Alkylhalides Arylhalides Aromatic Compounds 1

12.
ALKYL HALIDES,
ARYL HALIDES
A N D A R O M AT I C
COMPOUNDS
ALKYL HALIDES
1. INTRODUCTION
When hydrogen atoms or atoms of alkanes are replaced by a corresponding number of halogen atoms, the
compounds are called halogen derivatives of alkanes.
They are classified according to the number of halogen atoms that replace hydrogen atoms in the alkane.
Monohalogen derivatives: They contain only one halogen atom.
E.g. CH3Cl Methyl chloride
CH3CH(Br)CH3 2-bromopropane
Monohalogen derivatives of alkane are called alkyl halides
Dihalogen alkanes contain two halogen atoms.
Trihalogen alkanes contain three halogen atoms.
Monohaloalkanes
The general formula is RX where R is an alkyl group and X is a halogen.
Flowchart 12.1: Classification of haloalkanes

1 2 . 2 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Common system: ‘Alkyl halides’ are the monohalogen derivatives of alkanes. These are named by naming the alkyl
group attached to halogen and adding the name of the halide. E.g. Methyl halide, Isobutyl halide.
The name of the alkyl group and halide are written as two separate words. The prefixes used to distinguish alkanes
like n-, iso-, sec-, tert, etc. are also written.
IUPAC system: Rules for naming haloalkanes that have branches in carbon chains:
The monohalogen derivatives of alkanes are called haloalkanes. The name of haloalkanes are written by prefixing
the word ‘halo’ (bromo or chloro or iodo or fluoro) to the name of the alkane corresponding to the longest
continuous carbon chain holding the halogen atom. E.g. Bromoethane E.g. Trichloromethane
(a) The longest continuous chain containing the carbon attached to halogen group is selected as the parent alkane
(principal chain or parent chain). While naming alkanes, all the rules that apply to alkane names should be followed.
(b) The carbon atoms are numbered in such a way that the halogen carrying carbon atom gets the lowest number.
(c) The position of the halogen atom and other substituents are indicated by numbers 1,2,3….etc.
E.g. 1-Iodo-2-methylpropane
Dihalo derivatives
(a) When two halogen atoms are attached to the same Carbon-atom, these are called geminal dihalides. Alkylidene
dihalides or alkylidene dihalides are also names used for such compounds. E.g. ethlydine dichloride
(b) When two halogen atoms are attached to adjacent Carbon-atoms, they are called vicinal dihalides. As they
are prepared from alkenes, they are named as the dihalide of the alkene from which they are prepared. E.g.
ethylene dichloride
Polyhalo derivatives: Polyhalo derivative are compounds with multiple halogen atom. These have important
application in agricultural industry.
Fully halogenated hydrocarbons are also called perhalohydrocarbons under a common system.
Nomenclature of aryl halides: Aryl halides are termed Haloarenes in IUPAC systems. ‘Halo’ (bromo or chloro or
iodo or fluoro) is prefixed before the name of the aromatic hydrocarbon. In case of disubstituted compounds, the
relative positions are indicated by (1,2), (1,3) or (1,4). Ortho, meta and para are also used to indicate the positions.
E.g. Chlorobenzene, Bromobenzene.
2. PHYSICAL PROPERTIES OF ALKYL HALIDES

(a) Boiling point: The below chart shows the boiling point of some simple haloalkanes.
B.P(K)
400
Chlorides
Bromides
Room 300 Iodides
temperature
200
Gas
Gas
100
0
CH3X CH3CH2X CH3CH2CH2X
Figure 12.1: Boiling points of haloalkanes
Notice that three of these have b.ps’ below room temperature (taken as being about 20° C). These will be gaseous
at room temperature. All the other you are likely to come across are liquids.
Chem i str y | 12.3
PLANCESS CONCEPTS
•• The only methyl halide which is a liquid is iodomethane.

•• Chloroethane is a gas.
The pattern in b.p. reflects the patterns in intermolecular attractions.
Vaibhav Krishnan (JEE 2009, AIR 22)
(b) Boiling point of some isomers: The example shows that the boiling point fall as the isomers go from a
primary to a secondary to a tertiary haloalkane.
CH3
|
CH3 − CH2 − CH2 − CH − Br CH3 − CH2 − CH − CH3 CH3 − C − CH3
| |
Br Br
B.P.s' 375 K 364 K 346 K
To put it simply, this is the result of the fall in the effectiveness of the dispersion forces. The temporary dipoles are
greatest for the longest molecule. The attractions will also be stronger if the molecules can lie closely together. The
tertiary haloalkane is very short and fat, and won’t have much close contact with its neighbours.
(c) Solubility of haloalkanes

