1. IIT-JEE Syllabus
Electrophilic substitution reactions, bromination, nitration, sulfonation, friedel
crafts alkylation and acylation. Effect of o, m, p directing groups in mono
substituted benzenes.
2. Aromaticity
The modern definition of aromaticity is the ability to sustain induced ring current by a flat
or nearly flat cyclic system with (4n + 2) delocalised electrons, where n is zero or any
whole number.
Benzene is the ideal molecule possessing aromaticity. It has a planar hexagonal ring
structure with (4 1 + 2) or 6 electrons. There are six p-orbitals, one on each sp2 atom.
All the six p electron orbitals being parallel to each other and perpendicular to the plane
of the molecule, they form a delocalised electron cloud below and above the plane.
When a magnetic field is applied perpendicular to the plane of the benzene molecule,
the circulation of delocalized electrons takes place in one direction and thereby a ring
current, which induces a counteraction magnetic field inside the ring, is produced (see
figure). The benzene has the ability to sustain induced ring current.
Induced magnetic field
inside the ring
Ring Currnt
Ring Currnt
Systems possessing aromaticity have some physical and chemical properties which are
also collectively known as aromatic character.
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a) Diamagnetic susceptibility
i) Valence bond theory: This theory tells us that resonance stabilization of a planar
cyclic structure is the cause of its aromaticity.
ii) Molecular orbital theory: According to this theory high delocalisation energy is the
cause of aromaticity of planar cyclic systems.
Six p-orbitals, one form each sp2C atom remain perpendicular to the plane of the
hexagonal benzene ring and parallel to each other. All the six p A.O.s overlap to
form six delocalised M.O’s-three bonding and three anti-bonding. The three
boding M.O.’s accommodate all six electrons.
iii) The Hückel 4n + 2 rule: One the basis of M.O. theory Hückel stated that the
presence of 4n+2 delocalized electrons in the flat or nearly flat cyclic systems is
the cause of aromaticity and is known as Hückel’s rule. Here n may be 0, 1, 2, 3
etc., whole number. According to him 4n+2 delocalized -electrons of a cyclic
system develop high delocalization energy or high resonance energy in it. Thus a
compound to be aromatic it must be cyclic planar structure containing (4n+2)
delocalized electrons in a closed shell. This rule is applicable to monocyclic,
fused ring, heterocyclic and cyclic ionic systems.
C
HC H
2H
H CH CH
C CH
H
I II
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2H
H
III IV
H
On the other hand, if a cyclic compound contains higher -electron energy than its
acyclic counterpart, the compound is called anti-aromatic, in fact planar cyclic
conjugated systems with 4n-electrons are called anti-aromatic. Hence cyclobutadiene
is an anti-aromatic compound. If in the case of hypothetical conversion of an acyclic
conjugated system into cyclic conjugated system the -electron energy remains
unchanged the cyclic system is said to be non-aromatic.
+
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+ + +
O O O O
.
Hückel number of delocalized
-electrons are present in a planar
d) N H N H
cyclic structure Hence it is
aromatic.
Cyclooctatetraene has 8 -
electrons. It has a puckered ring
f) structure and proper overlap of -
electrons is not possible. Hence it is
not an aromatic compound.
Exercise 1 a) dentify which of the following compounds are aromatic, anti aromatic
or non aromatic. Reasons also.
+
S
(I) (II) (III) (IV) (V) (VI)
The most characteristic reactions of benzenoid arenes are the substitution reactions that
occur when they react with electrophilic reagents. These reactions are of the general
type shown below.
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ArH + E+ –– Ar – E + H+ or
E
+ +
+ E + H
The electrophiles are either a positive ion (E+) or some other electron-deficient species
with a large partial positive charge. For example, benzene can be brominated when it
reacts with bromine in the presence of FeBr3. Bromine and FeBr3 reacts to produce
positive bromine ions, Br+. These positive bromine ions act as electrophiles and attack
the benzene ring replacing one of the hydrogen atoms in a reaction that is called an
electrophilic aromatic substitution (EAS).
X
X2, FeX3 + H2O Halogenation
(X = Cl, Br)
SO3H
Sulfonation
SO3
H2SO4
R
RCl, AlCl3 + HCl Friedel-Crafts Alkylation
(R can rearrange)
O
O C
R-C AlCl 3
R
Cl + HCl Friedel-Crafts Acylation
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species) e.g. toluene form a 1:1 complex with HCl at –78°C, the reaction being readily
reversible. DCl also forms complex with toluene. This complex on decomposition does
not form deuterium substituted toluene. Formation of complex leads to a solution that is
a non-conductor of electricity.
H D H D H D
H + + H
-
+ DCl + AlCl3 AlCl4
+
H
H D
+ AlCl4
-
complex
Of course one may assume that an aromatic substitution reaction consists of four stpes
involving two and are complexes as shown below.
1. Formation of a -complex
+
E
+
+ E
E E
+ +
H H
TS (1)
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E E
+ +
H H
TS (2)
+
E E + H
Step 1: +E+ H
E
E
H
Step 2: +
Of the following two steps, step 1, the formation of the arenium ion, is the rate-
determining step in electrophilic aromatic substitution.
+
+ E + Slow, rate determining
Step 1:
E H
+
+ + H Fast
Step 2:
H E E
Step 2, the loss of a proton, occurs rapidly relative to step 1 and has no effect on the
overall rate of reaction.
TS I
TS II
Energy
complex
Substrate
Product
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ii) 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 electrophile substitution reaction. If the C – H bond breaking is the r/d,
step, then the reaction will exhibit a primary kinetic isotope effect. By contrast
C6H6 and C6D6 are found to undergo nitration at essentially the same rate, thus C
– H bond breaking cannot be involved in the r/d step, that means complex
formation is the r/d step.
Benzene reacts slowly with hot concentrated nitric acid to yield nitrobenzene. The
reaction is much faster if it is carried out by heating benzene with a mixture of
concentrated nitric acid and concentrated sulfuric acid.
NO 2
H3O HSO 4
50 55 C
HNO 3 H2SO 4
Concentrated sulfuric acid increases the rate of the reaction by increasing the
concentration of the electrophile –– the nitronium ion (NO2+).
H + NO 2 -
O + HSO4
+ HOSO3H O
H NO 2 (H2SO4)
Step 1:
H
Step 2: H + NO 2
+ + -
O + H2SO4 NO 2 + H3O + HSO4
Nitronium ion
H
In step 1 nitric acid acts as a base and accepts a proton from the stronger acid, sulfuric
acid. In step 2 the protonated nitric acid dissociates and produces a nitronium ion. The
nitronium ion reacts with benzene by attacking the cloud and forming an arenium ion.
