH3 O)2O O

C CH2CH2-OCOCH3

2. Aromatic Ketones may undergo reductions;

(a) Mg amalgam (Mg/Hg)

OH OH
COCH3
C C
Mg/Hg CH3 CH3

(b) Zn/Hg and conc. HCl

COCH3
CH2CH3
Zn/Hg
conc. HCl

(C) WOLFF/KISHNER REDUCTION

COCH3
H2NNH2/OH, 1500c in CH2CH2 (Solvent) CH2CH3

OH OH

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3. Oxidation

(a) Partial Oxidation

O
COCH3

CCOOH
MnO4 (aq)
cold
(glyoxic acid)

(b) Strong oxidation

COCH3

COOH
CrO3/H+
MnO4-/H+ heat

4. Base catalysed condensation reactions

COCH3 O CH3

C CH=C
OH (aq)

Mechanism
O
O O O OH
PhC CH2 PhC CH2 PhC CH3 PhC CH C CH3
H
Ph
:OH
H+ shift -OH

O
PhC C C CH3
H
Ph

5. Benzilic acid rearrangement reaction specific for 1,2-diketones

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 O O O
O O O
PhC C Ph Ph C C Ph Ph C C OH

OH Ph
:OH H+shift
fast

O
OH H+ O
C OH OH
Ph C
Ph C C O-
Ph
Ph

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