Synopsis & Assignments - EAS by Prof. Ajay Yashpal Kapoor

CHEMISTRY ELECTROPHILICAROMATIC SUBSTITUTION
ELECTROPHILIC AROMATIC SUBSTITUTION
THE STRUCTURE OF BENZENE
A Resonance Picture of Benzene: In1865, August Kekulé, the originator of the structural theory
proposed the first definite structure for benzene, a structure that is still used today (although as we
shall soon see, we give it a meaning different from the meaning Kekulé gave it). Kekulé suggested
that the carbon atoms of benzene are in a ring, that they are bonded to each other by alternating
single and double bonds, and that one hydrogen atom is attached to each carbon atom. This structure
satisfied the requirements of the structural theory that carbon atoms form four bonds and that all
the hydrogen atoms of benzene are equivalent.
H
H H
or
H H
H
The Kekulé formula for benzene

The Stability of Benzene: We have seen that benzene shows unusual behaviour by undergoing
substitution reactions when, on the basis of its Kekulé structure, we should expect it to undergo
addition. Benzene is unusual in another sense. It is more stable than the Kekulé structure suggests.
To see how, consider the following thermochemical results.
Cyclohexene, a six-membered ring containing one double bond, can be hydrogenated easily to
cyclohexane. When the H0 for this reaction is measured it is found to be –120kJ mol–1, very
much like that of any similarly substituted alkene.
 H 2 
Pt
 H 0  120kJmol1
cyclohexene cyclohexane
We would expect that hydrogenation of 1,3-cyclohexadiene would liberate roughly twice as much
heat and thus have a H° equal to about –240 kJ mol–1. When this experiment is done, the result
is H° = – 232 kJ mol–1. This result is quite close to what we calculated, and the difference can be
explained by taking into account the fact that compounds containing conjugated double bonds are
usually somewhat more stable than those that contain isolated double bonds.
In addition reaction with H2 / Pt 1, 3 diene is definitely more reactive than monoene because of
more unsaturation. But between two different dienes, conjugated and isolated, conjugate is more
stable because of higher stabilisation.
Calculated
 2H 2 
Pt H 0  (2   120)  240kJmol 1
Observed
cyclohexa-1,3-diene cyclohexane H   232kJ mol -1
If we extend this kind of thinking, and if benzene is simply 1,3,5-cyclohexatriene, we would predict
benzene to liberate approximately –360 kJ mol–1 (3 × –120) when it is hydrogenated. When the
experiment is actually done the result is surprisingly different. The reaction is exothermic, but only
by –208 kJmol–1.
Prof. Ajay Yashpal Kapoor 1

ELECTROPHILICAROMATIC SUBSTITUTION CHEMISTRY
Calculated
H 0  (3  120)  360kJmol 1
 3H 2 
Pt
 Observed H  208kJ mol-1
___________________________
benzene cyclohexane Differnece = 152kJ mol -1
When these results are represented as in figure, it becomes clear that benzene is much more
stable than we calculated it to be. Indeed, it is more stable than the hypothetical 1,3,5-cyclohexatriene
by 152 kJ mol–1. This difference between the amount of heat actually released and that calculated
on the basis of the Kekulé structure is now called the resonance energy of the compound.
The Resonance Explanation of the Structure of Benzene
A basic postulate of resonance theory is that whenever two or more Lewis structures can be
written for a molecule that differ only in the positions of their electrons, none of the structures will
be in complete accord with the compound’s chemical and physical properties. If we recognize this,
we can now understand the true nature of the two Kekulé structures (I and II) for benzene. The
two Kekulé structures differ only in the positions of their electrons. Structure I and II, then, do not
represent two separate molecules in equilibrium as Kekulé had proposed. Instead, they are the
closest we can get to a structure for benzene within the limitations of its molecular formula, the
classic rules of valence, and the fact that the six hydrogen atoms are chemically equivalent. The
problem with the Kekulé structures is that they are Lewis structures, and Lewis structures portray
electrons in localized distributions. (With benzene, as we shall see, the electrons are delocalized).
Resonance theory, fortunately, does not stop with telling us when to expect this kind of trouble; it
also gives us a way out. Resonance theory tells us to use structures I and II as resonance contributors
to a picture of the real molecules of benzene. As such, I and II should be connected with a double
headed arrow and not with two separate ones (because we must reserve the symbol of two
separate arrows for chemical equilibria). Resonance contributors, we emphasize again, are not in
equilibrium. They are not structures of real molecules. They are the closest we can get if we find
found by simple rules of valence, but they are very useful in helping us to visualize the actual
molecule as a hybrid.

)
(not 

I II
Look at the structures carefully. All of the single bonds in structure I are double bonds in structure
II. If we blend I and II, that is, if we fashion a hybrid of them, then the carbon-carbon bonds in
benzene are neither single bonds nor double bonds. Rather, they have a bond order between that of
a single bond and that of a double bond. Bond order of benzene ring is found to be 1.5. This is
exactly what we find experimentally. Spectroscopic measurements show that the molecule of
benzene is planar and that of all of its carbon-carbon bonds are of equal length. Moreover, the
carbon-carbon bond lengths in benzene figure are 1.39Å, a value in between that for a carbon-
carbon single bond between sp2 hybridized atoms (1.47Å) and that for a carbon-carbon double
bonds (1.33Å)
H H
120
H 120 H
1.09Å
120
1.39Å
H H
Bond lengths and angles in benzene
2 Prof. Ajay Yashpal Kapoor

The hybrid structure is represented by inscribing a circle in the hexagon, and it is this new formula
(III) that is most often used for benzene today. There are times, however, when an accounting of
the electrons must be made, and for these purposes we may use one or the other of the Kekulé
structures. We do this simply because the electron count in a Kekulé structure is obvious, whereas
the number of electrons represented by a circle or portion of a circle is ambiguous. With benzene
the circle represents the six electrons that are delocalized about the six carbon atoms of the
benzene ring. With other systems, however, a circle in a ring may represent numbers of delocalized
electrons other than six.
III
Resonance theory also tells us that whenever equivalent resonance structures can be drawn for a
molecule, the molecule (or hybrid) is much more stable than any of the resonance structures would
be individually if they could exist. In this way resonance theory accounts for the much greater
stability of benzene when compared to the hypothetical 1,3,5-cyclohexatriene. For this reason the
extra stability with benzene is called its resonance energy. It is this very large increment of resonance
energy that places benzene and related compounds in a separate category that we call aromatic.
H H
H H
H H
Huckel’s Orbitals in benzene’s orbital overlap is indicated by the dashed lines

AROMATICITY & AROMATIC COMPOUNDS
Aromatic compound are those that meet the following criteria
1. The structure must be cyclic, containing some number of conjugrated pi bonds.

2. Each atom in the ring must have an unhybridized p orbital. (The ring atoms are usually sp2 hybridized
or occasionally sp hybridized.
3. the unhybridized p orbitals must overlap to form a continuous ring of parallel orbitals. In most
cases, the structure must be planar (or nearly planar) for effective overlap to occur.
4. Delocalization of the pi electrons over the ring must lower the electronic energy.
An antiaromatic compound is one that meets the first three criteria, but delocalization of the pi
electrons over the ring increases the electronic energy.
A cyclic compound that does not have a continuous, overlapping ring of p orbitals cannot be
aromatic or antiaromatic. It is said to be nonaromatic, or aliphatic. Its electronic energy is similar
to that of its open-chain counterpart. For example, 1, 3-cyclo-hexadiene is about as stable as cis,
cis-2, 4-hexadiene.
Once these criteria are met, Huckel’s rule applies:
Huckel’s Rule: If the number of pi electrons in the cyclic system is:

(4n + 2), the system is aromatic;

(4n), the system is antiaromatic.
When n is an integer.
Common aromatic systems have 2, 6, and 10 pi electrons, for n = 0, 1, and 2. Antiaromatic systems
might have 4, 8, or 12 pi electrons, for n = 1, 2, or 3.
Large-Ring Annulenes
Like cyclooctatetraene, large annulenes with 4n systems do not show antiaromaticity because
they have the flexibility to adopt nonplanar conformations. Even though [12] annulene, [16] annulene,
and [20] annulene are 4n systems (with n = 3, 4, and 5, respectively), they all react as partially
conjugated polyened.
H
H
Repulsion of two H's

all-cis makes it out of plane naphthalene
nonaromatic nonaromatic aromatic
Pyridine
Pyridine is an aromatic nitrogen analogue of benzene. It has a six-membered heterocyclic ring
with six pi electrons. Pyridine has a nitrogen atom in place of one of the six C – H units of benzene,
and the nonbonding pair of electrons on nitrogen replaces the bonds to a hydrogen atom. These
nonbonding electrons are in an sp2 hybrid orbital in the plane of the ring. They are perpendicular to
the pi system and do not overlap with it.
N
Pyrrole
Pyrrole is an aromatic five-membered heterocycle, with one nitrogen atom and two double bonds.
Although it may seem that pyrrole has only four pi electrons, the nitrogen atom has a lone pair of
electrons. The pyrrole nitrogen atom is sp2 hybridized, and its unhybridized p orbital overlaps with
the p-orbitals of the carbons atoms to form a continuous ring. The lone pair on nitrogen occupies
the p-orbital, and (unlike the lone pair of pyridine) these electrons take part in the pi bonding
system. These two electrons, added to the four pi electrons of the two double bonds, complete an
aromatic sextet. Pyrrole has a resonance energy of 22 kcal/mol (92 kJ/mol.)
..
N
|
H
Furan and Thiophene
Furan is an aromatic five-membered heterocycle-like pyrrole, but the heteroatom is oxygen instead
of nitrogen. The classical structure for furan shows that the oxygen atom has two lone pairs of
electrons. Theoxygen atom is sp2 hybridized, and one of the lone pairs occupies an sp2 hybrid
orbital. The other lone pair occupies the unhybridized p orbital, combining with the four electrons

in the double bonds to give an aromatic sextet. Furan has a resonance energy of 16 kcal/mol (67
kJ/mol).
..
..O
Furan
Thiophene is similar to furan, with a sulfur atom in place of the furan oxygen. The bonding in
thiophene is similar to that in furan, except that the sulfur atom uses an unhybridized 3p orbital to
overlap with the 2p orbitals on the carbon atoms. The resonance energy of thiophene is 29 kcal/
mol (121 kJ/mol).
..
..S
Thiophene
Anthracene and Phenanthrene

As the number of fused aromatic rings increases, the resonance energy per ring continues to
decrease and the compounds become more reactive. Tricyclic anthracene has a resonance energy
of 84 kcal/mol (351 kJ/mol), or 28 kcal (117 kJ) per aromatic ring. Phenanthrene has a slightly
higher resonance energy of 91 kcal/mol (381 kJ/mol), or about 30.3 kcal (127 kJ) per aromatic
ring. Each of these compounds has only 14 pi electrons in its three aromatic rings, compared with
18 electrons for three separate benzene rings.
Anthracene
Phenanthrene
ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS
It has been stated that an aromatic ring has negative charge cloud below and above its plane.
Electrophiles being positively charged or electron-deficient species, they are very prone to attack
the negative charge cloud of the delocalized e’s. Therefore, it might be expected that electrophilic
reactions will occur on aromatic rings much readily; but an aromatic compound wants to preserve
its aromatic character and hence its stability,and therefore it is to some extent relactant to utilize its
e’s. For this reason the electrophiles react with aromatic compounds but not readily, rather slowly.
However, the most important type of reactions tht the aromatic compounds undergo is the
bimolecular electrophilic substitutions which are designated as SE2 aromatic.
Aromatic SE2 reactions are supposed to occur in two discrete steps:
Step I: In this step the electrophile, E+, is attacked by the aromatic substrate laterally i.e., perpendicular
to thie ring and forms a sigma-complex or Wheland complex (or cyclohexadienyl cation in the case
of benzene) in which a specific atom of the electrophile forms a covalent bond with a specific C
atom of the ring; the involved sp2 hybridised C atom of the ring then assumes sp3 hybridised state.
Let us represent the step taking benzene as an aromatic substrate.