Step 3: H H + H
NO 2
NO 2 NO 2 NO 2
slow
+ +
Arenium Ion
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The arenium ion then transfers a proton to some base in the mixture such as HSO 4- and
becomes nitrobenzene.
Step 4: Cl
+ Cl
FeCl 3
+ HCl
25 C
chlorobenzene
Br
+ Br2 + HBr
FeCl 3
25 C
bromobenzene
Benzene does not react with bromine or chlorine unless a Lewis acid is present in the
mixture, (as a consequence, benzene does not decolorize a solution of bromine in
carbon tetrachloride). When Lewis acids are present, however, benzene reacts readily
with bromine or chlorine, and the reactions give bromobenzene and chlorobenzene in
good yields.
The Lewis acids most commonly used to effect chlorination and bromination reactions
are FeCl3, FeBr3, and AlCl3 all in the anhydrous form. Ferric chloride and ferric bromide
are usually generated in the reaction mixture by adding iron to it. The iron then reacts
with halogen to produce the ferric halide :
Step 1: + -
Br Br + FeBr Br + FeBr4
Step 2:
H H
+ Br Br
+ Br
slow
etc
+ +
Arenium Ion
Step 3: H
Br
Br -
Br FeBr3
fast
+ H Br + FeBr3
+
The function of the Lewis acid can be seen in step 1. The ferric bromide reacts with
bromine to produce a positive bromine ion, Br+ (and FeBr4-). In step 2 this Br+ ion attacks
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the benzene ring to produce an arenium ion. Then finally in step 3 the arenium ion
transfers a proton to FeBr4-. This results in the formation of bromobenzene and hydrogen
bromide –– the products of the reaction. At the same time this step regenerates the
catalyst FeBr3.
Hypo-halous acids (HO – Hal) in presence of strong acid also become a very powerful
halogenating agent.
Hal + H
+ + +
HO H2O Hal H2O + Hal
Fluorine reacts so rapidly with benzene that aromatic fluorination requires special
conditions and special types of apparatus. Even then, it is difficult to limit the reaction to
monofluorination. Fluorobenzene can be made, however, by an indirect method.
Iodine, on the other hand, is so unreactive that a special technique has to be used to
effect direct iodination; the reaction has to be carried out in the presence of an oxidizing
agent such as nitric acid.
+ I2 HNO3
Kinetic isotope effects have not been observed for chlorination and rarely for
bromination, but iodination shows primary kinetic isotope effect.
O
Suffer trioxide Benzenesulfonic acid
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When sulfur trioxide reacts with benzene the following steps occur.
Step 2: H H + H
O
- - -
slow SO3 SO3 SO3
S O
+ +
O
Arenium Ion
Step 3: H
- SO3
SO3 -
+ HSO4 + H2SO4 Fast
+
All of the steps are equilibria, including step 1 in which sulfur trioxide is formed from
sulfuric acid. This means that the overall reaction is an equilibrium as well. In
concentrated sulfuric acid, the overall equilibrium is the sum of steps 1 - 4.
SO3H
+ H2SO4 + H2O
In fuming sulfuric acid, step 1 is unimportant because the dissolved sulfur trioxide reacts
directly.
Because all of the steps are equilibria, the position of equilibrium can be influenced by
the conditions we employ. If we want to sulfonate benzene we use concentrated sulfuric
acid or better yet fuming sulfuric acid. Under these conditions the position of equilibrium
lies appreciably to the right and we obtain benzenesulfonic acid in good yield.
On the other hand, we may want to remove a sulfonic acid group from a benzene ring.
To do this we employ dilute sulfuric acid and usually pass steam through the mixture.
Under these conditions with a high concentration of water the equilibrium lies
appreciably to the left and desulfonation occurs. The equilibrium is shifted even further to
the left with volatile aromatic compounds because the aromatic compound distills with
the steam.
We shall see later that sulfonation and desulfonation reactions are often used in
synthetic work. We may, for example, introduce a sulfonic acid group into a benzene ring
to influence the course of some further reaction. Later, we may remove the sulfonic acid
group by desulfonation. Like iodination, sulfonation exhibits a kinetic isotopic effect,
indicating that C – H bond breaking is involved in the rate determining step.
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In 1877 a French chemist, Charles Friedel, and his American collaborator James M.
Crafts, discovered new methods for the preparation of alkylbenzenes (ArR) and
acylbenzenes (ArCOR). These reactions are now called the Friedel - Crafts alkylation
and acylation reactions. We shall study the Friedel - Crafts alkylation reaction here and
then take up the Friedel - Crafts acylation reaction. A general equation for a Friedel -
Crafts alkylation reaction is the following :
+ R X
AlCl3
+ HX
The mechanism for the reaction (shown in following steps with isopropyl chloride as R –
– X) starts with the formation of a carbocation (step 1). The carbocation then acts as an
electrophile (step 2) and attacks the benzene ring to form an arenium ion. The arenium
ion (step 3) then loses a proton to generate isopropylbenzene.
H3C H3C
Isopropyl chloride Carbocation
Step 2:
CH3 H CH3
+
HC
+ HC +
CH3
H3C
Arenium ion
Step 3: CH3
H CH3
CH
HC - CH3 + HCl + AlCl3
+ + AlCl4 +
CH3
Isopropylbenzene
When R –– X is a primary halide, a simple carbocation probably does not form. Rather,
the aluminum chloride forms a complex with the alkyl halide and this complex acts as the
electrophile. The complex is one in which the carbon - halogen bond in nearly broken ––
and one in which the carbon atom has a considerable positive charge.
+ –
RCH2 ---- Cl : AlCl3
Even though this complex is not a simple carbocation, it acts as if it were and it transfers
a positive alkyl groups to the aromatic ring. These complexes are so carbocation like
that they also undergo typical carbocation rearrangements.
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Friedel - Crafts alkylations are not restricted to the use of alkyl halides and aluminum
chloride. 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(CH 3)2
0 C
+ CH3CH = CH2
C
+
0 C
C
+ OH
60 C
BF3
O
||
The R C group is called an acyl group, and a reaction whereby an acyl group is
introduced into a compound is called an acylation reaction. Two common acyl groups
are the acetyl group and the benzoyl group.
