AROMATIC COMPOUNDS

INTRODUCTION
(1) There were a large number of compounds which were obtained from natural sources, e.g. resins, balsams,
'aromatic' oils, etc., which comprised a group of compounds whose structures were arbitrarily classified as
aromatic (Greek : aroma, fragrant smell) compounds.
(2) These compounds contained a higher percentage carbon content than the corresponding aliphatic
hydrocarbons, and that most of the simple aromatic compounds contained at least six carbon atoms.
It was shown that when aromatic compounds were subjected to various methods of treatment, they often
produced benzene or a derivative of benzene.
(3) The benzene containing aromatic compounds are called benzenoid compounds, these are cyclic, but
their properties are totally different from those of the alicyclic compounds.
(4) Benzene was first synthesised by Berthelot (1870) by passing acetylene through a red-hot tube :
3C2H2  C6H6 + other products
(5) It is mostly prepared by the decarboxylation of aromatic acids, e.g. by heating benzoic or phthalic acid
with calcium oxide / (soda lime).

NaOH (CaO) NaOH (CaO)


 


1. Aromatic Character : [The Huckel (4n + 2) rule]

The following three rules are useful in predicting whether a particular compound is aromatic or non–aromatic.
1. Aromatic compounds are cyclic and planar.
2. Each atom in an aromatic ring is sp2 or sp hybridised and has close conjugation.
3. The cyclic  molecular orbital (formed by overlap of p-orbitals) must contain (4n + 2) electrons, i.e.,
2, 6, 10, 14 ........  electrons. Where n = an integer 0, 1, 2, 3,..............
Molecular orbital theory of aromaticity
According to molecular orbital theory benzene is a regular flat hexagon. Thus each carbon atom is in a
state of sp2 hybridisation. Hence, in benzene, there are six C–H bonds, six C–C bonds and 3C–C -bonds
six 2pz electrons (one on each carbon atom) are present in 2p z orbitals, which are all parallel the p-orbitals
are perpendicular to the plane of the ring. These electrons can be paired in two ways, both being equally
good (b and c). Each 2pz electron, however, overlaps its neighbours equally, and therefore all six atomic
orbitals a single hexacentric molecular orbitals.

In the ground state, the total energy of the three pairs of delocalised -electrons is less than that of three
pairs of localised -electrons (b) or (c), and hence the benzene molecule is stabilised by delocalisation
(resonance).
2. Comparison of Aromatic compounds with alkenes
Benzene is not as reactive as alkenes, which react rapidly with bromine at room temperature to give addition
products. For example, cyclohexene reacts to give trans-1, 2-dibromocyclohexane. This reaction is exothermic
by about 29 kcal/mol (121 kJ/mol.)

+ Br2 H° = – 29 kcal (– 121 kJ)

The analogous addition of bromine to benzene is endothermic because it requires the loss of aromatic
stability. The addition is not seen under normal circumstances. The substitution of bromine for a hydrogen
atom gives an aromatic product. The substitution is exothermic, but it requires a Lewis acid catalyst to
convert bromine to a stronger electrophile.
 + Br2 H° = + 2 kcal (+ 8kJ)

FeBr
3
+ Br2    + HBr H° = – 10.8 kcal (– 45 kJ)

Examples of Aromatic Compounds : (Table )

3. Aromatic Electrophilic Substitution (ArSE2) Reactions in Benzene Ring
Like an alkene, benzene has clouds of pi electrons above and below its sigma bond framework. Although
benzene’s pi electrons are in a stable aromatic system still they are available to attack a strong electrophile
to give a carbocation. This resonance-stabilized carbocation is called a sigma complex because the
electrophile is joined to the benzene ring by a new sigma bond.
The sigma complex (also called an arenium ion) is not aromatic because the sp3 hybrid carbon atom interrupts
the ring of p orbitals. This loss of aromaticity contributes to the highly endothermic nature of thus first step.
The sigma complex regains aromaticity either by a reversal of the first step (returning to the reactants) or by
loss of the proton on the tetrahedral carbon atom, leading to the substitution product.
 