The sigma complex so formed remains as a salt which is formed by the union of the cationic -
complex with an anion.
Step II: In this step, the -complex gives up a proton and gets converted into another aromatic
compound, a derivative of the aromatic substrate; the proton is removed by the anionic part of the
-complex salt.
H
E E E E
     E
H H H H H
H
In most of the cases the -complex formation step is the slower step and hence it is the rate-
determining step. Since the -complex consists of the electrophile and the substrate, the transition
state of the reaction involves each of them; and hence aromatic electrophilic substitution reactions
are usually bimolecular reactions. The T.S. of the step I, the rate-determining step, and that of the
step II may be represented as:
E  E
 

H H
T.S. I T.S. II
Therefore the over-all reaction may be written as:

E E E
+ +
E   
E H

H H H
T.S.I T.S.II
Since the T.S. of the rate-determining step of an aromatic SE2 reaction involves two species, it is
expected that the reaction will follow the second order kinetics.
T.S. I
T.S. II
 Complex
Reagent &
G Substrate Product
Progress of the reaction



The energy profile of an exothermic aromatic SE2 reaction without the formation of a -
complex
The evidences for the two step mechanism are:
i) Detection and isolation of -complexes: A large number of -complexes, as intermediates in Ar.
SE2 reaction, have been detected by n.m.r. spectroscopic study. Some of them have also been
isolated as -complex salts.
ii) Primary kinetic isotope effect: Displacement of an H (or D) atom of C6H6 (or C6D6) by a nitronium
ion NO2+; (formed by the action of concentrated H2SO4 on concentrated HNO3) is an aromatic
SE2 reaction. It has been found that the rate of formation of C6H5NO2 from C6H6 is almost equal
to the rate of formation of C6D5NO2 from C6D6 under the same set of conditions. This means that
the C —H bond breaks at the same rate as the C —D bond breakes. If the C—H bond breaking
step i.e., the step II of the Ar. SE2 reaction were a rate-determining step, then C6D5NO2 would
have been formed more slowly than C6H5NO2. Since this does not happen, the -complex formation
step i.e., the first step is the rate determining step.
There is no doubt that the -electron cloud of an aromatic system invites an electrophile to react,
nevertheless the electrophilic substitution reactions do not occur readily. Of course, strong
electrophiles and electron-donating substituents, which have +I, +R and /or hyperconjugative effects,
on aromatic rings are expected to enhance the rate. On the other hand substituents with electron-
withdrawing effects, –I and/or –R, and weak electrophiles decrease the rate of an Ar. S E2 reaction.
The groups which increase the rates of Ar . SE2 reactions by donating electron to the ring are
called activating groups; they activate the ring by +I, +R and hyperconjugative effects. –I and –R
groups withdraw electrons from an aromatic ring and thereby slow down Ar. SE2 reactions and,
therefore, they are called deactivating groups.
EFFECT OF SUBSTITUENTS ON RATES OF Ar. SE2 REACTIONS

(STANDARD OF COMPARISON IS H ATOM)
Electrical effect
Nature of group     +R effect predominates over
Activating  O,  NR2 ,  NR2 ,  OH, the —I effect
 

 
NHCOR,  OR,  O COR  O : does not have –I effect

 
—Ar Conjugative effect
—R +I and hyperconjugative effect
Deactivating  –I-effect predominates over the

—X: +R-effect

—CX3
—CHO,—COOH,—COCH3,—CN,—SO3H, — —I-effect
NO2 –I and —R-effects
SR2+, NR3+ –I-effect
Illustration 1: Write down the relative rate order of monobromination of the following
compounds and assign reasons for the order PhNH 2, PhCOOH, PhH, PhBr, PhNO 2,
PhCH3
Solution : Among the given compounds PhNH2 and PhCH3 have activating groups, —NH2, and —CH3
respectively. NH2 has a strong +R-effect and CH3 has +I-effect and hyperconjugative effet; +R
effect being stronger than the +I and hyperconjugative effects, PhNH2 will undergo the reaction

more readily than PhCH3. Again, PhCOOH, PhBr, PhNO2 have deactivating groups; the order of
increasing deactivating effects is:
Br  — COOH  —NO2
So among these three the rate order will be:
PhBr  PhCOOH  PhNO2
PhH has neither a deactiving nor an activating group; so it will be more reactive than the compounds
with deactivating groups. Therefore, the decreasing rate order is:
PhNH2  PhCH3  PhH  PhBr  PhCOOH  PhNO2
ORIENTATION AND REACTIVITY IN ELECTROPHILIC ARMATIC SUBSTITUTION

In the case of benzene we get just one monosubstituted product in electrophilic aromatic substitution
as all the positions are equivalent. However, for substitution in a compound which already has a
group attached to the ring, three disubstituted products, (1,2), (1,3), (1,4) commonly called ortho,
meta and para meaning next to, between and opposite respectivey are possible. These are
abbreviated as o, m and p.
Y Y Y Y
E
 E 
  
E
1, 2 1, 3
ortho m eta E
1, 4
para
One may think, are all the three products formed in equal amounts or is there some kind of
preference? Let us take two examples.
CH 3 CH 3 CH 3 CH 3
NO2 


HNO3 / H 2 SO 4
300 K
NO 2
58% 5% NO 2
37%
NO 2 NO 2 NO 2 NO 2
NO 2
 fumin  
g HNO 3 / H 2 SO 4
  
375 K
NO 2
6% 93% NO 2
1%

Donation of electrons into a benzene ring by resonance
OCH3 OCH3 OCH3 OCH3 OCH3
If a substituent is attached to the benzene ring by an atom that is doubly or triply bonded to a more
electronegative atom, the  electrons of the ring can be delocalized on to the substituent. Such
substituents are said to withdraw electrons by resonance. Substituents such as —C=O, —C  N,
and NO2 withdraw electrons by resonance. These substuents also withdraw electrons inductively
because the atom attached to the benzene ring is more electronegative than a hydrogen.
Withdrawal of electrons from a benzene ring by resonance
O + O O + O O + O O + O O + O
N N N N N
Notice the difference in the electron densities of the benzene rings in the electrostatic potential
maps for anisole and nitrobenzene.
The substituent already attached to benzene determines the location of the new substituent. There
are two possibilities - a substituent will direct an incoming substituent either to the ortho and para
positions or will direct an incoming substituent to the meta position. All activating substituents and
the weakly deactivating halogens are ortho/para directors, and all substituents that are more
deactivating than the halogens are meta directors.
1. All activating substituents direct an incoming electrophile to the ortho and para positions.
CH 3 CH 3
Br CH 3
 Br2  FeBr
 3  
toluene o-brom otoluene
Br
p-brom otoluene
2. The weakly deactivating halogens also direct an incoming electrophile to the ortho and para positions.
Br Br
Cl Br
 Cl 2  FeCl
 3
 
bromobenzene o-bromochlorobenzene
Cl
p-bromochlorobenzene

3. All moderately deactivating and strongly deactivating substituents direct an incoming electrophile
to the meta position.
O CH3 O CH3
C C
HNO3 
H 2SO 4

NO2
acetophenone m-nitroace tophenone
NO2
NO2
Br2 
FeBr3

Br
nitrobenzene m-bromonitrobenzene
To understand why a substituent directs an incoming electrophile to a particular position, we must
look at the stability of the carbocation intermediate formed in the rate-determining step. When a
substituted benzene undergoes an electrophilic substitution reaction, three different carocation
intermediates can be formed. Which one is more likely to be formed depends on their relative
stabilities. Comparing the relative stabilities of the three carbocations allow us to determine the
preferred pathway of the reaction because the more stable the carbocation, the less energy required
to make it.
CH3 CH3 CH3

Y Y Y
H H H

ortho
attack
 
 

most stable
CH3 CH3 CH3 CH3
 Y  
meta
attack
 Y 
 Y 

Y
H H H
toluene
CH3 CH3 CH3

para
attack
 
 

H Y H Y H Y
most stable
The structure of the carbocation intermediates formed from the reaction of an electrophile with
toluene at the ortho, meta, and para positions. As the ortho & para complexes are relatively more
stable hence it is ortho, para orienting.
anisole at the ortho, meta, and para positions is shown below.

OCH3 OCH3 OCH3

Y Y Y
H H H

ortho
attack
 
 

OCH3
Y
H relatively more stable
OCH3 OCH3 OCH3 OCH3
 Y  
meta

attack Y 
 Y 

Y
anisole
H H H
OCH3 OCH3 OCH3

para
attack
 
 

H Y H Y H Y
OCH3
H Y
relatively more stable
anisole at the ortho, meta, and para positions. As the ortho & para complexes are relatively more
stable hence it is ortho, para orienting.
NH 3 NH 3 NH 3
Y Y Y
H H H

ortho
attack
 
 

least stable
NH 3 NH 3 NH 3 NH 3
 Y  
meta
 Y 
 Y 

attack Y
protonated
aniline
H H H
NH 3 NH 3 NH 3

para
attack
 
 

H Y H Y H Y
least stable

The structures of the carbocation intermediates formed from the reaction of an electrophile with
protonated aniline at the ortho, meta, and para positions.

Now let us apply the method to determine the directing nature of the NH group. The three
2
possible -complexes are:
NH2 NH2 NH2 NH2

H H H H
Ortho  E E E E

attack
 H
 
 

1 2 3 4
H Extra-stable
NH2 NH2 NH2 NH2


E Meta 
  H
attack H 
 H
H


H
H E
5 6 E 7 E
NH2 NH2 NH NH2

Para 

attack


  H
 H

H
E H E H E H E H
8 9 10 11
Extra-stable
Thus, we see that each of the ortho and the para complexes has one extra resonating structure
(4 and 10 respectively) in their resonance hybrids; these structures are extra-stable since all the C
and N atoms are in the octet state. These two structures bring extra stability to the ortho and the
para complexes. Therefore two T.S. for the o-attack and that for the p-attack will have lower
energy than the T.S. for the m-attack; as a consequence the rates of reaction at the o- and p-
positions will be greater than the rate of reaction at the m-position which will lead to form predominant
o/p-products.

CHO CHO
H H CHO
H
E E
Ortho E

attack
H least stable
2 H 3
4
CHO H O H O H O
H H
E Meta 
 
attack H H
H
5 E 6 E H E
7
H O H O H O
Para 

attack H H
E 8 H E 9 H E 10 H
least stable

The effect of substituents on the reactivity of a benzene ring toward electrophilic substitution
Activating substitutents most activating

—NH2 
—NHR
 strongly
—NR 2  activating

—OH 
—OR 
O 

—NHCR  moderately
O 
 activating

—OCR 
ortho/para
—R  directing
—Ar  weakly
—CHCR
2
 activating
Standard of comparision 
—H
Deactivating substituents 
—F
—Cl
 weakly
—Br
 deactivating
—I
O
—C—H
O
—C—R
O moderately
deactivating
—COR
O
meta directing
—COH
O
—CCl
—C N 
—SO3H 
 
—NH 3

—NHR2  strongly
   deactivating
—NHR 2 —NR 3 
—NO2 
most deactivating
ORTHO / PARA RATIO
Directive influence of the groups during substitutions in benzene ring
a) The position of new incoming group (guest) in C6H6 nucleus is decided by the group
already present in nucleus (host). This is known as directive influence of the host group
present in the nucleus.
b) Directive influence of the host group is of two types i.e. the group already present in nucleus
during further substitution of a group acts as

i) either ortho and para directing nature

ii) or meta directing nature
Cl Cl Cl

Chlorination Cl + Since 'Cl' is o- and p- directing
Cl
Cl
Cl Cl

Nitration NO2+
NO2
NO2 NO2

Chlorination
 Since 'NO 2' is meta directing
Cl
NO 2 NO 2
 Nitration
  
NO 2
c) On the basis of their directive influence, the substituents have been classified as:
‘o’- and ‘p’- directing groups: –NH2, –NHR, –NR2, –OH, –OR, –SH, –SR, –CH3,
–CH 2R, –CHR 2, –CR 2, –C 6H5, –Cl, –Br, –I, –CH 2OH, –CH 2Cl, –CH 2NH 2, –CH 2CN, –
CH2COOH, –CH = CH – COOH
‘m’-directing groups: –NO2, –SO2H, –SO2Cl, –CHO, —SO3H, –COCl,
–COOR, –COR, –COCOOH, –CCl3, –N+H3, –N+H2R, –N+R3
When elecrophilic substitution reactions are carried out on a benzene derivative containing an
ortho-para directing group, the ratio of the yield of the ortho-product to that of the para-product is
found to vary from reaction to reaction and substrate to substrate. Since there are two o-positions
and one p-position relative to the substituent in a monosubstituted benzene, it may seem that the o/
p ratio will be 2 : 1 in all reactions irrespective of any substituent; but this is not true. The products
never form corresponding to that ratio. Several factors need consideration to explain the o/p ratios
observed in aromatic substitution reactions. The factors are:
i) Steric effect
ii) electronic effects of the substituent already present in the benzene ring
iii) interaction between the substituent and the attacking electrophile
iv) effect of temperature
v) solvation effect
When alkylbenzenes are nitrated under the same set of conditions, the o/p-ratio is found to be the
highest in the case of toluene and the lowest in the case of t-butylbenzene as shown in the table.