O
C
O CH3
CH 3C
Acetyl group Benzoyl group
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. Unless the aromatic compound is one that is highly
reactive, the reaction requires the addition of at least one equivalent of a Lewis acid
(such as AlCl3) as well. The product of the reaction is an aryl ketone.
O
O C
CH3
+ H3C C
AlCl3
excess benzene
80 C
Cl
acetyl chloride Acetophenon (methyl
phenyl ketone
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Acyl chlorides, also called acid chlorides, are easily prepared by treating carboxylic
acids with thionyl chloride (SOCl2) or phosphorus pentachloride (PCl5).
O O
H3C C + SOCl2 H3C
80 C
+ SO2 + HCl
OH Thionyl chloride Cl
acetic acid acetyl chloride
O O
+ PCl 5 + POCl3 + HCl
OH Cl
Phosphorus
benzoic acid pentachloride benzoyl chloride
Friedel - Crafts acylations can also be carried out using carboxylic acid anhydrides. For
example :
O O
H3C C C O
CH3
+ O
AlCl3
+ H3C
excess benzene
H3C C OH
Acetophenone
O
acetic anhydride
In most Friedel - Crafts acylations the electrophile appears to be an acylium ion formed
from an acyl halide in the following way :
O O
-
R C + AlCl3 R AlCl3
+
Cl Cl
O
- + + -
R C + AlCl3 C O C O + AlCl4
+
Cl R R
The remaining steps in the Friedel - Crafts acylation of benzene are the following :
O
H
C
R
+ R C +
+
O
Arenium ion
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O O
H
C C
R R
-
+ + AlCl4 + HCl + AlCl3
R R
O O -
+ AlCl3 AlCl3
+
In the last step aluminum chloride (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.
H3C R
H3C H5C6
Several important synthetic applications of the Friedel - Crafts reaction are later in the
package.
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.
When benzene is alkylated with butyl bromide, for example, some of the
developing butyl cations rearrange by a hydride shift –– some developing 1o
carbocations (see following reactions) become more stable 2o carbocations.
Then benzene reacts with both kinds of carbocations to form both butylbenzene
and sec-butyl-benzene :
+
AlCl3 CH 2 CH3
H3C Br H3C H3C
+
CH3
H3C
H3C
butylbenzene
sec-butylbenzene
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We shall learn that groups present on an aromatic ring can have large effect on
the reactivity of the ring towards electrophilic aromatic substitution. Electron -
withdrawing groups make the ring less reactive by making it electron deficient.
Any substituent more electron withdrawing (or deactivating) than a halogen, that
is, any meta-directing group, makes an aromatic ring too electron deficient to
undergo a Friedel - Crafts reaction. The amino groups, –NH2, –NHR, and –NR2,
are changed into powerful electron - withdrawing groups by the Lewis acids used
to catalyze Friedel - Crafts reactions. For example :
H
H H
N H +N AlCl3
+ AlCl3
3. Aryl and vinylic halides cannot be used as the halide component because they
do not form carbocations readily.
Cl
No Friedel-Crafts reaction
AlCl3
No Friedel-Crafts reaction
CH3
Cl
H3C
CH3
4. Polyalkylations often occur Alkyl groups are electron - releasing groups, and
once one is introduced into the benzene ring it activates the ring toward further
substitution.
CH3 CH3
H3C
+ CHOH
BF3
+
60 C
H3C
Isopropyl benzene (24%)
CH3
p-diisopropylbenzene (14%)
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Polyacylations are not a problem in Friedel - Crafts acylations, however the acyl
group (RCO–) by itself is an electron - withdrawing group, and when it forms a
complex with AlCl3 in the last step of the reaction, it is made even more electron
withdrawing. This strongly inhibits further substitution and makes monoacylation
easy.
Rearrangements of carbon chain do not occur in Friedel - Crafts acylations. The acylium
ion, because it is stabilized by resonance, is more stable than most other carbocations.
Thus, there is no driving force for a rearrangement. Because rearrangements do not
occur, Friedel - Crafts acylations often give us much better routes to unbranched
alkylbenzenes than do Friedel - Crafts alkylations.
Br
AlCl3
+ HBr
+ H3C
isopropylbenzene
By contrast, the Friedel - Crafts acylation of benzene with propanoyl chloride produces a
ketone with an unrearranged carbon chain in excellent yield.
O
Cl
H3C + HCl
+
AlCl3
CH3
O
propanoyl chloride Ethyl phenyl ketone
zinc. [Caution : As we shall discuss later zinc and hydrochloric acid will also reduce nitro
groups to amino groups.]
O
CH3
Zn (Hg )
HCl reflux
CH3
Zn (Hg ) Ar
HCl, reflux
Ar R R
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When cyclic anhydrides are used as one component, the Friedel - Crafts acylation
provides a means of adding a new ring to an aromatic compound.
O
Solution:
O
+
AlCl3
O
O OH
excess Succinic anhydride O
3-benzoylpropanoic acid
OH Cl
SOCl 2
80 C
O O
AlCl3-CS2
O
-Tetralone
Exercise 2: Nitrobenzene, but not benzene, is used as a solvent for the Friedel-Craft
alkylation of bromo-benzene. Explain.
We can divide substituent groups into two classes according to their influence on the
reactivity of the ring. Those that cause the ring to be more reactive than benzene itself
we call activating groups. Those that cause the ring to be less reactive than benzene
we call deactivating groups.
We also find that we can divide substituent groups into two classes according to the way
they influence the orientation of attack by the incoming electrophile. Substituents in one
class tend to bring about electrophilic substitution primarily at the positions ortho and
para to themselves. We call these groups ortho - para directors because they tend to
direct the incoming group into the ortho and para positions. Substituents in the second
category tend to direct the incoming electrophile to the meta position. We call these
groups meta directors.
Several examples will illustrate more clearly what we mean by these terms.
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The methyl group in an activating group is an ortho - para director. Toluene reacts
considerably faster than benzene in all electrophilic substitutions.
CH3
An activating group
We observe the greater reactivity of toluene in several ways. We find, for example, that
with toluene, milder conditions –– lower temperatures and lower concentrations of the
electrophile – can be used in electrophilic substitutions than with benzene. We also find
that under the same conditions, toluene reacts faster than benzene. In nitration, for
example, toluene reacts 25 times as fast as benzene.
We find, moreover, that when toluene undergoes electrophilic substitution, most of the
substitution takes place at its ortho and para positions. When we nitrate toluene with
nitric and sulfuric acids, we get mononitrotoluenes in the following relative proportions.