The overall reaction is the substitution of an electrophile (E ) for a proton (H) on the aromatic ring: electrophilic
aromatic substitution.
Step 1 : Attack of an electrophile on benzene ring forms the sigma complex

Resonance hybrid
[  – complex]
Arenium Ion
Step 2 : Loss of a proton gives the substitution product.

Nu :  + Nu – H
 

4. Activating Groups or Electron Releasing Groups (ERG)

All groups having one or more lone pair of electrons are activating groups because they release electrons
towards the nucleus increasing electron density and hence energy of the system. Reaction rate is increased
due to low energy of activation. Examples :
> > > > > –OR > > –Ar > –R
All the groups which are electron donating etc. are ortho–para directing and
facilitate electrophilic substitution in the benzene ring.
Ex.1 Compare the activating effects of the following o, p-directors and explain your order
.. ..
(a) , , (b)  NH2 and  NH  C  CH3
||
O
Sol. (a) The order of activation is > – OH > – OCOCH3. The , with a full negative charge, is best able to
donate electrons, there by giving the very stable uncharged intermediate

O
|| ..
In  OCCH3 , the C of the has a positive charge and makes demands on the  O
..
 for electron
density this cross-conjugation diminishes the ability of the too donate e–s to the arenium ion.
(b) The order is – NH2 > – NHCOCH3 because of cross - conjugation in the amide, .
5. Deactivating Group or Electron Withdrawing Group (EWG)
Such groups have tendency to withdraw  electrons from the benzene nucleus and thus decreasing its
electron density are known as deactivating groups.
Due to decrease in electron density of the ring, the rate of electrophilic substitution is retarded. These groups
develop positive charge at ortho and para positions leaving the meta-positions as the point of relatively high
electron density and hence the electrophilic substitution occurs at m–position, not at o–and p–positions.

eg.

6. Halogenation
(a) Bromination of Benzene :
Bromination follows the general mechanism for electrophilic aromatic substitution. Bromine itself is not
sufficiently electrophilic to react with benzene, but a strong Lewis acid such as FeBr3 catalyzes the reaction.

Step 1 : Formation of a stronger electrophile.

Step 2 : Electrophilic attack and formation of the sigma complex.

  + FeBr4¯

Step 3 : Loss of a proton gives the products.

Formation of the sigma complex is rate determining and the transition state leading to it occupies the
highest-energy point on the energy diagram. This step is strongly endothermic because it forms a non-
aromatic carbocation. The second step is exothermic because aromaticity is regained and a molecule of
HBr is evolved. The overall reaction is exothermic by 10.8 kcal/mol (45 kJ/mol.)
 (b) Chlorination of benzene
Chlorination of benzene works much like bromination, except that aluminum chloride (AlCl3 ) is most often
used as the Lewis acid catalyst.

AlCl3
+ Cl2  + HCl


(c) odination of benzene

odination of benzene requires an acidic oxidizing agent such as nitric acid. Nitric acid is consumed in the
reaction, so it is a reagent (an oxidant) rather than a catalyst.

1
+ I + HNO3  + NO2 + H2O
2 2


Iodination probably involves an electrophilic aromatic substitution with iodonium ion ( I ) acting as the
electrophile. The iodonium ion results from oxidation of iodine by nitric acid.

 1 
H + HNO3 + I  I + NO2 + H2O
2 2
iodonium
ion

7. Nitration
Nitration is brought about by the action of concentrated nitric acid or a mixture of concentrated nitric acid and
sulphuric acid often called nitrating mixture. HNO3 alone is a weak nitrating agent where as the mixture is
strong nitrating mixture when concentrated HNO3 and concentrated H2SO4 are mixed to form the nitrating
mixture, NO2+ (Nitronium ion) is produced as follows :

H3 O  +

HNO3 + 2H2SO4

Now, the NO2+ ion attacks the benzene nucleus and forms an intermediate cation (a benzenonium ion) which
loses a proton to yield the nitro derivative.