o/p ratios in the nitration of alkylbenzenes

Substituents % of o-product % of p-product o/p-ratio
Me 58 37 1.57
Et 45 49 0.92
i.Pr 30 62 0.48
t-Bu 16 73 0.22
The reveals that as the volume of the substituent (alkyl group) increases down the series (me to t-
Bu) the yield of o-nitroproduct decreases and that of the p-nitroproduct increases and as a
consequence o/p-ratio decreases.
Alkylation of toluene by the Friedel-Crafts reaction and the % of o-product
Increasing bulk Attacking electrophile % of o-product

 Me 53.8
 Et 45.0

i-pr 37.5

t-Bu 0
SE reaction on chlorobenzene and the o/p-ratio
Increasing Attacking % of % of o/p-ratio

bulk electrophile o-product p-product
 Cl+ (chlorination) 39 55 0.71
 +
NO2 (Nitration) 30 70 0.43
 +
Br (Bromination) 11 87 0.14

SO3 1 99 0.01
(Sulphonation)
However, the steric-factor alone should not be held responsible for the observed o/p-ratio in different
reactions. The electronic effects should also be considered among other factors. When halobenzenes
are nitrated under the same set of conditions, the yield of o-product increases and that of the p-
product decreases despite the increase in the size of the substituents, F to I, as shown in the table.
Electronic effects and the o/p-ratio in the nitration of halobenzenes
Increasing  Substituent % of % of o/p-ratio

volume and o-product p-product
decreasing –I 
 F 12 88 0.14
effect
 Cl 30 69 0.44
Br 37 62 0.60
I 38 60 0.63
–I effect of the halogen groups is supposed to be responsible for the observed o/p-ratios as shown
in the table.
The –I-effect decreases on going from F to I as the electronegativity of the group decreases.

Mechanism of o and p-directing groups: The o- and p-directing groups (except alkyl and COO–)
have unshared pair of electrons on the atom attached on benzene nucleus. The mechanism is
therefore discussed in terms of two aspects.
Mechanism of o- and p-directing groups not have unshared pair of electrons: Consider an alkyl
group attached on C6H6 nucleus. It is an electron repelling group. The +I.E. of alkyl group and +
Electromeric effect along with + Mesomeric effect give rise to an increase in electron density at
o- and p-positions and thus provide site for electrophile to attack these centres. This can also be
explained in terms of hyperconjugation.
R R R R
Mechanism of o- and p-directing groups having unshared pair of electron(s): Consider –OH
group attached on C6H6 nucleus having two unshared pair of electron on O atom. One of the such
unshared pair of electron shifts towards nucleus following +E effect and +M effect and give rise
to an increase in electron density at o- and p-position and thus provide seat for electrophile to
attack these centres.
+ + +
O H O H O H O H
Note :
1. A free electron pair charge or increased density at o- and p-position activates ring for
further substitution. That is why nucleus having o- and p-directing groups are more reactive
than benzene for SE reactions.
2. The o- and p-directing groups (except halogens) are thus also known as activating groups.
3. Halogens, although increase electron density at o- and p- positions due to +E and +M effect,
but they also deactivate the ring due to strong –I effect. (Halogens are strong electron
withdrawing groups).
Mechanism of m-directing groups: The m-directing groups except CCl3, either possess a –ve charge
or the atom of such group attached to nucleus has a multiple bond on it. The –E, –M and –I effect
of all such groups leading the displacement of the electrons away from the nucleus and withdraw
the electron from o- and p-position, thereby producing a decrease in electron density at o- and p-
position.
O O O O O O O O
N N N N
The electron density at meta position remains unchanged, however, the relative electron density at
meta position becomes more and thus electrophile attacks m-positions in all such cases.

Note:
1. The meta position electron density remains unaffected in presence of m-directing groups and thus
these groups provide no extra facility for electrophile. On the country they deactivate the ring for
further substitution. That is why presence of m-directing group on benzene nucleus give rise to S E
reactions with difficulty in comparison to benzene itself.
2. –CCl3, NH3 and NR3 groups undergo –I effect followed with –M effect.
Competitive orienting effect of two substituents

1. Two groups reinforce (provide same place for SE reaction) each other
CH3 CH3
E

E

CH3 CH3
Electrophilic attacks o- and p- positions of each CH3 group, which are same and only one possible
product is formed.
CH3 CH3
E

E

NO2 NO2
Electrophile attacks o- and p-positions of CH3 group and m-positions of –NO2 group which are
same and only one possible product is formed.
2. Two groups, one o- and p-directing and one meta directing provides different positions
for SE reactions: The o- and p-directing group activates the ring by supplying electrons at o- and
p-positions, whereas m-directing group deactivates ring by withdrawing electrons from o- and p-
positions. In such cases the power of o- and p-directing group overpowers the m-directing group
e.g.
CH3 CH3 CH3 CH3
1
NO2 O2N
6 2

Nitration
mixture  
5 3
4 NO2 NO2 NO2 NO2
NO2
CH3 group supplies electrons to 2,6 and 4 positions; NO2 withdraws electrons from 2,6,4 positions.
The power of CH3 group predominates and no substitution occurs at m-position of –NO 2 group i.e.
CH3
is not formed
O2N NO2
3. Two o- and p-directing groups – one is strong activating and other one is weak: The o-
and p-directing group having strong nature to supply electron pair and o- and p-position overpowers
the effect of other o- and p-directing group having weak nature to supply electron pair at o- and p-
position e.g. OCH3 is relatively stronger o- and p-directing group than methyl group and thus
substitution occurs with respect o- and p-positions of OCH3 group.

CH3 CH3

Nitration

NO2
O O
H3C H3C
strong
Note:
1. p-position is not vacant for OCH3 group and thus only at o-position substitution occurs.
2. No substitution at o-position of CH3 group.
4. Two weak activating or deactivating groups or two strong activating or deactivating
groups are present: All possible isomers are formed.
DIFFERENT TYPES OF REACTIONS :

NITRATION
Nitration reaction is generally carried out with a mixture of concentrated nitric acid and sulphuric
acid. The reagents which cause nitration are called nitrating agents.
The various nitrating agents which are commonly employed are:
1. N2O5 in CCl4 in the presence of P2O5 is used when anhydrous conditions are required.
2. Ethyl nitrate (C2H5ONO2) is used to carry out nitration in alkaline medium.
3. In the case of polycyclic hydrocarbons N2O4 and nitronium salts such as NO2 BF4

NO2 PF6 , N O2 SO3– can be used. The electrophile involved in nitration reaction is nitronium ion
NO  .

2
MECHANISM
1. Generation of electrophile from nitrating agent:
a) In a mixture of nitric acid and sulphuric acid, an acid base reaction takes place in which
nitric acid acts as the base.

HO – NO2 + H2SO4    H – O – NO2 + HSO4
Base |
 H

H – O – NO2   NO2 + H2O
|
H
+
H2O + H2SO4  
  H3O +HSO4
 
HNO3 + 2H2SO4   NO2 + H3O + 2HSO4
b) N2O5 in CCl4 when used, results in a spontaneous dissociation reaction.


N2O5 NO2 + NO3

c) With concentrated HNO3 alone


 NO 2  NO3  H 2 O
2HNO3  
Illustration 2 : The electrophile generated in this case is obtained by the behaviour of one nitric acid as
the base and other molecule as the acid, but the equilibrium lies in the reactant side
Convert benzene  p-bromonitrobenzene
Br Br Br
NO 2

Br2

N.A.
  (Separate)
Fe
Solution:
NO 2
SULPHONATION
The process of introducing SO3H-group into an aromatic nucleus by the action of concentrated
sulphuric acid or fuming sulphuric acid (oleium; H2S2O7 – sulphur trioxide in sulphuric acid) or
sulphur trioxide in an organic solvent (nitromethane, pyridine etc) or chlorosulphonic acid in carbon
tetrachloride on aromatic compounds is called aromatic sulphonation.
Alkylbenzenes, amines, phenols, phenolic ethers, thiosphene, furan, pyridine, naphthalene etc,
undergo the reaction. Of course, the condition of reaction differs from substrate to substrate.
Aromatic sulphonation is a reversible reaction. At low temperatures, the reaction is practically
irreversible since the reverse reaction, known as desulphnation reaction, is very slow. Since
sulphonation and desulphonation are very simple processes, they have some synthetic values.
Several aromatic compounds and  -substituted naphthalenes are prepared with the help of
sulphonation and desulphonation process. Desulphonation is usually done by heating the sulphonic
acid derivative with HCl at an elevated temperature.

i) Synthesis of o-bromotoluene.
CH3 CH3 CH3 CH3

Br Br
  
H2SO 4
  
F e /B r2   HCl
150o C
SO 3 H SO 3 H
The mechanism of the reaction is supposed to be as follows. When the reagent for sulphonation is
concentrated sulphuric acid or fuming sulphuric acid or sulphurtrioxide in organic solvent,the
electrophile is SO3; the S atom is the cetnre of positive charge.
2H2SO 4    SO3  H3O  HSO 4
H2S2O7    H2SO4  SO3
2/3
O O O
O 
S O 2/3
S O S O S O
O O O O 2/3
Step I: Electrophilic attack by the SO3 on a nuclear carbon of the aromatic compound to form -
complex.
H SO 3
 O
S O 
 k 1
O k –1
 complex
Step II: Deprotonation of the -complex and aromatization.
SO 3 SO 3 H
H SO 3
fast
k 2 slow
  slow
  
  H   fast
 
Deportonation step is the slow rate-determining step. This has been proved by the primary kinetic
istope effect. However arguments tell us that as an Ar . SE2 reaction, the -complex formation
step should be the R.D. step.
When the reagent is oleum the second step is supposed to be the rate-determining step.
SO 3 H
H SO 3 H SO 3 H
H 
    H
 H 

HALOGENATION
Halogenation of an aromatic ring is a synthetically important reaction. It takes place in the presence
of varied reaction condition depending on the reactivity of the aromatic ring. For very reactive
aromatic compounds in polar solvents, the molecular halogens themselves may acts as electrophiles.
In the case of nonpolar solvents,halogenation is catalysed by a Lewis acid like AlCl3 , or FeCl3 ,
Reactivity of halogens has the following order,
I2  Br2  Cl2
Let us take chlorination as a representative reaction to understand the mechanism of halogenaton.
Chlorine, in the presence of AlCl3 or FeCl3 forms a complex, Cl2 — AlCl3 . This complex can
itself be the reactive electrophile or it may dissociate to give Cl .
 
 
Step: 1 Cl — Cl  AlCl3  
 Cl Cl ACl3   Cl  AlCl4
 
(anhydrous)
H Cl
 
Step: 2  Cl Cl ACl3 

Slow
  AlCl 4
Cl
Cl H
Step : 3  AlCl3  HCl
 AlCl 4 
Fast
FRIEDEL - CRAFTS ALKYLATION
Alkyl halides react with benzene in presence of aluminium chloride to yield alkyl benzenes.
Alkylation of benzene with alkyl halides in the presence of aluminium chloride was discovered by
Charles Friedel and James. M. Crafts in 1877.
A general equation for a Friedel - Crafts alkylation reaction is the following.
R
 R — X 
 AlCl3
 HX
Alkyl halides by themselves are insufficiently electrophilic to react with benzene. AlCl3 serves as
a Lewis acid catalyst to enhance the electrophilicity of the alkylating agent. The mechanism for
the reaction (shown in the following steps, with isopropyl chloride as R–X) starts with the formation
of carbocation (step I). The carbocation then acts as an electrophile (Step–II) and attacks the
benzene ring to form an arenium ion. The arenium ion (Step III) then loses a proton to generate
isopropyl benzene. Some times carbocation rearrange to a more stable carbocation.