NO 2
HNO3 + +
H2SO4
o-nitrobenzene (59%) NO 2
NO 2 m-nitrotoluene (4%)
p-nitrobenzene (37%)
Of the mononitrotoluenes obtained from the reaction, 96% (59% + 37%) has the nitro
group in an ortho or para position. Only 4% has the nitro group in a meta position.
Predominant substitution at the ortho and para positions of toluene is not restricted to
nitration reactions. The same behavior is observed in halogenation, sulfonation, and so
forth.
All alkyl groups are activating groups, and they are all also ortho – para directors. The
methoxy group, CH3O–, and the acetamido group, CH3CONH–, are strong activating
groups and both are ortho – para directors.
The hydroxyl group and the amino group are very powerful activating groups and are
also powerful ortho – para directors. Phenol and aniline react with bromine in water (no
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catalyst is required) to produce products in which both of the ortho positions and the
para position are substituted. These tribromo products are obtained in nearly quantitative
yield.
OH OH
Br Br
Br2
H2O
Br
2,4,6-tribromophenol
NH2 NH2
Br Br
Br2
H2O
Br
2,4,6-tribromoaniline
The nitro group is a very strong deactivating group. Nitrobenzene undergoes nitration
at a rate only 10-4 times that of benzene. The nitro group is a meta director. When
nitrobenzene is nitrated with nitric acid sulfuric acids, 93% of the substitution occurs at
the meta position.
NO 2 NO 2 NO 2 NO 2
NO 2
HNO 2
+ +
H2SO4
NO 2
(6%)
NO 2 (93%)
(1%)
The carboxyl group (–CO2H), the sulfo group (–SO3H), and the trifluoromethyl group (–
CF3) are also deactivating groups; they are also meta directors.
The chloro and bromo groups are weak deactivating groups. Chlorobenzene and
bromobenzene undergo nitration at rates that are, respectively, 33 and 30 times slower
than for benzene. The chloro and bromo groups are ortho - para directors, however. The
relative percentages of monosubstituted products that are obtained when chlorobenzene
is chlorinated, brominated, nitrated, and sulfonated are shown in Table 1.
TABLE 1 Electrophilic Substitution Of Chlorobenzene
Para Product Total Ortho and Para Meta Product
Reaction Ortho Product (%)
(%) (%) (%)
Chlorination 55 94
39 6
Bromination 87 98
11 2
Nitration 70 100
30
Sulfonation 100 100
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7. Classification of Substituents
Studies like the ones that we have presented in this section have been done for a
number of other substituted benzenes. The effects of these substituents on reactivity
and orientation are included in Table 2.
TABLE 2 Effect of substituents on electrophilic aromatic
substitution
ORTHO - PARA DIRECTORS META DIRECTORS
Strongly Activating Moderately Deactivating
–NH2, –NHR, –NR2 –C N
. . –O:-
–OH, –SO3H
.. –CO2H, –CO2R
Moderately Activating –CHO, –COR
–NHCOCH3, –NHCOR
–OCH3, –OR Strongly Deactivating
–NO2
Weakly Activating –NR3+
–CH3, C2H5, –R –CF3, –CCl3
–C6H5
Weakly
. . . . Deactivating
.. ..
–F:,
. . –Cl:,
. . –Br:,
. . .–I:
.
We have also seen that we can account for relative reaction rates by examining the
transition state for the rate-determining steps. We know that any factor that increases
the energy of the transition state relative to that of the reactants decreases the relative
rate of the reaction. It does this because it increases the free energy of activation of the
reaction. In the same way, any factor that decreases the energy of the transition state
relative to that of the reactants lowers the free energy of activation and increases the
relative rate of the reaction.
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we mean that S can be in any position – ortho, meta, or para – relative to the
electrophile, E. Using these conventions, then, we are able to write the rate-determing
step for electrophilic aromatic substitution in the following general way.
When we examine this step for a large number of reactions, we find that the relative
rates of the reactions depend on whether S withdraws or release electrons. If S is an
an electron - releasing group (relative to hydrogen), the reaction occurs faster than the
corresponding reaction of benzene. If S is an electron withdrawing group, the reaction
occurs slower than that of benzene.
S
S
+ Reaction is
+ E + faster
S releases
electrons H H
Arenium ion
is stabilized
S S
+ Reaction is
+ E + slower
S withdraws
electrons H H
Arenium ion is
destabilized
It appears, then, that the substituent (S) must affect stability of the transition state
relative to that of the reactants. Electron - releasing groups apparently make the
transition state more stable, while electron withdrawing groups make it less table. That is
so is entirely reasonable, because the transition state resembles the arenium ion, and
the arenium ion is a delocalized carbocation.
The inductive effect of a substituent S arises from the electrostatic interaction of the
polarized S to ring bond with the developing positive charge in the ring as it is attacked
by an electrophile. If, for example, S is a more electronegative atom (or group) than
carbon, then the ring will be at the end of the dipole:
-
S (e.g. S = F, Cl or Br)
Attack by an electrophile will be retarded because this will lead to an additional full
positive charge on the ring. The halogens are all more electronegative than carbon and
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X+
O–
O
NR; (R-alkyl or H) C+ X+ N S+—OH
+
O– O
X+
O O
Then resonance effect of a substituent S refers to the possibility that the presence of S
may increase or decrease the resonance stabilization of the intermediate arenium ion.
The S substituent may, for example cause one of the three contributors to the resonance
hybrid for the arenium ion to the better or worse than the case when S is hydrogen.
Moreover, when S is an atom bearing one or more nonbonding electron pairs, it may
lend extra stability to the arenium ion by providing a fourth resonance contributor in
which the positive charge resides on S.
E E +
+ S S
H H
This electron-donating resonance effect applies with decreasing strength in the following
order:
This is also the order of the activating ability of these groups. Amino groups are highly,
activating, hydroxyl and alkoxyl groups are somewhat less activating, and halogen
substituents are weakly deactivating. When X = F, this order can be related to the
electronegativity of the atoms with the nonbonding pair. The more electronegative the
atom is the less able it is to accept the positive charge (fluorine is the most
electronegative, nitrogen the least). When X = Cl, Br, or I, the relatively poor electron-
donating ability of the halogens by resonance is understandable on a different basis.
These atoms (Cl, Br, and I) are all larger than carbon and, therefore, the orbitals that
contain the nonbonding pairs are further from the nucleus and do not overlap well with
the 2p orbital of carbon. (This is a general phenomenon: resonance effects are not
transmitted well between atoms of different rows in the periodic table.)