H+ +

8. Sulphonation
The electrophilic reagent, SO3, attacks the benzene ring to form the intermediate carbocation.

2H2SO4 SO3 + +
 Sulphonation, is reversible and takes place in concentrated sulphuric acid.

+ SO3 + H

9. Friedel Craft reaction

 
(a) Alkylation : The carbon atom of alkyl halides, R  X , is an electrophile. The presence of a Lewis acid
catalyst is also required. Anhydrous aluminium chloride. AlCl3, being a Lewis acid, accepts a lone pair of
electrons from halogen (Chlorine atom) of R – . This makes R (alkyl) group to be sufficiently polar so as to
act as an electrophile. The mechanism for Friedal Craft’s reaction involves the following steps.

(i)

(ii)

(iii) + AlCl4¯

Nature of Lewis acid as catalyst

The order of effectiveness of Lewis acid catalyst has been shown to be
AlCl3 > FeCl3 > BF3 > TiCl3 > ZnCl2 > SnCl4
Ex.2 What would be the major product of a friedal-Crafts alkylation reaction using the following alkyl halides ?
(a) CH3CH2Cl (b) CH3CH2CH2Cl (c) CH3CH2CH(Cl)CH3
(d) (CH3)3CCH2Cl (e) (CH3)2CHCH2Cl (f) CH2 = CHCH2Cl
Sol. (a) Ethylbenzene (b) Isopropylbenzene (c) Sec-butylbenzene
(d) Tert-pentylbenzene (e) Tert-butylbenzene (f) 3-Phenylpropene

(b) Acylation : Acylation of benzene may be brought about with acid chlorides or anhydrides in presence of
Lewis acids.
Mechanism
Step 1 : Formation of an acylium ion.

Step 2 : Electrophilic attack.

 Step 3 : Loss of a proton. Complexation of the product.

e.g. +

Note : Friedal - Crafts acylations are generally free from rearrangements and multiple substitution. They do
not go on strongly deactivated rings.

e.g.

10. Preparation of Aromatic compound :

(A) preparation of Benzene
(1) By polymerisation of Acetylene :

Re d hot iron tube

3HC  CH   

(2) By decarboxylation of Benzoic acid :

NaOH
NaOH  
 + Na2CO3
  (CaO )

(3) By catalytic reforming of n-Hexane :

Pt, 873 K Pt, 873 K

CH3 – (CH2)4 – CH3      
 H2  3H2

(4) By reduction of Benzene diazonium Chloride :

+ H3PO2 + H2O  + N2

 (B) Preparation of Toluene :
(1) By Friedel-Crafts reaction :

3 AlCl
+ CH3Cl 
 + HCl

Toluene
(2) By Wurtz fitting reaction :

dry ether
+ 2Na + CH3Br  + 2NaBr

Bromobenzene Toluene

(3) From Grignard reagents :

+ CH3Br  + MgBr2

(4) By catalytic reforming of n-Heptane :

873 K, Pt 873 K, Pt
     
(  H2 ) (  3H2 )

Methylcyclohexane Toluene

(C) Preparation of Xylene :

CH X, AlCl
3
  3
  +
11. Chemical Reactions of Benzene :

Ex.3 Gives the products of the following reactions :

(a) + AlCl3 AlCl3

  X (b) CH3 – Cl +   Y

CH3
| AlCl
3
(c) H3 C  HC  C  CH3 +  
  Z
| |
Cl CH3
Sol. X= phenylcyclohexane

Y=

O - methyl anisole p – methyl anisole

Z = 1 - Isopropyl – 4 – (1, 1, 2 – trimethylpropyl) benzene

Ex.4 Predict the products (if any) of the following reactions

Cl
|
(a) excess + H3C  C  CH3  AlCl3  X
|
CH3
Isobutylchloride

(b) + H3C  CH2  CH2  CH2  OH  BF3  Y

1  butanol

(c) + H3C  CH  CH3  AlCl3  Z

|
Cl
nitrobenzene (excess)
CH3
|
(d) + H3C  C  HC  CH2  HF  P
|
CH3

Sol. X= Y= or

Z = No reaction P = (1, 1, 2-Trimethylpropyl) benzene

12. ARYL HALIDES
(A) Preparation of Aryl Halides
1. Halogenation :

Lewis acid
+ X 2   + HX

X2 = Cl2, Br2
Lewis acid = FeCl3, AlCl3, ZnCl2, etc.