Mechanism
Cl H 3C Cl H 3C
H 3C
+
CH Cl  Al  
 CH Cl Al Cl  
 CH  AlCl4
Step I
Cl Cl H 3C H 3C
H 3C Cl
CH3 CH3
 HC  
 
 other canonical forms
Step II
CH3 H CH
3
CH3 Cl CH3
 Cl Al Cl  
  HCl  AlCl3
Step III H CH3
Cl CH3
with R–X is a primary halide, a simple carbocation probably does not form. Instead, the AlCl3
forms a complex with the alkyl halide and this complex acts as the electrophile. In the complex the
carbon halogen bond is nearly broken and one in which the carbon atom has a considerable +ve
charge.
 –
R — CH 2 Cl Al Cl3
These complexes are so carbocation like that they also undergo typical carbocation rearrangements.
Friedel-Crafts alkylations are not restricted to the use of alkyl halides and AlCl3 . Many other
pairs of reagents that form carbocations (or carbocation like species) may be used as well. These
possibilities include the use of a mixture of an alkene and an acid.
CH(CH3)2
OC
 CH3 — CH  CH 2 
HF

propene
Isopropyl benzene
A mixture of an alcohol and an acid may also be used.
60 C
 HO 
BF3

FRIEDEL - CRAFTS ACYLATION
The group is called an acyl group and a reaction whereby an acyl group is introduced into a
compound is called an acylation reaction.
The Friedel-Crafts acylation reaction is an effective means of introducing an acyl group into an
aromatic ring. The reaction is often carried out by treating the aromatic compound with an acyl
halide.

O CH2 CH3
 H3C  HCl
Cl  
AlCl3
Acyl chlorides (also called acid chlorides) are early prepared by treating carboxylic acids with
thionyl chloride ( SOCl2 ) or phosphorous pentachloride ( PCl5 ).
H3C OH H3C Cl
 SOCl 2 
 80 C
 SO 2  HCl
O O
Friedel-Crafts acylations can also be carried out using carboxylic acid anhydrides. eg.
O C CH3
O
H3C
O    H3C OH
AlCl3

H3C
Mechanism
In most Friedel-Crafts acylation reactions the electrophile appears to be an acylium ion formed
from an acyl halide in the following way.
O O
Step I
R C Cl  AlCl3  
 R C Cl – AlCl3
O
R C Cl — AlCl3  
 R C O  AlCl4
Step II
R —CO
H R
Step III
R — C  O 
 O
R
H R
O
Step –IV
O  AlCl 4 
  HCl  AlCl3

R R
O O — AlCl3
Step-V
 AlCl3  

In the last step, AlCl3 (a Lewis acid) forms a complex with the ketone (a Lewis base). After the
reaction is over, treating the complex with water liberates the ketone.
R R
O AlCl3  2H 2 O 
 O  Al (OH)3  3HCl
C6 H5 C6 H5
Limitations of Friedel - Crafts Reactions
Several restrictions limit the usefulness of Friedel-Crafts reactions.
1. When the carbocation formed from an alkyl halide, alkene, or alcohol can rearrange to a more
stable carbocation, it usually does so, and the major product obtained from the reaction is usually
the one from the more stable carbocation.
H
H 3C Br  
AlCl3
 H 3C  H 3C
CH 2 BrAlCl 3  
– AlCl3 Br
 CH 3
–AlCl3 –H 
–HBr
H 3C CH CH 2 CH 3
H2C CH 2 CH 2 CH 3
major
minor
2. An aromatic ring less reactive than that of halobenzene don’t undergo Friedal Craft’s reaction.
Aromatic ring containing - NH2 , –NHR,  NR2 , groups does not undergo friedal craft’s alkylation
due to formation of anilinum complex which is meta directing and has more electron withdrawing
power than halogen in benzene ring.
H H
+
H N H N AlCl3
 AlCl3 

meta directing group and

does not go Friedal
Craft's reaction

3. Aryl and Vinylic halides cannot be used as the halide component because they do not form
carbocations readily. Cl
No reaction
 
AlCl3

No reaction
Cl
4. Polyalkylations often occur - Alkyl groups are electron releasing groups, and once one is introduced
into the benzene ring it activates the ring towards further substitution.
CH(CH3)2 CH(CH3) 2
H3C
CHOH 
BF3
 60 C 
H3C 24% Isopropyl benzene
CH(CH3) 2
14% diisopropylbenzene
REACTIONS OF ALKYL BENZENES
HALOGENATION OF THE SIDE CHAIN: The side chain halogenation of alkyl benzenes takes place in
the presence of light or high temperatures. Side chain halogenation is mostly carried out by
using the reagent N-bromosuccinimide (NBS) in the presence of light.
CH3 O CH2Br
| || |
h
+ NBr CCl4
|| Benzyl bromide
O
An alkyl benzene with side chain other than methyl may lead to the formation of more than one
products.
CH – CH3
CH2CH3 |
| Br
Br2 (I)
Heat, light
CH2 – CH2Br
(II)
Order of stability of free-radials.

Allyl > Benzyl > 3° > 2° > 1° > CH3  vinyl (from bond dissociation energy data).

Oxidation of side chain: Although benzene itself is not susceptible to oxidation but side chain attached
to the benzene ring undergoes oxidation and converts itself into a –COOH group. Oxidation of side
chain takes place after substance is heated for a long time with KMnO4.
R COOH
| |
KMnO 4
 
The above reaction can be used for identifying substitution pattern in aromatic compound. If any
compound gives pthalic acid on heating with KMnO4, then we can infer that it is ortho disubstituted
benzene.
CH3
R COOH |
| R | H3C – C – CH3
COOH
KMnO 4
|
 

Neutral KMnO4
 No reaction
There is no reaction because of the absence of a benzylic hydrogen.
Illustration 3 : Find the product
CHO

KMnO 4
Product?
COOH
Solution:

KEY CONCEPTS
1. Huckel rule: Compound having 4n + 2 delocalized  electrons is called aromatic compound where
n must be zero or any wholenumber.
2. Benzene and some heterocyclic compound i.e. pyrrole, furan, thiophene and pyridine also exhibit
aromaticity.
3. Aromatic compound have a tendency to give electrophilic aromatic substitution reaction.
4. General electrophilic aromatic substitution reaction:

CH3
NO2

HNO3 /H2SO4
(P)

H3C
CH3
Cl Cl

Cl2 /Fe
(Q)
H3C
Cl
CH3
CH3

H2S2 O7
(R)

H3C
SO 3H
H3C CH3
CH2CH3


CH3 CH2 Cl/ AlCl3
(S)
H3C
CH3
Br Br

Br2 /FeBr3
(T )
H3C
Br
CH3 O
R

RCOCl/ AlCl3
(U)

H3C
5. In Friedel-Craft reaction, generally AlCl3 give rearranged product while FeCl3 give unrearranged
product.
6. Friedel-Crafts reaction do not occur when powerful electron with-drawing groups for example
NO2 is present.

7. The amino groups –NH2, –NHR and NR2 changes into powerful electro-withdrawing groups by
the Lewis acids used to catalyze Friedel-Crafts reactions.
8. Nitro benzene is better solvent for Friedel-Crafts reaction rather than benzene due to less reactivity.
Due to strong withdrawing effect.
9. In case of nitration HNO3 behave as base while H2SO4 behave as an acid.
10. In case of Sulfonation all steps are reversible. (Deprotonation step is the slow rate-determining
step).
  
11.  OH,  R,  OR,  NH2 are called activating group and ortho-para director..
 
12. —NR3+, —NO2, —CN, —SO3H, —COOH, —CHO,
R O
—X etc. are called deactivating group and except halogen all group are meta director.
13. The side chain halogenation of lakyl benzene takes place in the presence of light or high temperatures.
14. In case of oxidation of side chain there must be benzylic hydrogen on benzene.

CONCEPTUAL QUESTIONS
1. In which of the following molecules, the substituent does not exert its resonance effect

(A) C6H5NH2 (B) C6H5 NH3 (C) C6H5OH (D) C6H5Cl
2. Which of the following species would be expected to exhibit aromatic character?
(I) (II) (III) (IV)
(A) I and IV (B) II and IV (C) I and III (D) II and III
3. When Nitrobenzene is treated with Br2 in presence of FeBr3, the major product formed is m-
bromonitro benzene. Statements which are related to obtain m-isomer are:
(A) The electron density on meta carbon is more than that on ortho and para positions.
(B) The intermediate carbonium ion formed after initial attack of Br+ at the meta position is least
destabilized.
(C) Loss of aromaticity when Br+ attacks at the ortho and para positions not at meta position
(D) Easier loss of H+ to regain aromaticity from the meta position than from ortho and para
positions.
4. Terepthalic acid is obtained by oxidation of which of following compounds?

CH3
CH3 CH3 CH3
CH3
(A) (B) (C) (D)
CH3
CH3
5. The most basic compound among the following is:

(A) Benzylamine (B) Aniline (C) Acetaniline (D) p-nitroaniline

SINGLE CORRECT ANSWER TYPE
LEVEL - 1
1. A group which deactivates the benzene ring towards electrophilic substitution but directs the
incoming group towards o- and p- positions is
(A) –NH2 (B) –Cl (C) –NO2 (D) –C2H6
2. Which one of the following compounds will be most easily attacked by an electrophile?
Cl OH CH3
(A) (B) (C) (D)
3. Which of the following groups is ortho and para directing?

Cl CH3
(A) (B) –– CHO (C) –– OH (D)

O O
4. Among the following compounds, the decreasing order of reactivity towards electrophilic substi-
tution is
C H3 O CF 3
H3C
I II III IV
(A) III > I > II > IV (B) IV > I > II > III (C) II > I > IV > III (D) I > III > II > IV
5. In which of the following case, the rate of Electrophilic Aromatic Substitution will be fastest.
H CH3
CH3 CH3
H3C CH3 H3C CH3
(A) (B) (C) (D)
6. Which of the following is the most reactive towards electrophilic aromatic substitution?
CH3
O O NH2 OH
(A) (B) (C) (D)

7. Arrange the following in order of increasing rate of nucleophilic substitution

F Cl Br I
(I) (II) (III) (IV)
(A) I  II  III  IV (B) II  III  IV  I (C) IV  III  II  I (D) IV  III  I  II

8. Which of the following will show aromatic behaviour
(a) (b) (c) (d)
9. Electrophile involved in the nitration reaction of benzene by nitrating is

 
(A) NO 2 (B) NO (C) NO3 (D) NO
2
10. Which of the following is the major organic product of the following reaction?
H3C
 
AlCl3
?
H3C Cl
CH3
H3C
CH3 CH3
(A) CH3 (B) CH3 (C) (D)

CH3
CH3
11. Which of the following is correct for the mononitration of phenyl benzoate?
COO
O
O
O
O
NO 2
(A) (B)
NO 2

COO
(C) (D) COO

NO 2
H3C
12. The reaction of OH with HBr gives:
CH3 CH3
Br
(A) OH (B) OH
Br
CH3 CH3
Br
(C) Br (D) Br
Br
13.  (CH 3CO) 2 O 

BF3
P, P is
O
O
O
O CH3 O
(A) CH3 (B) (C) O (D) CH3
O
O CH3 O
O O
14. Benzene on reaction with ICl in presence of anhydrous AlCl 3 gives?

I
Cl
(A) Cl (B) I (C) (D)
I Cl
15. Which of the following species is aromatic?
CH2


(A) (B) (C) (D)

N:
16. Imidazole N has following number of basic sites.