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All meta-directing groups have either a partial positive charge or a full positive charge on
the atom directly attached to the ring. As a typical example let us consider the
trifluoromethyl group.
The trifluoromethyl group, because of the three highly electronegative fluorine atoms, is
strongly electron withdrawing. It is a strong deactivating group and a powerful meta
director in electrophilic aromatic substitution reactions. We can account for both of these
characteristics of the trifluoromethyl group in the following way.
The trifluoromethyl group affects reactivity by causing the transition state leading to the
arenium ion to be highly unstable. It does this by withdrawing electrons from the
developing carbocation thus increasing the positive charge in the ring.
+ +
+ Highly unstable
E contributor
Meta Attack
CF 3 CF 3 CF 3 CF 3
+ +
E E E
+
H H
+ H
E
Para Attack
CF 3 CF 3 CF 3 CF 3
+ +
+
E H E H E
H E
Highly unstable
contributor
We see in the resonance structures for the arenium ion arising from ortho and para
attack that one contributing structure is highly unstable relative to all the others because
the positive charge is located on the ring carbon that bears the electron-withdrawing
group. We see no such highly unstable resonance structure in the arenium ion arising
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from meta attack. This means that the arenium ion formed by meta attack should be the
most stable of the three. By the usual reasoning we would also expect the transition
state leading to the meta - substituted arenium ion to be the most stable and, therefore,
that meta attack would be favoured. This is exactly what we find experimentally. The
trifluoromethyl group is a powerful meta director.
CH3 CH3
+ HNO 3
H2SO4
CH3
Trifluoromethyl)benzene
(-100%)
We bear in mind, however, that meta substitution is favoured only in the sense that it is
the least unfavorable of three unfavourable pathways. The free energy of activation for
substitution at the meta position of (trifluoromethyl) benzene is less than that for attack at
an ortho or para position, but it is still far greater than that for an attack on benzene.
Substitution occurs at the meta position of (trifluoromethyl) benzene faster than
substitution takes place at the ortho and para positions, but it occurs much more slowly
than it does with benzene.
The nitro group, the carboxyl group, and other meta-directing groups are all powerful
electron-withdrawing groups and all act in similar way.
Except for the alkyl and phenyl substituents, all of the ortho-para-directing groups in
Table 2 are of the following general type:
H H H
SH N O Cl
Non-bonding electrons as in
All of these ortho-para directors have at least one pair of nonbonding electrons on the
atom adjacent to the benzene ring.
This structural feature - an unshared electron pair on the atom adjacent to the ring -
determines the orientation and influence reactivity in electrophilic substitution reactions.
The directive effect of these groups with an unshared pair is predominantly caused by an
electron - releasing resonance effect. The resonance effect, moreover, operates
primarily in the arenium ion and, consequently, in the transition state leading to it.
Except for the halogens, the primary effect on reactivity of these groups is also caused
by an electron-releasing resonance effect. And, again, this effect operates primarily in
the transition state leading to the arenium ion.
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In order to understand these resonance effects let us begin by recalling the effect of the
amino group on electrophilic aromatic substitution reactions. The amino group is not only
a powerful activating group, it is also a powerful ortho–para director. Aniline reacts with
bromine in aqueous solution at room temperature and in the absence of a catalyst to
yield a product in with both ortho positions and the para position are substituted.
The inductive effect of the amino group makes it slightly electron withdrawing. Nitrogen,
as we know, is more electronegative than carbon. The difference between the
electronegativities of nitrogen and carbon in aniline is not large, however, the carbon of
the benzene ring is sp2 hybridized and thus is somewhat more electronegative than it
would be if it were sp3 hybridized.
The resonance effect of the amino group is far more important than its inductive
effect in electrophilic aromatic substitution, and this resonance effect makes the
amino group electron releasing. We can understand this effect if we write the resonance
structures for the arenium ions that would arise from ortho, meta, and para attack on
aniline.
Exercise 3: Classify the following substituents as activating or deactivating groups and
write the structural formula of mono-substitution products.
a) C6H5CF3, Mono bromination
b) C6H5CH(CH3)CH2CH3, mono sulfonation
c) Mononitration, C6H5COOCH3
+ +
Relative stable
contributor
Meta Attack
NH2 NH2 NH2 NH2
+ +
E E E
+
H H
+ H
E
Para Attack
NH2 NH2 NH2 NH2 NH2
+ + +
+
E H E H E H E H E
Relatively stable
contributor
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We see that four reasonable resonance structures can be written for the arenium ions
resulting from ortho and para attack, whereas only three can be written for the arenium
ion that results from meta attack. This, in itself, suggests that the ortho- and para-
substituted arenium ions should be more stable. Of greater importance, however, are the
relatively stable structures that contribute to the hybrid for the ortho- and para-
substituted arenium ions. In these structures, nonbonding pairs of electron from nitrogen
form an extra bond to the carbon of the ring. This extra bond – and the fact that every
atom in each of these structures has a complete outer octet of electrons – makes these
structures the most stable of all of the contributors. Because these structures are
unusually stable, they make a large – and stabilizing– contribution to the hybrid. This
means, of course, that the ortho- and para-substituted arenium ions themselves are
considerably more stable than the arenium ion, that results from the meta attack.
Phenol reacts with acetic anhydride, in the presence of sodium acetate, to produce the
ester, phenyl acetate.
OH
( CH3CO )2 O
O
CH3CO 2Na
CH3
phenol O
phenyl acetate
Phenyl acetate, like phenol is an ortho - para director, (a) What structural feature of
phenyl acetate explains this ? (b) Phenyl acetate, although an ortho - para director, is
less reactive toward electrophilic aromatic substitution than phenol. Use resonance
theory to explain why this is so. (c) Aniline is often so highly reactive toward electrophilic
substitution that undesirable reactions take place. One way to avoid these undesirable
reactions is to convert aniline to acetanilide (above), by treating aniline with acetyl
chloride or acetic anhydride.
NH2
( CH3CO )2 O
NH
CH3
aniline O
N-phenylacetamide
What kind of directive effect would you expect the acetamido group (CH3CONH–) to
have ? (d) Explain why it is much less activating than the amino group, –NH2.
The directive and reactivity effects of halo substituents may, at first, seem to be
contradictory. The halo groups are the only ortho - para directors (in Table 2) that are
deactivating groups. All other deactivating groups are meta directors. We can readily
account for the behavior of halo substituents, however, if we assume that their
electron-withdrawing inductive effect influences reactivity and their electron-
donating resonance effect governs orientation.