2. Decarboxylation :

NaOH / CaO + CO2

 


3. From Phenol :

5PCl
  + POCl3 + HCl


(B) Chemical reaction of Aryl halide (Bimolecular nucleophilic substitution)

Mechanism :

Step I  X  ( fast )
+ Nu     
RDS Step II

Intermediate ion is stabilized by resonance.

Note : 1. A group that withdraws electrons tends to neutralize the negative charge of the ring and so to become
more negative itself; this dispersal of the charge stabilizes the carbanion.

G withdraws electrons : stabilizes carbanion, activates

(– (CH3)3, –NO2, –CN, –SO3H, –COOH, –CHO, –COR, –X)

2. A group that releases electrons tends to intensify the negative charge, destabilizes the carbanion, and
thus slows down reaction.

G releases electrons : destabilizes carbanion, deactivates

(–NH2, –OH, –OR, –R)

 Orientiation in nucleophilic aromatic substitution :
(a) At para position :

(b) At meta position :

(c) At ortho position :

Note : If electron withdrawing group in present at ortho and para position it especially activates the aromatic
nucleophilic substitution reaction.

13. PHENOLS (ArOH) :

(A) Preparation of Phenol

(1) (2)

(3) (4)

(5) (6) +
Mechanism :

(B) Properties of phenol

These are characteristic of monohydric phenols. Phenol is a colourless crystalline solid, m.p. 43°, b.p.
182°C, which turns pink on exposure to air and light.
Phenol is used as an antiseptic and disinfectant and in the preparation of dyes, drugs, bakelite, etc.

(C) Chemical Reactions of Phenols

Phenol generally gives electrophilic substitution with electrophlile

(1)

(2)

(3) (Major is oxidative cleavage of ring) + Picric acid (small amount)

(4)

(5) Reimer-Tiemann formylation reaction :

 
Mechanism : Step (I) CHCl3 + NaOH CCl3 : CCl2

(6) Reimer-Tiemann carboxylation reaction :

(7) Kolbe reaction :

(8) Fries Rearrangement :

(9) (polymer)

(10)

(11)

(12)

(13)
Test of Phenol :
(i) Phenols turn blue litmus red. Phenols behave as acids because of the presence of polar O–H group in them.
they ionise in aqueous solutions to give H+ ions.

(ii) Reaction with Ferric Chloride

Phenol gives a violet-coloured water soluble complex with ferric chloride.
6C6 H5 OH + FeCl3 [Fe(OC6 H5 )6]–3 + 3H+ + HCl
Violet complex
(iii) Libermann’s test
When a sodium nitrite (NaNO2) is added to a phenol dissoved in conc. sulphuric acid red or brown colouration
is produced. The colour changes to blue or green by the addition of a strong alkali. This test can be used to
distinguish phenols from alcohols.
2NaNO2 + H2SO4 2HNO2 +Na2SO4
Sodium nitrite Nitrous acid

HNO
2


15. Nitrobenzene
(A) Preparation

(B) General properties of nitrobenzene

(i) Yellow liquid (ii) Denser than water. Thus insoluble in water but soluble in organic solvents
(iii) b.p. = 211°C (iv) steam - volatile

(C) Chemical Reactions of Nitrobenzene

(1)

(2)
(3)

(4)

(5)

(6)

(7)

(8)

(9)

(10)

Test of Nitro Benzene : (Mulliken- Barker’s Test)

+ Zn + NH4Cl  AgNO NH OH

3 
4  
 
Test of Benzaldehyde (Aromatic aldehyde)