H
(A) Two (B) Three (C) One (D) None of these.
17. Which of the following compound is the least soluble in water?
(A) Phenol (B) Benzene (C) Ethanol (D) Benzoic acid.
18. Which does not burn with a sooty flame:
(A) C6H5 OH (B) C6H5NH2 (C) C6H5 CH2 OH (D) C6H6 .
CH3
19. 
conc. H 2SO 4
conc. HNO3
 A, 'A' is
CH3
CH3
CH3
NO2
(A) (B)
CH3
CH3
NO2
CH3 CH3
NO2 O2N NO2
(C) (D)
CH3 CH3
NO2 NO2
20. In which case, SE will not be in meta position?
(A) CF3 (B) N(CH3)3
O
(C) CCl3 (D) NH C CH3

21. Cyclo octatetraene is:

(A) aromatic (B) antiaromatic (C) nonarmoatic (D) None of these.
22. Cyclo octatetraene is nonaromatic because:
(A) it is planar (B) it shown electrophilic addition reaction
(C) it is a tub-shaped molecule (D) all of these.
23. For a compound to be aromatic, which of the following is/are true:
(A) Obey(4n + 2) electron Huckel rule
(B) Molecule must be planar with sp2 hybridisation
(C) High resonance energy (D) All of these.
24. Nitrobenzene used as solvent in Friedel-Crafts reaction because:
(A) it cannot undergo F.C.R.
(B) it forms stable acid-base complex with Lewis acid so it is inert towards F.C.R.
(C) F.C.R. electrophiles are not good enough to attack on the highly deactivated ring.
(D) all of the above.
25. What is the value of n in Huckel’s rule, when a compound has 9 pairs of electrons?
(A) 4 (B) 6 (C) 2 (D) 1
LEVEL - 2
H3PO4
26. + CH3–C=CH2 ‘A’ ‘A’ is
CH3 CH3
CH3–CH–CH3
CH2–C–CH3 CH3–C–CH3
(A) H (B) (C) (D) none of these
27. Which is the most reacting towards electrophilic substitution reaction?
NO2 Cl
(A) (B) (C) (D)
28. Write the major product of the following reaction:

H5 C6
 
1. Br2 , heat, light
2. NaCN
?
CH3
CH3
H3C (o)NC C 6 H4 m-NC C6 H4
(A)H5 C6 (B) (C) (D) CH3
CN CH3
CN

29. Among the following compounds (I – III), the correct order in reaction with electrophile is
NH2 CHO
(I) (II) (III)
(A) II  III  I (B) III  I  II (C) I  II  III (D) I = II  III

30. Identify the correct order of reactivity in electrophilic substitution reactions of the following
compounds:
CH3 Cl NO2
1 2 3 4
(A) 1 > 2 > 3 > 4 (B) 4 > 3 > 2 > 1 (C) 2 > 1 >3 > 4 (D) 2 > 3 > 1 > 4
31. Which of the following not aromatic
(A) (B) (C) (D)

+
32. The treatment of benzene with isobutene in the presence of sulphuric acid gives
(A) isobutyl benzene (B) tert-butyl benzene (C) n-Butyl benzene (D) No reaction
33. Which of the following compounds will be most easily attacked by an electrophile?
NO 2 Cl NH2 CH3
(A) (B) (C) (D)
34. In Friedel Craft’s alkylation, besides AlCl3, the other reactants are
(A) C6H6 + NH2 (B) C6H6 + CH4 (C) C6H6 + CH3Cl (D) C 6 H 6 +
CH3COCl
35. The correct order of C – C bond lengths in benzene (I), ethane (II), ethylene (III) and acetylene
(IV) is
(A) II  III  IV  I (B) IV  III  II  I (C) II  I  III  IV (D) IV  III  I  II
36. Which of the following undergoes electrophilic aromatic substitution at the fastest rate?
O
(A) (B)

O O
(C) O (D)

Ph – NH2   A   B   C, C is
HNO HF
37. 0o C
2
BF3
(A) Ph  N  N BF4

(B) F
(C) F F (D) Ph – F
38. In the reaction sequence
NH2

   
NaNO 2 /conc. HCl
0o C

NaNO 2 /Cu
 (B) 
Sn/HCl
 (X)
(X) will be
NO2 NH2 F HN NH
(A) (B) (C) (D)
NHCOCH3
 
H3 O , 
  
NaNO2 /HCl
 
KNO2 /Cu
39.
NO2
Cl NH2 NO2
NO2
(A) (B) (C) (D)

NO2
NO2 NO2 NO2

40. In the given reaction sequence
Br
X 
Br2 /H2O
 Y 
NaNO2 /HCl
 Z 
C2H5OH


Br Br
(X) will be:
(A) Benzoic acid (B) Salicylic acid (C) Phenol (D) Aniline
LEVEL - 3
41. The three tribomobenzenes can be identified by the korner method.The number of mononitro
products of I, II and III tribromobenzenes are respectively.
Br Br Br
Br Br
Br Br Br
Br
1, 3, 5-Tribromobenzene 1, 2, 3-tribromobenzene 1,2, 4-tribromobenzene
(I) (II) (III)
(A) 1, 2, 3 (B) 3, 2, 1 (C) 2, 1, 3 (D) 1, 3, 2
42. 
Cl2 /Fe
(A) 
HNO3
H2 SO4
(B) 
HNO3
H2 SO4
(C) 
NaOH

 (D) 
HNO3
H2 SO 4
(E)
The compound (E) is:

Cl Cl
O 2N NO 2 HO NO2
(A) (B)
NO 2 NO2
OH OH
Cl NO 2 O2N NO2
(C) (D)
NO 2
NO 2 NO2

43. Amongst the following which one will undergo the fastest SN reaction?
Cl Cl Cl
Cl
(A) (B) (C) (D)

Me Me
NO2
NO2 NO2 NH2
CN

(CH3 )2 NH
Cu2O, 
 The product is
44.
NMe2 CN CN NMe2
NMe2
(A) (B) (C) (D)
NMe2 NMe2 F F
45. In which case SN2 Ar reaction is the fastest?
Cl Br Br
Cl NO2 NO2
(A) (B) (C) (D)
NO2 NO2 NO2

46. Identify the product in the following reaction
Cl
NO2
C6H5 CH2 SK, 

(1 eq)
Br
CH3
SCH 2 C 6 H 5 Cl
NO 2
(A) (B) C H CH S
Br NO 2 6 5 2
CH 3 CH 3

SCH 2 C 6 H 5 Cl
NO 2 C 6 H 5 CH 2 S NO 2
(C) (D)
Br Br
CH3 CH 3
47. The final product of the following reaction is

NO2
O 2N X H N
NO2
N
O 2N
(A) N (B) O2N X
NO2
NO 2 NO 2
(C) N X (D) O 2 N N X
H
CH3
(i) aq. Na 2 CO3

48.   
Cl2 /hv ( excess )
 (X)  
(ii) H
 (Y) . The product ‘Y’ is:
SO 2 H
CCl3 COOH
(A) (B) (C) (D)
SO 2H SO2H SO 2H

49. Compounds Z and S are
O
Br2

FeBr2
 X 
Mg
Et 2 O
 Y 
1.
H
Z

NBS.  tert BuO

CH3 CH2Br
AlCl3
P   Q  R 
1. BH3 /THF
2. HO , H O , H O
S
2 2 2
(A) Isomers (B) Identical

(C) Homologs (D) Have different functional group
Br C CNa
50 . 
  2


Hg / H 3 O / 
 Product is
NO 2
(A)Br NO2 (B) Br OH
NO2
C
O
(C) (D)
Br

MULTIPLE CORRECT ANSWER TYPE
LEVEL - 1
1. Cyclic hydrocarbon molecule ‘A’ has all the carbon and hydrogen in a single plane. All the
carbon-carbon bonds are of same length less than 1.54Å (C–C), but more than 1.34Å (C–C).
The C=C bond angle will be
(A) 10928 (B) 100 (C) 180 (D) 120
2. p-Chlorotoluene on nitration gives
Cl Cl Cl
NO2
(A) (B) (C) (D)

NO 2 CH3
CH3 CH3 NO2
Cl
O2N CH3
CH3
3. The E will attack which ring in the following compounds and what is the rate of ESR in this?
O O
C O C O
(Y) (Q)
(X) (P)
(A) (B)
(A) In A, ring X will take part in electrophilic substitution reaction
(B) In A, ring Y will take part in electrophilic substitution reaction
(C) In B, ring Q will take part in electrophilic substitution reaction
(D) Compound B is more reactive than compound A
4. In the reaction sequence given below

CH2 X
CH2 CN

 P
S 
SnCl2 / HCl
 Q 
H 2 O/ H
R
CH2NC

 

OH / H 2 O
D

OH
(A) P, Q and R are respectively AgCN; CHO
; HC
OH
CH2CH NH ; CH2CHO
(B) P, Q and R are respectively AgCN;
(C) S and D are respectively AgCN and None
CH 2NH2
(D) S and D are respectively AgCN and + HCOOH
CH3
ozonolysis
5. Products ; The products formed are
CH3
O O O
(a) CH3 C CHO
(B) CHO – CHO (c) CH3 C (D) HCOOH
C CH3
6. Benzyl chloride (C6H5CH2Cl) can be prepared by chlorination with
(A) SO2Cl2 (B) Cl2 (C) SOCl2 (D) NaOCl
7. The major products of the following bromination reaction
Br2 ,h

400  600 C

CH3
Br
(A)Br (B)
CH3
CH3
CH3
(C) (D)
Br Br
8. Isopropylbenzene can be prepared by
CH3
Benzene + H3C  
(A)
H2SO 4
(B) Benzene + H3C 
H2SO 4

CH2
Cl
CH3

AlCl3
 Benzene + H3C 
AlCl3

(C) Benzene + H3C (D)
Cl Cl

9. The reaction of biphenyl with HOCl in the presence of a strong acid gives
Cl Cl
(A) (B)
Cl
(C) Cl (D) Cl
10. The meta directing groups among the following are :

(A) –COOH (B) –CN (C) –COCH3 (D) –NHCOCH3
11. Which of the following groups are ortho and para-directing?

(A) – OH (B) – CHO (C) – CN (D) – NHCOCH3
12. Which of the following explains aromatic character of benzene?

(A) It has 6  electrons
(B) It is planar and has conjugated double bonds
(C) It has 4  electrons
(D) It has high resonance energy
13. Whiich of the following is an electrophilic substitution reaction?
SO3H
(A) + H2SO4+SO3 + H2O

conc.
Cl
Cl Cl
hv
+ 3Cl2
(B) conc.
Cl Cl
Cl
NO2
(C) conc. H2SO4

+ HNO3 + H2O
conc.
CH3–CH–CH3
(D) +CH3–CH = CH2

H2PO4

14. Which of the following are electrophiles?

(A) SO 3 (B) –COCH3
(C) H 3O +
(D) (CH3)4N+
15. Tulene can be prepared by

(A) heating sodium salt of p-toluic acid with soda lime
(B) distillation of m-cresol with Zn dust
(C) treating phenyl magnesium bromide with methanol
(D) reduction benzyle alcohol with HI and red P.
LEVEL - 2
16. m-Nitrobenzoic acid can be obtained by

[O] HNO
(A) toluene 
KMnO4
 A  3
H2 SO 4

[O] HNO [O]

(B) toluene 
CrOCl2
 A  3
H2SO 4
 B 
KMnO4

nitration [O]
(C) toluene 
HNO3 H2 SO 4
 A 
KMnO4

(D) all these methods
17. The necessary conditions for halogenation of benzene are

(A) low temperature (B) darkness
(C) the presence of a halogen carrier (D) I2 + conc. HNO3
18. Benzene can undergo

(A) substitution (B) addition
(C) elimination (D) oxidation
19. Iodobenzene can be obtained by

HNO3
(A) C6H6  I2  (B) C6H6  I2 
(C) C6H5N2 Cl  KI  (D) C6H6  HI 
20. Toluene, when treated with Br2/Fe, gives p-bromotoluene as the major product because the –
CH3 group
(A) is ortho - para directing (B) is meta directing
(C) activates of the ring by hyperconjugation (D) deactivates the ring
21. Ethylbenze can be prepared from