Let us apply these assumptions specifically to chlorobenzene. The chloro atom is highly
electronegative. Thus, we would expect a chloro atom to withdraw electrons from the
benzene ring and thereby deactivate it.
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Cl
On the other hand, when electrophilic attack does take place, the chloro group stabilizes the
arenium ions resulting from ortho and para attack relative to that from meta attack. The
chloro group does this in the same way as amino groups and hydroxyl group do – by
donating an unshared pair of electron. These electrons give rise to relatively stable
resonance structures contributing to the hybrids for the ortho- para-substituted arenium ions.
Ortho Attack
Cl Cl Cl Cl
+
Cl
+
E E E E E
H H + H H
+ +
Relative stable
contributor
Meta Attack
Cl Cl Cl Cl
+ +
E E E
+
H H
+ H
E
Para Attack
+
Cl Cl Cl Cl Cl
+ + +
+
E H E H E H E H E
Relatively stable
contributor
We see that four reasonable resonance structures can be written for the arenium ions
resulting from ortho and para attack, whereas only three can be written for the arenium
ion that results from meta attack. This, in itself, suggests that the ortho- and para-
substituted are
What we have said about chlorobenzene is, of course, true of bromobenzene. We can
summarize the inductive and resonance effects of halo substituents in the following way.
Through their electron-withdrawing inductive effect halo groups make the ring more
positive than that of benzene. This causes the free energy of activation for any
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electrophilic aromatic substitution reaction to be greater than that for benzene, and,
therefore, halo groups are deactivating. Through their electron donating resonance
effect, however, halo substituents cause the free energies of activation leading to ortho
and para substitution to be lower than the free energy of activation leading to meta
substitution. This makes halo substituents ortho-para directors.
i) If the two substituents belong to the activating group, the stronger o/p director will
control the orientation; nevertheless several tri-substituted isomers will form. The
order of decreasing directing powers of the activating groups is.
ii) When both groups belong to the deactivating groups then its difficult to introduce
a third group. However the order of decreasing directing powers of deactivating
groups are
O
||
NMe 3 NO 2 CN SO 3H CHO C Me CO 2H
iii) If one substituent belongs, to activating group and other belongs to deactivating
group the first group determining the orientation. Further, if the orientations
reinforce each other, the third group enters almost entirely one position. The
above scheme is purely qualitative.
Exercise 4: a) Cl b) Br
+ (C6H5)3 C K A
KNH2
B
Cu
NH3
200 C
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The side halogenation of alkyl benzenes takes place in the presence of light or high
temperatures. Side chain halogenation is many times carried out by using the reagent N-
bromosuccinimide (NBS) in the presence of light.
CH3 O
CH 2Br
C
H2C h
+ NBr
CCl 4
H2C
C
O
An alkyl benzene with side chain other than methyl may lead to the formation of more
than one products.
Br
CH3
CH3
(I)
Br2
Heat, light
Br
(II)
Product (I) is the only product obtained, and formation of such product can be attributed
to mechanism governing this reaction. Side chain halogenation has a similar mechanism
as that of alkanes. It involves the formation of free radical intermediates. Now if we
observe the free radicals formed by attack of Bromine free radical on Ethyl benzene, we
will find that product (I) involves formation of Benzyl free radical and (II) involves
formation of Primary free radical.
CH3 Br CH3
HC
h
Br2
CH3
Br
CH 2
h
Br2
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The benzyl free radical is more stable than primary free radical because its bond
dissociation energy is 19 kcal/mole less than that of primary free radical.
Order of stability of free-radicals. Benzyl > Allyl > 3° > 2° > 1° (from bond dissociation
energy data).
The above reaction can be used for identifying substitution pattern in aromatic
compound. If any compound gives phthalic acid on heating with KMnO4, then we can
infer that it is ortho disubstituted benzene.
CH3
R COOH H3C CH3
R COOH
KMnO 4
No reaction
KMnO 4
Cl Cl Cl Cl
NO 2
chlorobenzene 1-chloro-3-nitrobenzene
NO 2 NH2
4-chloroaniline
1-chloro-4-nitrobenzene
Any halogen compound that contains a benzene ring is not classified as aryl halide. e.g.
Benzyl chloride is not an aryl halide, but is a substituted alkyl halide.
Halogenation
Ar – H + X2 Ar – X + HX
Lewis acid
(X = Cl, Br)
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For introducing only the halogen at para position, the Lewis acid thallium acetate is
used.
CH3 CH3
CO CO
NH NH
Br
T l( OAc )3
Acetanilide
CH3
Ar H Ar NO 2
HNO 3
Ar NH 2
reduction
NaNO 2
H2SO4 Sn / HCl HCl( 0 5 )
+
N2Cl F
HBF4 (Schiemann reaction)
+
N2Cl Cl
CuCl (Sandmayer's reaction)
+
N2Cl Cl
Cu Powder
(Gatterman reaction)
HCl
+
N2Cl I
KI
heat
Reactivity: Unlike alkyl halides, aryl halides are less reactive towards Nucleophilic
substitution reactions, this can be attributed to their electron release via resonance.
+ + +
Cl Cl Cl Cl Cl
H H
H
(I) (II) (III) (IV) (V)
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Structures III, IV and V stabilise chlorobenzene molecule and give a double bond
character to the carbon-chlorine bond. Now because of this the carbon-chlorine bond
has more strength and hence aryl halides are more stable towards Nucleophilic
substitution reactions. In Alkyl halides the carbon atom attached to halogen is sp 3
hybridized and in aryl halides it is sp2 hybridized, as sp2 hybridized carbon is more
electronegative it does not permit the chlorine atom to get displaced with the bonded pair
of electrons.
Cl Z Cl Z Cl Z Cl Z Cl
H H
Fast H
+ Cl
Any factor that stabilizes the carbanion will increase the rate of Nucleophilic substitution
reaction by dispersing the charge present on resonating structures. An electron
withdrawing group present at meta position does not activate the ring as much as it does
from ortho and para position. This can be known by looking at following resonance
structures.
Z Cl Z Cl Z Cl
(Meta)
NO 2 NO 2 NO 2
Z Cl Z Cl Z Cl
(Para)
NO 2 NO 2 NO 2
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+ X
NH2 NH2
+ NH 2 + NH 3 + NH 2
Isotopic labelling confirmed that there is an equal chance of abstraction from both
carbons. An aryl halide which does not contain alpha hydrogen with respect to halogen
does not undergo this reaction. In the reactions involving Benzyne intermediates, two
factors affect the position of incoming group, the first one is direction of aryne formation.