 
 PhCO O N H4

16. ANILINE
(A) Prepartion of Aniline

(1)

(2)

(3)

(B) Chemical Reactions of Aniline

(1)

(2)

(3)

(4)
(5)

(6)

(7)

(8)

(9) (oxidation)

(10)

Test of Aniline :

(i) Carbylamine Reaction

Primary amines (alphatic as well as aromatic) react with chloroform (CHCl3 ) on heating in the presence of
ethanolic solution of KOH to form isocyanides (also called carbylamines) which are foul smelling substances.
Secondary and tertiary amines do not undergo this reaction, therefore this reaction is used as a test for
amino group (–NH2 ).
(ii) Reaction with Nitrous Acid
Amines of different classes react with nitrous acid (unstable acid) is prepared in situ by the reaction of
sodium nitrite (NaNO2) and dilute hydrochloric acid.

Primary aromatic amines react with nitrous acid at low temperature (273-278 K) to give aromatic diazo-
nium salts. This reaction is known as diazotisation.

Primary aliphatic amines also react with nitrous acid to form diazonium salt, however, the aliphatic diazo-
nium salts being unstable, decompose to yield mixture of alcohols, alkenes along with nitrogen gas.So this
reaction is used to distinguished between aromatic and aliphatic 1º amine.

H O
NaNO2 / HCl
C2H5NH2    2 C2H5OH + CH2 = CH2 + N2 + H2O

Secondary aliphatic and aromatic amines react with nitrous acid to produce nitroso-amines that are
insoluble in the aqueous solution and separate out as a yellow oily layer.

(C2H5)2 NH + HNO2  (C2H5)2 NH — NO + H2O

Diethyl amine N-Nitrosodiethylamine

Tertiary aliphatic amines reaction with nitrous acid to form salts which decompse on warming to ni-
trosoamine and alcohol while tertiary aromatic amines undergo electrophilic substitution at the ring.
R3N + HNO2  R3N .HNO 2 
 R 2N  N  O + ROH
Nitrite salt Nitrosoa min e

(iii) Hofmann mustard oil reaction


CH3CH2NH2 + S = C=S   HgCl2
    CH3CH2 –N = C=S + HgS + 2HCl

(1º amine) Ethyl isothiocyanate

17. Reaction of Benzenediazonium salt (chloride)

(1)

(2)
(3)

(4)

(5)

(6)

(7)

(8)

(9)

(10)

(11)
(12)

(13)

(14)

(15)
 MISCELLANEOUS SOLVED PROBLEMS (MSPS)
Complete the following reactions :

1. (a) + HClO4  (b) + 2 AgClO4 

Ans. (a) (b) + AgCl

Sol. Aromatic compounds are -

(i) cyclic (ii) planer
(iii) contains (4n + 2) no of -electrons where n = o , 1,2,3 .......
(iv) does cyclic resonance between (4 n + 2)  - electrons

2. AlCl3
+ CH3 – CH2 – CH2 – Cl  

Ans.

Sol. Aromatic compounds undergo electrophilic substitution reaction, and if possible then there is rearrangement
of carbocation occurs.

3. (a) + H


(b) +

(c)

Ans. (a) (b) (c)

Sol. Since the fridel craft acylation is faster than alkylation.

4. + H2SO4 

Ans.

Sol. 2H2 SO4 + +

5.

Sol. +

6.

Ans.

Sol. n case of biphenyl one ring is electron donor and other is electron acceptor.

7. Br / Fe
2  

Sol.

8. Br / Fe
2  

Ans.
9. Br / H O
2 2

Ans.

Sol. (a) ion increases the reactivity towards electrophile due to increases the electron density in ring.

1. CHCl3
10. (a)   
2. aq.KOH

1. CCl4
(b)   
2. aq.KOH

Sol. (a) (b)

Na2Cr2O7
11.    
H2SO 4

Ans. -

Sol. Oxidation of phenol with chromic acid produces a conjugated diketone known as benzoquinone.