(A) acetophenone with Zn(Hg) and conc. HCl
(B) acetophenone with NH2NH2, KOH and ethylene glycol.
(C) benzene reacts with C3H5Cl in presence of AlCl3
(D) toluene reacts with CH3Cl in presence of AlCl3

22. Which of the following are more reactive towards electrophilic then that of benzene
NO2 OH O
CHO
NH–C–CH3
(A) (B) (C) (D)
C2H5
Me
23. NBS Mg ether (1) H C
A B
(2) H+
Hence
Br MgBr
(A) A = C2H5 (B) B = C2H5
H OH H OH
(C) C = CH3 (D) C =

C2H5 C2H5 CH3
24. When is reacted with conc. H2SO4 and heated then the intermediates and products
OH
formed are
(A) (B)
(C) (D)

25. Which of the following statement(s) is/are correct about benzene?

(A) It burns with sooty flame
(B) It undergoes electrophilic substitution reaction
(C) Its resonance energy is 36 kcal mol–1
(D) It is highly unstaturated and deecolourises bromine water.
LEVEL - 3
26. Which of the following substituted benzene derivatives would furnish three isomers when one
more substitution introduced?
Br
Br Br
Br
(A) (B) (C) (D)

Br
Br
Br
OH

NaNH 2
liq. NH 3
[Intermediate] 
NaNH 2 / liq.NH 3
Pr oduct
27.
Br
Choose the correct statement (s)
OH
(A) is formed (B) Intermediate formed is aromatic

NH2
OH
is formed involving non-aromatic intermediate

(C)
NH2
is also formed
(D)
OH OH

28. Which of the following are aromatic:
(A) (B) (C) H

H
2–
(D)
29. Which of the following heterocyclic compound/s might be aromatic?
(A)
NH (B)
BH (C) (D) B H
O
30. The compound

X
(where X is an O – P, directing group and Y is m-directing group)

is subjected to electrophilic substitution reaction for introduction of Z. The compound formed
would be
X
X
X
Z
(A) (B) (C) (D) Both (B) and (C)
Y
Z Y Y
Z

COMPREHENSION TYPE QUESTIONS
Comprehension - I
A third group is least likely to enter between two groups in the meta relationship. This is the
result of steric hindrance and increases in importance with the size of the groups on the ring and
with the size of the attacking species.
When a Meta-directing group is meta to an ortho-para directing group, the incoming group primarily
goes ortho to the meta directing group rather than para.
1. Chlorination of m-chloro nitro benzene gives
NO2
NO2 NO2 NO2
Cl
(A) Cl
(B) (C) (D)
Cl Cl Cl Cl Cl
CH3
OH

2. 
E

CH3
CH3 CH3 OH
OH OH
(A) (B) (C) (D) (A), (B)
E E
E
HN CH3
3.

Cl2 / CH3COOH

O O O O
HN CH3
HN CH3 HN CH3 HN
Cl Cl
(A) (B) (C) (D)
Cl Cl
CH3
4. 
HNO3
H 2SO 4

NO2
CH3 CH3
CH3 CH3
NO2 O2 N
(A) (B) NO2 (C) (D)
NO2 NO2 NO2 NO2

Comprehension - II
The typical reaction of benzene and other aromatic compounds are electrophilic substitution.
Presence of electron donating group activates the ring towards electrophilic substitution, while
presence of electron withdrawing group deactivates the ring towards electrophilic substitution
but at the same time activates the ring towards nucleophilic substitution. Some groups are
predominantly meta-directing and all of these are deactivating. Except halogen, most of the O–
and P– directing groups are activating groups.
COCH 3
H3C CH3
5. Conc. H 2 SO 4
(A)
(A) is
H3C
COOH COOH
CHOH
HOOC COOH H3 C CH3 H 3C CH3
(A) (B) (C) (D)
H3C CH3
C 2 H 5 Cl, AlCl 3
6. (A)
A is trisubstituted benzene. The structure of A is

C2H5
C2H5 C2H5
C 2 H5
(A) (B) C 2H 5 (C) (D)

H5C2 H5C2 H5C2 C2H5
CH2CH2CH2CH3
7. Among the three isomers shown below

HO HO HO
COOH
and
,
OH HO COOH
HOOC OH
(I) (II) (III)
Which one is correct increasing order of ease of decarboxylation in acid

(A) II < I < III (B) I < II < III (C) II < I < II (D) II < III < I
8. Which of the following compound is not formed.
CH 2 CH 3
(i) NBS, CCl 4

(X)
(ii) NaOEt, EtOH,
(iii) Br 2 /FeCl 3

X represents mixture of organic compounds. The mixture does not contain.

CHBrCH 2 Br HC CH 2
CHBrCH2Br CHBrCH2Br
Br (c) (d)
(a) (b)
Br Br
Comprehension - III
It is not always easy to predict the position of attack on multiple substituted benzene. If the
benzene ring bears different ortho/para directing group at the 1 and 4 positions, the position of
further substitution is not immediately clear. Sometimes steric effects determine the outcome. In
other cases, electronic factors determine the outcome, and further reaction will be at the position
activated by the more strongly activating group.
Some substituents are so strongly activating that no catalyst is needed, and it is often difficult to
stop substitution after mono substitution. Mild conditions are needed to restrict the reaction to
mono-substitution.
It is possible to reduce the activity of such groups (by side chain reaction) so that the reaction
can be stopped after mono substitution then and again by a side chain reaction the original group
is restored. Effective use can sometimes be made of removable blocking groups on the ring.
9. Which of the following synthesis could not be done without involving blocking position on the
ring?
OH OH OH OH
Br Br
(A) (B)
Br Br
NH2 NH2
OH OH
Br
(C) (D)
Br
10. Which of the following is not the correct major product?
CH3 CH3 O
OH OH CH3
O
||
CH3  C  Cl
CH3
CH3  
(A) 

(CH 3 )2 CHBr (B) AlCl3 ,CS2 5 C
AlCl3 ,15 25 C
CH3 CH3 H3C CH3 H3C CH3
NH2 NH2 OH OH
Br Br Br Br
(C) 
Br2 .H 2 O
40 50 C
 (D) 
 Br2
CS2 0o C
OH O
O Br OH Br

MATRIX - MATCH TYPE QUESTIONS
1. Match the following

Column – I Column - II
A) Cyclic conjugated polyenes (p) Arenes and alkyl halides in
with (4n + 2)  -electrons presence of anhydrous AlCl3
B) o-dichlorobenzene does not (q) Aromatic compounds
exist as two isomers
(C) Friedel crafts reaction (r) Delocalization of  -electrons
(D) Meta directing group (s) Deactivates the ring towards
electrophilic substitution
2. Match the following
3. Match the column

Column – I Column – II
Me
(a)
(p) meta position is more deactivated
Me
NO2
(b) (q) ortho with respect to methyl group

NO2
NO2
(c)
(r) only one mono substituted product
Me
NO2 OH
(d) > (s) meta with respect to NO2

ASSERTION - REASON TYPE QUESTIONS
(A) Statement – 1 is True, Statement – 2 is True; Statement – 2 is a correct explanation for

Statement – 1.
(B) Statement – 1 is True, Statement – 2 is True; Statement – 2 is NOT a correct explanation
for Statement – 1.
(C) Statement – 1 is True, Statement – 2 is False.
(D) Statement – 1 is False, Statement – 2 is True.
1. STATEMENT – 1: Cyclobutane is less stable than cyclopentane.

STATEMENT – 2: Presence of bent bonds causes loss of orbital overlap.
2. STATEMENT – 1:Benzene is a solvent for the Friedel Craft’s alkylation of bromobenzene.

STATEMENT – 2:Friedel Craft’s reaction is used to introduced alkyl or acyl group in benzene
nucleus.
3. STATEMENT – 1: Nitration of toluene is easier than benzene.

STATEMENT – 2: The methyl group in toluene is electron releasing.
4. STATEMENT – 1: Tropylium cation + is aromatic in nature
STATEMENT – 2: The only property that determines its aromatic behaviour is its planar
structure.
5. STATEMENT – 1: Benzene does not decolourise alkaline KMnO4.

STATEMENT – 2: Benzene is stabilized by resonance and  -electrons are delocalised.

INTEGER ANSWER TYPE QUESTIONS
CH3
1. How many products are formed by the nitration of compound ?
CH3
2. How many methods can be used for the preparation of the isopropyl benzene ?
(i) Benzene + CH3 H2SO4
CH2
CH3
(ii) Benzene + CH3 H2SO4
Cl
CH3
(iii) Benzene + CH3 AlCl3
Cl
AlCl3
(iv) Benzene + CH3
Cl
CH3
H SO
(v) Benzene + H3C C CH2 
2 4

3. Out of the following how many groups are meta directing ?

(i) -COOH (ii) - CN
(iii) -COCH3 (iv) -NHCOCH3
4. How many methods can be used for the preparation of iodobenzene ?
HNO3
(i) C6H6+ I2 (ii) C2H6+ I2
(iii) C6H5N2+Cl– + K I (iv) C6H6 + HI
5. How many species would be expected to exhibit aromatic character ?
(–) (+)
(–) (+)
I II III IV

SUBJECTIVE QUESTIONS
1. What would be the major product in following reaction?

O
N 
1 eq.Br2 / Fe
?
2. When benzene is treated with DCl at low temperatures a compound C6H6DCl, is formed. On
warming the reactants, C6H6 and DCl are re-formed. However, in the presence of AlCl3 an
isomer of C6H6DCl(D) is produced, which on warming, gives mainly C6H5D and HCl. Explain
3. Account of the following
Br
Ph Ph
h
CH3  1 eq. Br2   CH3
H3C H3C
with little or no PhCH2C(Br)(CH3)2 formed.

H5 C6
CH3   A 

B
alc. KOH HBr
4. heat
Br
5. Oxidation of toluene by acidic KMnO4 gives poor yield of benzoic acid while oxidation of p-
nitrotoluene gives good yield of p-nitrobenzoic acid. Why?
6. What happens when p-xylene is treated with concentrated sulphuric acid and the resultant product
is fused with KOH?
CH3
7. 
conc. HNO3 – conc. H 2SO 4
 In the above reaction which product is most likely to be formed?
NO 2
8. Give the products of the following reactions
N F F
a) b)
 Br2 
  Cl2 
anhy.FeCl3

9. A compound (C8H10O) upon treatment with alkaline solution iodine gives a yellow precipitate.
The filtrate on acidification gives a white solid E (C7H6O2). Write the structures of D, E and
explain the formation of E.

10. Give the product(s) obtained from the reaction each of the following compounds with Br 2/FeCl3.
NO2
a) b)
O
H3C O
11. Write the structures of the compounds from the following data.
Ph
a) CH3  Br2 (A) 
hv
(B)  (C) 
alc. KOH cold dil
(D) hot
KMnO 4 KMnO 4
Ph H
b)  Br2  FeBr3 (anhy.) 

(E) HBr

peroxide
(F)
H CH3
H3C
CH3
Br H3C
12. CH3
 Br2 
AlBr3
 CH2  HBr

H3C
13. Compounds (A) and (B) are isomers having the formula C8H10. On oxidation (A) gives benzoic
acid while (B) gives phthalic acid which forms an anhydride (C) on heating. Identify (A), (B) and
(C).
14. How will you synthesize
CH3
from benzene?
15. Identify A to C in the following:

CH3
alkaline
 KMnO4
ALiAlH
 4
Bconc.
 HCl
ZnCl, 
C
16. Complete the following reactions:

a) 4-bromo-2-methylphenol treated with 2-methylpropene and sulphuric acid.
b) p-cresol treated with propanoyl chloride and aluminium chloride.
c) 2,5-dichlorophenol reacts with chlorine in acetic acid.