When there are groups ortho or para to the leaving group, then, the following
intermediates should be formed.
Z Z Z
X
NH2
N H2
Intermediate
X
when a meta group is present, aryne can form in two ways, In such cases
Z Z
or
X
more acidic hydrogen is removed, i.e., an electron attracting ‘Z’ favours removal of ortho
hydrogen while an electron donating ‘Z’ favours removal of para hydrogen.
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b)
In pyrole lone pair of nitrogen
take part in resonance. Electron
N density on N atom decreases
H
In pyrridine the lone pair of nitrogen is free and it can donate this lone
pair of electron easily. So pyrridine is more basic than pyrrole.
N
Solution 3: CH3
deactivating, F3C
b) CH3
activating, H O3S
CH3
c) NO 2
O
deactivating,
H3C O
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Solution: Phenol is 0-,p-directing due to the +M effect of its O H group.
+ +
OH OH OH
Also O H has –I effect.
But in alkaline medium, phenol is converted to phenoxide ion which
has both +M and +I effect. Hence ring is more activated and hence
electrophilic substitution occurs more readily.
( A )
H2SO4
(B)
i ) NaOH / fusion
(C)
i ) CO 2 , KOH
ii) H ii) H
Solution: OH
SO3H OH
A= B= C=
CO 2H
from benzene?
Solution: O
Cl CH3
+ H3C
ACl2
O
Zn(Hg)/HCl
(Clemmensen reduction)
CH3
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Problem 4: Phenyl group is known to exert –I effect. But each phenyl ring in
biphenyl (C6H5 – C6H5) is more reactive than benzene towards
electrophilic substitution. Why?
Solution: In biphenyl, one of the phenyl groups acts as electron donor and the
other electron acceptor. This makes the phenyl ring more reactive
than benzene towards electrophilic substitution.
Problem 5: The alkylation of phenol and aniline with alkyl halide in presence of
AlCl3 gives poor yields. Explain.
Solution: In presence of Lewis acid (e.g. AlCl3), the group (–NH2 or –OH)
becomes electron withdrawing.
C C
3 3 ?
(H C) Cl
AlCl3
Solution: O O
C AlCl3 C + AlCl3
C Cl C Cl
C + O
+
(H3C) 3 C CO + Me3 C
Problem 7: The rates of bromination (FeBr3 catalyst) of C6H6 and C6D6 are the
same. Discuss.
H Br
+ 1
+ Br FeBr4
+ HBr + FeBr3
+ 2
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Steps 1 and 2 are bimolecular and so either could be the r/d step.
Since no kinetic isotope effect is observed when H is replaced D, C–H
or C–D bond fission cannot be involved in r/d step. Hence, 1 is the r/d
step and so the rate of bromination is the same for C6H6 and C6D6.
OCH3
m-position more favoured for attack
CH3
Br
i) EtOHH2O ii)
+ KCN ?
Δ
+ HNO 3 ?
Ac 2O
AcOH
Cl
CHO
NO 2
iii) ?
HNO 3
iv) + NaI ?
DMF
OMe
OMe
NO 2
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CH O
CHO
OMe Me
O
OMe MeO
iv) Cl
I
NO2
DMF NO2
+ NaI
+ NaCl
NO2
NO2
This is an example of activated nucleophilic substitution (also
compare with the Finkelstein reaction.
AlCl3 HCl
Solution:
SOCl
anhydrous
AlCl3
int ramolecular
COOH COCl F.C. reaction
Zn Hg
HCl
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OBJECTIVE
Problem 1. 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.
Solution: The intermediate carbonium ion formed after initial attack of Br+ at the meta
position is least destabilized.
Hence (B) is correct.
| CH3
CH3
Problem 3. When –N+ (CH3)3 group is attached to the benzene ring, it orients the incoming
electrophile into
(A) Meta position (B) Ortho position
(C) Para position (D) Equally directs group to ortho-para position
Solution: (A)
Problem 4. When benzene is treated with isobutyl bromide in the presence of AlCl3 it mainly gives
(A) Tertiary butyl benzene (B) Isobutyl benzene
(C) n-butyl benzene (D) Secondary butyl benzene
Solution: (A)
Problem 5. Nitrobenzene can be prepared from benzene by using a mixture of conc. HNO 3 and
conc. H2SO4. In the nitrating mixture HNO3 as a
(A) Base (B) Acid
(C) Reducing agent (D) Catalyst
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RSM79-Ph-III-EAS-CH-41
16. Assignments
16.1 Subjective
LEVEL – I
NaNO2 HCl
( A ) (B)
CuCN
(C)
H3O
( 0 5C )
S
I II III IV V VI
9. CH3
HNO3 H2SO4
NO 2
In the above reaction which product is not likely to be formed and why?
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RSM79-Ph-III-EAS-CH-42
[O]
KMnO 4
CrO2Cl2
[Etard Reaction]
ii) CH3
[O]
KMnO 4
CrO2Cl2
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RSM79-Ph-III-EAS-CH-43
LEVEL – II
3. During reaction of benzene with neopentyl chloride with benzene in the presence
of AlCl3 the major product is 2-methyl-2-phenylbutane and not
neopentylbenzene. Explain
4.
CH3 CHCH2
A
HF or BF3
CH3 AlCl3
+ H3C
Cl
H3C
7. Explain Friedel Crafts acylation requires on excess of the catalyst but Friedel
Crafts alkylation requires only a catalytic amount.
9. Convert
i)
Cl Cl CO 2H
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RSM79-Ph-III-EAS-CH-44
LEVEL - I
2. Benzyne carbon is
(A) sp-hybridised (B) sp2 hybridised
(C) Fluctuates between sp and sp2 (d) None of the above
5.