PREVIOUS YEAR IIT - JEE PROBLEMS
1. In the reaction p-chlorotoluene with KNH2 in liq. NH3, the major product is
(A) o-toluidine (B) m-toluidine [1992]
(C) p-toluidine (D) p-chloroaniline
2. Product on monobrominationof this compound is [2004]

H O
N
H 3C CH 3
Fe / Br 2
H O H O
N N
H 3C CH 3 H 3C CH3
(A) (B)
Br Br
H O H O
N N
H 3C CH 3 H 3C CH3
(C) (D)
Br Br
More than one options are correct
3. An aromatic molecule will [1999]
(A) have 4n  -electrons (B) have (4n + 2)  -electrons
(C) be planar (D) be cyclic
AlCl3 (i) O2/

4. + Cl – CH2CH2–CH3 P +
Q + Phenol
(ii) H3/O
The major products P and Q are [2006]
(A) and CH3CH2CHO (B) and CH3COCH3
(C) and CH3COCH3 (D) and CH3CH2CHO

Subjective Questions
5. Write the structure of the major organic product expected from the following reaction [1992]
AlCl3
+(CH3)2 CHCH2Cl
6. Predict the major product in the following reactons: [1994]

H2SO 4
(i) C6H6  (CH3 )2 CHCH2OH   .....
1. Br2 ,beat, light
(ii) C 6H5 C 2H5      .....
2. NaCN
7. Give reasons for following in one or two setences: [1998; 2M]

“Nitrobenzene does not undergo Friedal Craft’s reaction”.
8. 7-bromo-1, 3, 5-cycloheptatriene exists as ionic species in aqueous solution while 5-bromo-1, 3

cyclopentadiene doesnot’ ionise even in presence of Ag+(aq). Explain. [2004; 2M]
9. Given reasons: [2005]

H3C
Br
(A) (i) CH3

C2H5OH(aq)
acidic solution
CH3
(ii) Br
C2H5OH(aq)
neutral
CH3
F
NaOH (aq)
F (liberated)
(B) (i) O2N
CH3
F
NaOH
F is not liberated
(ii)
CH2NO2

ANSWER KEY
1. (B) 2. (D) 3. (B) 4. (C)
5. (A)

LEVEL - 1
1. (B) 2. (C) 3. (C) 4. (A)
5. (A) 6. (A) 7. (A) 8. (B)
9. (B) 10. (B) 11. (A) 12. (B)
13. (B) 14. (B) 15. (A) 16. (C)
17. (B) 18. (D) 19. (B) 20. (D)
21. (C) 22. (C) 23. (D) 24. (D)
25. (A)
LEVEL - 2
26. (B) 27. (A) 28. (A) 29. (C)
30. (C) 31. (C) 32. (B) 33. (C)
34. (C) 35. (C) 36. (D) 37. (D)
38. (B) 39. (D) 40. (D)
LEVEL - 3
41. (A) 42. (D) 43. (B) 44. (B)
45. (B) 46. (C) 47. (D) 48. (B)
49. (B) 50. (C)
LEVEL - 1
1. (D) 2. (A), (B) 3. (B), (C), (D) 4. (B), (C)
5. (A), (B) 6. (A), (B) 7. (D) 8. (A), (B), (C), (D)
9. (A), (C) 10. (A), (B), (C) 11. (A), (D) 12. (A), (B), (D)
13. (A), (C), (D) 14. (A), (B) 15. (A), (B), (D)
LEVEL - 2
16. (A), (B) 17. (C) 18. (A), (B), (C) 19. (B), (C)
20. (A), (C) 21. (A), (B), (C) 22. (B), (C) 23. (A), (B), (D)
24. (A), (B), (C), (D) 25. (A), (B), (C)
LEVEL - 3
26. (A), (C) 27. (A), (B) 28. (C) 29. (B), (C)
30. (B), (C)
COMPREHENSION TYPE
1. (D) 2. (D) 3. (C) 4. (B)

5. (D) 6. (C) 7. (A) 8. (D)
9. (D) 10. (A)
MATRIX MATCHING TYPE
1. (A – q,r); (B – q,s); (C – p); (D – s) 2. (A – p); (B – q); (C – s); (D – t)

3. (A – q, r); (B – p, r, s) (C – q, r);(D – p, s)
ASSERTION REASONING TYPE

1. (A) 2. (D) 3. (A) 4. (C)
5. (A)
INTEGER ANSWER TYPE

1. 1 2. 4 3. 3 4. 2
5. 2

HINTS & SOLUTIONS
PREVIOUS YEAR IIT-JEE PROBLEMS
1. (B) 2. (B) 3. (B), (C), (D) 4. (C)

1. In C6H5 NH3 there is no lone pair electrons on the N- atom and hence it cannot exert its resonance
effect.
2. II and III have delocalized six  electrons and hence are aromatic.
3. The intermediate carbonium ion formed after initial attack of Br+ at the meta position is least
destabilized.
4. Terepthalic acid is a para dicarboxylic acid
5. Rest all show less tendency to donate electron pair due to resonance.

LEVEL - 1
1. Halogen acts as ‘+M’ group due to lone pair and ‘-M’ due to high EN
2. Due to hig activating nature
3. Electron releasing group
4. Electron releasing group order CH 3O   CH 3  CF3
5. High hyper conjugration
6. O- is strong activating group due to more electron density.
7. F is easily leaving group and creates +ve charge at carbon.
8. (B)
(1) molecule is planar.

(2) 6  electrons are present.
10. The product obtained by the more stable carbocation

11. Major is para and minor is ortho.
12. The benzylic carbocation is more stable.
13. Fridel-Craft acylation
 
14. When ICl is heated with AlCl3 I AlCl complex formation is more farourable than Cl AlCl3I
4
complex. So iodiobenzene is formed.

LEVEL - 2
26. (B) is correct because 3° carbocation is most stable.
H+ 
CH3–C = CH2 CH3–C – CH3
CH3 CH3
electrophile
CH3
CH3–C – CH2
]
+ (CH3)3C +H
+
(A) is not possible because 1° carbocation is less stable.
(C) is not possible because CH3 – 

CH – CH3 is not formed
(D) is ruled out
27. (A) Explanation : (B) is wrong because NO2 is a deactivating group.

(C) is wrong because Cl is a deactivating group.
In (D), one benzene deactivates the other, while in (A), there is neither activation nor deactivation,
hence is more electron rich than
Hence, (A) is correct and (D) is wrong.
28. C6H5CH2CH3  C6H5CH(Br) CH3  C6H5CH (CN) CH3
30. Electron releasing group increases the reactivity towards ESR.

31. Non planar non aromatic
C
|
32. Due to the formation of C  C  C

33. Strong Electron releasing group favour ESR effectively
34. Conceptual
35. C - C ------ 1.54 A0
C = C ------ 1.34 A0
C  C ------ 1.20 A0
Benzene ------ 1.39 A0

36.
is most powerful electrons donating group.
LEVEL - 3
41.
42. A = Chloro benzene; B = Para chloro Nitro benzene; C = O, P Di nitro chloro benzene; D = O,
P Di nitro phenol; E = 2, 4, 6 - tri nitro phenol.
43. Due to strong -M effect of NO2 at para position
44. F- is replaced by base
45. More the -M effect, faster the rate. Cl - creates more +ve charge and nucleophile attack is easy
46. Cl - is better leaving group than Br - in aromatic compunds
47. Aromatic nucleophilic substrtution reaction
48. FSR occurs at benzylic carbon followed by basic hydrolysis produces an acid.
49. X = C6H5 Br; Y = C6H5 MgBr; Z = C6H5CH2CH2 OH
P = C6H5 CH2 CH3 ; Q = C6H5 CH (Br) CH3 ; R = C6H5 CH = CH2 ; S = C6H5CH2CH2 OH
50.
Br C C Na
NaBr

 O 2N C C Hg2 , H
 O 2N CH C
OH
NO 2
O2N CH2 C


LEVEL - 1
3. In compound A, ring Y is both activated and deactivated while ring X is only deactivated, hence
Y is more electron rich than X and ESR takes place on Y ring.
In compound B, ring Q is both activated and deactivated while ring P is only deactivated.
In B, ring Q is attached to N. In A, ring Y is attached to O.
. .
N group is a stronger +R group than O
4.
CH 2 X (P)
CH 2 CN CH 2 CH CN

KCN
 CH 2 CHO
  
SnCl 2 / HCl
Stephen's  H 
2O / H


reduction
Q  R 
CH 2 X
CH 2 NC
 AgCN
S   H

 
2 O / OH
No hydrolysis
Hence (b) and (c) are correct while (a) and (d) are incorrect.
7. Benzyl free radical is more stable
8. C  C  C  Cl 
AlCl3
C  C  C  C  C  C
9. HOCl  HO   Cl  Electrophilic substitution
10. Conceptual
11. Conceptual
12. (A,B,D)
(A) and (B) are correct according to Huckel’s rule. (D) is correct because greater the resonance
energy, more is the stability.
(C) is not possible because benzene has three double bonds, therefore has 6 electrons and not 4
electrons.
13. (A,C,D)
(A) is electrophilic substitution reaction i.e., sulphonation because –SO3 in an electrophilie.

(C) is electrophilic substitution reaction because NO is an elecrophile.
2

(D) is Friedel-Crafts alkylation, i.e., elctrophilic substitution reaction because CH  CH CH is
3 3
an electrophile.
(B) is a free radical addition reaction.
14. (A, B)
O
(A) is an electrophile because oxygen is more electronegative than sulphur,
O=S=O

O
(B) is an electrophile because oxygen is more electronegative than carbon
–C–CH3
(C) is not an electrophile because H3O+ has lone pair of electrons
(D) is not an electrophile because N cannot accept a pair of electrons because is doe not have d-
orbital.
15. (a,b,d)
CH3 CH3

+ NaOH (CaO) + Na2CO3
(A)
COOH
CH3 CH3

(B) + Zn(dust) + ZnO
OH
CH3OH CH3
(D) red P
+ 2HI + ZnO
(C) is not possible because is gives benzene and not toluene.

MgBr
Br
+CH3OH + Mg
OCH3
LEVEL - 2
16. Etard reaction
17. Conceptual
18. Conceptual
19. HNO3 oxidises HI to HIO3. and prevent back word reaction.
20. Elctrophilic substitution.
CH2CH3
COCH3 Zn(Hg)
conc. HCl + H2O
CH2CH3
21.
NH2NH2
+ H2O
KOH, glycol

C2H5
anhy. AlCl3
+ C2H2Cl
+ HCl
(D) is not possible because o and p-xylene will be formed.

22. A compound will be reactive towards electrophile if the benzene ring is electron rich.
O
In (B) and (C) –OH group and –NH–C–R group will make the benzene ring highly electron rich
due to there ability to donate their electrons inside the benzene ring hence (B) and (C) are correct.
In (A) and (D) since –NO2 and –CHO are electron withdrawing groups they will push electrons
from the benzene system and make it electron deficient.
Hence (A) and (D) are wrong.
Br
C2H5 NBS C2H5
(A)
Mg/ether
H OH MgBr
23. CH2
C2H5 Me Me C2H5
(B)
Hence choices (A), (B) and (D) are correct while (C) is incorrect.
 

H
 
 
Re arrangement
 H
  +
24.
OH OH 2
(C) (D) (A) (B)
Hence (A), (B), (C) and (D) are correct.
25. (A), (B) and (C) are correct statments.

(D) is wrong due to delocalization of -electrons

LEVEL - 3
Br Br Br Br
X
26.

  
X
X
Br Br Br Br
X

  
Br Br Br X Br
X
OH O O O
27.

NaNH 2
liq. NH 3

NH 2
 
NH2
Br NH2
(Major) (Minor)
+
H H
OH OH
NH2
NH2
28. Huckle rule is obeyed.

29. In (B) and (C) planarity and Huckle’s rule are followed
30. The orientation is decided by the activating group i.e. o, p- directing

(B) and (C)

COMPREHENSION TYPE
1. Cl is O,P directing when both +M, -M groups are present, the ESR is the governed by +M only.
2. Strong +M of OH.
3. NH - COCH3 is +M group
4. +M group
5. IPSO Substition
6. Thermodynamically more stable.
7. More acdic acid undergo decarboxylation easily
8. NBS  FSR
Br2/FeCl3  ESR
9. NH2 is strong +M group it is blocked by acylation
10. Steric factor
MATRIX MATCHING TYPE
2. Conceptual
3. +M group activating towards ESR & -M is deactivating
ASSERTION REASONING TYPE

2. Conceptual
3. Conceptual
4. Huckel
SUBJECTIVE
1. N Br
2. Since D is not incorporated into the benzene ring in the absence of AlCl 3, isomer C has no C –
D  bond. Instead, the D end of DCl is attracted to the  cloud of benzene to form a loosely
bound  complex, indicated by an arrow in the structural formula.  complexes are also called

charge – transfer complexes, because the electron – rich benzene ring, the donor molecule,
transfers some electron density to the electron-poor D of DCl, acceptor molecule. With the
catalyst AlCl3, exchange of D+ for H+ occurs on warming. This exchange requires the formation
of a C – D bond to give the  complex. with D+. The benzene ring is reformed by losing an H
rather than the D because the C – H bond is weaker than the C – D bond. Notice the delocalization
of the positive charge in the  bond.

D  Cl   C6 H 6  DCl
 complex, C
Ph Ph Ph
3.
CH3 
Br2 / h
 CH3 and CH3
H3C H3C H3C

2 benzylic 3 alkyl
Br Br
Br
CH3
Ph
Ph
CH3 Br
H3C
H3C
(major) (little yield)
This reaction proceeds via free radical mechanism forming 2 free radicals, of which 2° benzylic
free radical is stabilized more by resonance of phenyl ring and with hyperconjugation of –
CH3 group, thus resulting in the formation of PhCH(Br)CH(CH3)2 as the major product.
Br
H5 C 6
H5 C6
4. A= CH3
B=
CH3
5. Oxidant is an electrophile, it can attack and destroy the ring in case of toluene. But in p-
nitrotoluene, the –NO2 group deactivates the electrophilic attack on benzene nucleus and thus
increases the yield of p-nitrobenzoic acid.

CH3 CH3 CH3

SO3H
conc. OH
  fusion
 
6. H 2SO4 with KOH
CH3 CH3 CH3

p-Xylene
2-5,Dimethylphenol
CH3
O2 N
7.
NO2
N N N
Br Br
 Br2 
 
8. a)
(minor)
Br
(major)
F F
F F F F
b)
 Cl2 
FeCl3

Cl
9. The reaction of C8H10O with alkaline solution of iodine is an iodoform reaction. This reaction is
possible if the compound D has –CO2 – CH3 or – CH(OH) – CH3 group. The high carbon
content in D indicates that D is an aromatic compound containing a benzene ring. To account for
the given formula, the compound D may be C6H5CH(OH)CH3. The given reactions are

CH3 CH3 O Na I

[O]
 
I2 / NaOH
  I
OH O O I
1-phenylethanol
H
OH
O
benzoic acid
NO2
Br
10. a) O Br b)
H3C O
Br
H5 C6
H5C6
11. a) A = B=
H3C
H3C
OH OH
H5 C6 O
C= D= O
OH  H3C
H3C C6 H5 OH
p-Br
p-Br C6 H4 Br
H4 C6 H
b) E = F=
CH3
H CH3

12. The Friedel-Crafts alkylation can be reversed especially when a 3° alkyl group such as Me 3C is
present. Dealkylation is effected with AlBr3 by transfer of Me3C+ to another arene used as
solvent, or at high temperature by protonation as H+ and loss of Me3C as Me2C = CH2.
H3C H3C
CH3 CH3
H3C
CH3 CH3 
 Br 
+

  CH2  HBr
H
Br Br H3C
CH3
CH3
CH3
13. (A) is (while (B) is
O
HO O
CH3 O O
CH3 O
OH 

[O]
 
  H2O
O
(B)
CH3 OH

[O]

(C)
O
H3C CH3
14.  O 
3

AlCl


Zn (Hg) / HCl
(Clemmensen reduction)
CH3
Cl
OH
OH
15. A= B=

Cl
C=
OH CH3 OH
H3C
CH3 CH3 CH3
 H3C 
H 2SO4
 H3C
16. a)
CH2
Br Br
OH O
OH
 H3C 
AlCl3

b) O CH3
CH3 Cl CH3
Cl Cl
OH OH
2Cl2

CH 3COOH

c)
Cl Cl
Cl Cl
PREVIOUS YEAR IIT-JEE PROBLEMS
SINGLE CHOICE
1. (B)
C2H5 CH3 CH3 CH3
NH2 NH3
+
–Cl –H
+ NH2
major product
Cl
carbon uses only two p-orbitals for hybridization.

2. (B)
H O H O
N N
H2C CH3 H2C CH3
Fe/Br2
+ HBr
Br
Major product
It is electrophilic substitution, so electrophile must be attacked o/p-positon due to higher electron

density on these position. In this ring the attached –NH– group will have high electron density due
to resonance and ortho position is blocked, so electrophile is attacked on para position.
MORE THAN ONE OPTIONS ARE CORRECT
3. (B, C,D)
An aromatic will have
(B) (4n + 2)-electrons (by Huckel’s rule)
(C) planar structure (due to resonance)
(D) Cyclic structure (due to presence of sp2-hybdird carbon atoms
4. (C)
It is cumene hydroperoxide rearrangment.
H3C CH3
CH
Anhy AlCl3
+ CH3–CH2–CH2–Cl

H3C H3C CH3 H3C CH3

CH3
CH C O OH C O O H
H
+
O2/ H /H2O
+
or H3H
‘P’ Cumene
hydroperoxide
O H –H2O
+ CH3  CH3
H O C C C
CH3 CH3
H2O
H O
CH3
 +O=O
–H+ CH3
Phenol Acetone
SUBJECTIVE QUESTIONS
CH3
H3C C CH3
5. +(CH3)2 CHCH2Cl + HCl

Anhy AlCl3
(In it (CH3)2 CH–CH2Cl Anhy AlCl3
+ – +
(CH3O)2CH–CH2 + AlCl4 (CH3)2C – CH3
p-carbonium ion ter-carbonium ion (more stable)

SE reaction on t-carbonium ion shows benzene nucleus.
C(CH3)3
conc. H2SO4 + H2O

6. (i) C6H6 + (CH3)2CH–CH2OH
Major product
In this reaction
H+ +
(CH3)2CHCH2OH (CH3)2CH–CH2 (CH3)2C+ – CH3
(–H2O)
p-carbonium ion t-carbonium ion
– (more stable)
(by H shifting)
(by H– shifting)
Hence, in this reaction, active species (electrophile) is (CH3)3C+, so it produces above product as
major product.
CH3 CH2Br
Br2
+ HBr
(ii) hv
Toluene Benzyle bromide
7. In nitrobenzene, –NO2 group is attached with carbon of benzene ring, such group deactivates the
 
benzene ring to such an extent that alkylation by CH or acylation by CH  C  O does not take
3 3
place
CH3 CH3
Anhydrous
H3C +H3C–C–CH2Br H3C –C–CH2
AlCl3
H CH3
CH3 CH3
+
(Note: CH3–C–CH2Br + AlCl3 CH3–C–CH2+ AlCl3(Br)+
H
H
CH3
+
CH3–C–CH3
stable carbonium ion (it is active species of this reaction)

8. The C–Br bond in the case of 7-bromo-1, 3, 5-cycloheptatriene is broken easily because the
intermediate carbocation formed is very stable (aromatic as it contains) (4n +2) number of e
i.e., follows Huckle rule) while it does not break easily in the case of 5-bromo-1, 3 cyclopenta
diene because carbocation formed here is highly unstable as it is anti aromatic i.e., does not follow
Huckel rule. (It contains 4 electrons)
H3C Br H3 C OC2H5
9. (A) CH3 C2H5OH(aq) CH3 +HBr

(acid)
In this compound Br is attched with sp3-hybrid C-atom hence it behaves alkyl halide and give
nucleophilic substitution reaction as S1N reaction.
H CH3
C C2H5OH(aq)
CH3 No reaction
Br
In this compound, Br is directly attached with C-of benzene ring (i.e., sp2-hybrid C-atom), so it is
more tightly attached with carbon and does not give S1N reaction.
F OH
–
OH
–
+F
of NaOH (aq)
(B) (i)
O 2N O2N
CH3 CH3
Given compound is activated aryl halide hence, it undergoes aromatic nucleophilic substitution
reaction due to presence of very strong electron withdrawing group (–NO2) at para-position and
electron releasing group (–CH3) at meta-position of fluorine atom.
F
NaOH (aq) –
F is not liberated
(ii)
CH2NO 2

It is not reactive towards aromatic nucleophilic substitution reaction as the ring is not highly
deactivated because electron attractive (–NO2) group is not directly attached to the benzene ring.
(C) (i) Due to presence of lone pair on nitrogen atomof NO group, it is electron donating group,
so it activates the benzene ring. Hence is ortho and para directive.
(ii) –NO2 group is deactivated group so the electron density on ortho and para positioof
benzene ring is decreased. Hence, it is meta directive in nature.
(D) Hydrogenation takes place on the surface of cataylst through adsorption desorption steps.
The three benzene rings attached to the central benzene ring are not in the same plane during
adospriton only central benzene ring will directly be adsorbed on the surface of Pd hydrogenation
will occur.

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CHEMISTRY ELECTROPHILICAROMATIC SUBSTITUTION

ELECTROPHILIC AROMATIC SUBSTITUTION

THE STRUCTURE OF BENZENE

The Kekulé formula for benzene

Prof. Ajay Yashpal Kapoor 1

Bond lengths and angles in benzene

2 Prof. Ajay Yashpal Kapoor

Huckel’s Orbitals in benzene’s orbital overlap is indicated by the dashed lines

Aromatic compound are those that meet the following criteria

1. The structure must be cyclic, containing some number of conjugrated pi bonds.

Prof. Ajay Yashpal Kapoor 3

(4n + 2), the system is aromatic;

Repulsion of two H's

4 Prof. Ajay Yashpal Kapoor

Anthracene and Phenanthrene

ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS

Prof. Ajay Yashpal Kapoor 5

Progress of the reaction

6 Prof. Ajay Yashpal Kapoor

EFFECT OF SUBSTITUENTS ON RATES OF Ar. SE2 REACTIONS

Deactivating  –I-effect predominates over the

Prof. Ajay Yashpal Kapoor 7

ORIENTATION AND REACTIVITY IN ELECTROPHILIC ARMATIC SUBSTITUTION

8 Prof. Ajay Yashpal Kapoor

Donation of electrons into a benzene ring by resonance

OCH3 OCH3 OCH3 OCH3 OCH3

Prof. Ajay Yashpal Kapoor 9

CH3 CH3 CH3

10 Prof. Ajay Yashpal Kapoor

OCH3 OCH3 OCH3

OCH3 OCH3 OCH3 OCH3

Prof. Ajay Yashpal Kapoor 11

NH2 NH2 NH2 NH2

NH2 NH2 NH2 NH2

NH2 NH2 NH NH2

12 Prof. Ajay Yashpal Kapoor

Prof. Ajay Yashpal Kapoor 13

Activating substitutents most activating

ORTHO / PARA RATIO

Directive influence of the groups during substitutions in benzene ring

14 Prof. Ajay Yashpal Kapoor

i) either ortho and para directing nature

Prof. Ajay Yashpal Kapoor 15

o/p ratios in the nitration of alkylbenzenes

Increasing bulk Attacking electrophile % of o-product

SE reaction on chlorobenzene and the o/p-ratio

Increasing Attacking % of % of o/p-ratio

Electronic effects and the o/p-ratio in the nitration of halobenzenes

Increasing  Substituent % of % of o/p-ratio

16 Prof. Ajay Yashpal Kapoor

Prof. Ajay Yashpal Kapoor 17

Competitive orienting effect of two substituents

18 Prof. Ajay Yashpal Kapoor

DIFFERENT TYPES OF REACTIONS :

b) N2O5 in CCl4 when used, results in a spontaneous dissociation reaction.

Prof. Ajay Yashpal Kapoor 19

c) With concentrated HNO3 alone

20 Prof. Ajay Yashpal Kapoor

CH3 CH3 CH3 CH3

Synopsis & Assignments - EAS by Prof. Ajay Yashpal Kapoor

Synopsis & Assignments - EAS by Prof. Ajay Yashpal Kapoor

Synopsis & Assignments - EAS by Prof. Ajay Yashpal Kapoor