ICl
X. Identify `X'
FeBr3
Cl I
(A) (B)
Br
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RSM79-Ph-III-EAS-CH-45
6. CH2
' Z'
KMnO 4 / H
‘Z’ may be
HO
CO 2H OH
(A) (B)
OH
7. Among the following which should be used as solvent in Friedel Craft’s reaction
(A) Toluene (B) Benzeen
(C) Nitrobenzene (D) Phenol
H H D D
H D
(I) (II)
(A) I is faster than II (B) II is faster than I
(C) They follow the same rate (D) cannot be determined
9. -phenyl ethyl chloride is the minor product obtained by reaction of chlorine with
CH2 CH 2CH 3
HC
(A) (B)
CH3 H
H3C C CH3 C C
(C) (D)
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RSM79-Ph-III-EAS-CH-46
CH3
CH3
(C) (D)
CH3
CH3
A
Br2 / FeBr3
Br
(A) (B)
Br
CH3
CH3 CH3
Br
(C) (D) +
50% 50%
Br
Br
N N N N
H H H
(I) (II) (III) (IV)
(A) IV > I > III > II (B) III > I > IV > II
(C) I > III > II > IV (D) II > I > III > IV
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RSM79-Ph-III-EAS-CH-47
(A) (B)
CH3 CH3
(C) (D)
16. NH2
O
N
(A) (B)
N OH
17.
Y. Identify Y
KMnO 4 / H
CH3
CO 2H
(A) (B) CO 2H
CO 2H
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RSM79-Ph-III-EAS-CH-48
CH3
CH3 H3C CH3
CH3 H3C CH3
19. F
Z
i ) PhLi
ii) H2O
OH
Identify Z
OH
(A) (B)
OH
OH
OH
20. Which of the following is not true about Friedal Craft Alkylation?
(A) AlCl3 is used as a catalyst
(B) Does not occur with phenol or aniline
(C) Polyalkylation does not occur
(D) All of the above
(C) (D)
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RSM79-Ph-III-EAS-CH-49
1 2 3 4
S O N N
H
(A) 1 2 3 4 (B) 4 1 2 3
(C) 3 2 1 4 (D) 4 1 3 2
23. When –N+ (CH3)3 group is attached to the benzene ring, it orients the incoming
electrophile into
(A) Meta position
(B) Ortho position
(C)Para position
(D) Equally directs group to ortho-para position
24. When Benzene is treated with isobutyl bromide in the presence of AlCl3 it mainly
gives
(A) Tertiary butyl benzene (B) Isobutyl benzene
(C) n-butyl benzene (D) Secondary butyl benzene
25. Chlorination of toluene in the presence of light and heat followed by treatment
with aqueous NaOH
(A) o-cresol (B) p-cresol
(C) 2,4-dihydroxytoluene (D) benzoic acid
CCl 3
26.
A. A is
Nitration
CCl 3 CCl 3
NO 2
(A) (B)
NO 2
CCl 3
NO 2
27. In the reaction of p-chlorotoluene with KNH2 in liq NH3, the major product is
(A) o–toluidine (B) p–toluidine
(C) p–chloroaniline (D) m-toluidine
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RSM79-Ph-III-EAS-CH-50
(A) (B)
CH3
H3C CH3
(A) Br (B)
CH3
CH3
CH3
(C) (D)
Br Br
3. The reaction of biphenyl with HOCl in the presence of a strong acid gives
Cl Cl
(A) (B)
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RSM79-Ph-III-EAS-CH-51
Cl
(C) Cl (D)
Cl
10. 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
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RSM79-Ph-III-EAS-CH-52
3. The reaction,
C6H6 + CH3Cl
Anhydous
AlCl
C6H5CH3 + HCl
3
is an example of :
(A) Friedel-Crafts reaction (B) Kolbe’s synthesis
(C) Wurtz reaction (D) Grignard synthesis [CPMT 1990]
4. Which of the following alcohols is dehydrated most readily with conc. H2SO4?
(A) p-O2NC6H4CH(OH)CH3 (B) p-ClC6H4CH(OH) CH3
(C) p-CH3OC6H4CH(OH)CH3 (D) C6H5CH(OH) CH3
NH2 NH2
(a) (b)
NO 2
NH2 NH2
NH 2
(c) (d)
NH2 [AMU (Aligarh) 1992]
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RSM79-Ph-III-EAS-CH-53
LEVEL - IV
A Matrix-Match Type
Me
NO 2 (q) ortho with respect to methyl group
(b)
NO 2
NO 2 (r) only one mono substituted product
(c)
Me
NO 2 OH (s) meta with respect to NO2
(d) >
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.
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RSM79-Ph-III-EAS-CH-54
NO 2 NO 2
(A) (B)
Cl
Cl Cl Cl
NO2 NO 2
Cl
(C) (D)
Cl Cl
2. CH3
OH
E
CH3 CH3
OH OH
(A) (B)
E E
CH3
OH
(C) (D) (A), (B)
E
3. O
HN CH3
Cl2 / CH3COOH
O O
HN CH3 HN CH3
(A) (B) Cl
Cl
O O
HN CH3
HN
Cl
(C) (D) Cl
Cl
4. CH3
HNO3
H 2SO 4
NO 2
CH3
CH3
NO 2
(A) (B)
NO2
NO 2
NO2
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RSM79-Ph-III-EAS-CH-55
CH3
CH3
O2 N
(C) (D)
NO 2
NO 2
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
5. H3C CH3
Conc. H2SO4
(A)
(A) is
COOH COOH
(a) HOOC COOH (b) H3C CH 3
H3C
CHOH
(c) H3C CH 3 H3C CH 3
(d)
C2H5Cl, AlCl3
6. (A)
(c)
(d)
H5C2 C2H5
7. Among the three isomers shown below
HO HO HO
COOH
and
,
OH HO COOH
HOOC OH
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RSM79-Ph-III-EAS-CH-56
CHBrCH 2Br HC CH 2
(c) (d)
Br Br
Comprehension - III
It is not always easy to predict the position of attack on multiply 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 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
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RSM79-Ph-III-EAS-CH-57
O
||
CH 3 C Cl
CH3
CH3
(A)
(CH 3 )2 CHBr
AlCl3 ,15 25 C (B) AlCl3 ,CS2 5 C
NH2 NH2 OH OH
Br Br Br Br
(C)
Br2 .H 2 O
40 50 C
(D) Br2
CS 0o C
OH O 2
O Br OH Br
11. Which of the following side chain reaction/s can be used to reduce the activity of strongly
activating groups like —OH?
(A) Benzoylation (B) Acetylation
(C) Both of the above (D) None of the above
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RSM79-Ph-III-EAS-CH-58
LEVEL - III
LEVEL – IV
A B
Match the following WRITE-UP
1. (A – Q, R) 1. (D)
(B – Q, S) 2. (D)
(C – P) 3. (C)
(D – S) 4. (B)
2. (A – Q, R) 5. (D)
(B – P, R, S) 6. (C)
(C – Q, R) 7. (A)
(D – P, S) 8. (D)
9. (D)
10. (A) 11. (c)
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