(i) Solubility in water: The haloalkanes are very slightly soluble in water. In order to dissolve haloalkane in
water, you have to break attractions between the haloalkane molecules (van der Waals dispersion and
dipole-dipole interactions) and break the hydrogen bonds between water molecules. Energy is released
when new attractions are set up between the haloalkane and the water molecules. These will only be
dispersion forces and dipole-dipole interactions. These aren’t as strong as original hydrogen bonds in
the water, and so not as much energy is released as was used to separate the water molecules.
(ii) Solubility in organic solvents: Haloalkanes tend to dissolve in organic solvents because the new
intermolecular attractions have the same strength as the ones being broken in the separate haloalkane
and solvent.
3. CHEMICAL REACTIVITY OF HALOALKANES
The importance of bond strengths: The pattern in strengths of the four carbon-halogen bonds are:
C-F C-Cl C-Br C-l

Figure 12.2: Carbon-halogen bond strength
Bond strength falls as you go from C-F to C-I(C-F being the strongest)
PLANCESS CONCEPTS
You will find almost as many different values for bond strengths (or bond enthalpies or bond energies) as
there are different sources! Don’t worry about this-the pattern is always the same. This is why you have
got a chart here rather than actual numbers.
Saurabh Gupta (JEE 2010, AIR 443)
In order for anything to react with the haloalkanes, the carbon-halogen bond has got to be broken. As that gets easier
when you go from fluoride to chloride to bromide to iodide, the compounds get more reactive in that order. Iodoalkanes
are the most reactive and fluoroalkanes are the least. In fact, fluoroalkanes are non-reactive and thus, not considered.
The influence of bond polarity: Out of the four halogens, fluorine is the most electronegative and iodine the
least. This means that the electron pair in the C-F bond will be dragged most towards the halogen end.
Let’s look at the methyl halides as a simple example:
+ - + - + -
F Cl Br l
No polarity
One of the important set of reactions of haloalkanes is substitute reactions, which involves replacing the halogen
by something else. These reactions involve:
(a) The carbon-halogen bond breaking to give positive and negative ions. The ion with the positively charged
carbon atom then reacts with something either fully or slightly negatively charged. Or,
(b) Something either fully or negatively charged attracted to the slightly positive carbon atom and pushing off
the halogen atom.
The thing that governs the reactivity is the strength of the bonds which have to be broken. It is difficult to
break a C-F bond, but easy to break a C-I one.
Illustration 1: (a) Dipole moment of CH3F is 1.85 D and that of CD3F is 1.86D. (JEE MAIN)
(b) 8-Hydroxy quinoline can be sepated from 4-hydroxy quinolone by steam distillation.
4
Sol: (a) Both the compound has dipole moment as they do not have structural symmetry
5
but CD3F has higher dipole moment compared to CH3F, It is due to the large size of CD3F, but
6 3
D is less EN than H. ( µ = q × d) 7 2
(b) 8-Hydroxy quinoline can be sepated from 4-hydroxy quinolone by steam distillation as it 8 N1
has higher boiling point due to intermolecular H-bonding. O H
Illustration 2: (a) The pK a of p-fluorobenzoic acid (I) is 4.14, whereas that of p-chlorobenzoic acid (II) is 3.99.
(b) Glycine exists as zwitterion, but PABA does not. (JEE MAIN)
Sol: (a) pKa is a quantitative measure of the strength of an acid in solution. The larger the pKa value, COOH
the more dissociation of the molecules in solution and thus the stronger the acid.
In p-Fluorobenzoic acid + R (resonance effect) is more due to more effective overlap of 2p of F
and 2p of C; combined effect of +R and –I, net e- donating by resonance is slightly more. So, it is
a weaker acid than p-chlorobenzoic acid. (2p)
:F:
(2p)
:
(I)
Chem i str y | 12.5
In case of p-chlorobenzoic acid +R (resonance effect )is very less, due to less effective overlap of COOH
3p of Cl and 2p of C. Combined effect of +R and –I; net e -withdrawing effect is more. So, it is a
‒
stronger acid than p-fluorobenzoic acid.

(b) At a particular pH certain organic molecule (amino acids) exist as a Dipolar ion. These are
called as Zwitter ion. Zwitter ion contains one positive and one negative charge and thus they are (2p)
electrically neutral. :Cl:
(3p)
:
Glycine is an amino acid it contains both acidic and basic functional group thus (II)
(H N − CH − COOH←
2
→H N
 3
⊕
)
− CH2 − COOΘ , the aliphatic ( −NH ) group is sufficiently basic to
2
(Dipolar or Zwitter Ion)
accept H⊕ from ( −COOH) and exists as a dipolar ion (zwitterion),
H2 N COOH
whereas in PABA (p-amino benzoic acid; an aromatic acid, due to presence of electron donating group ( −COOH)
is not strong enough to donate H⊕ to a much weaker base ( Ar − NH2 ) . So, the dipolar ion is not formed.
Illustration 3: Calculate the dipole moment of the following compound:

1.55D
Given: µC −CI = 3.95D
µC −NO =
2 o
180
O2N Cl O2N Cl
Sol: Dipole moment is given by μ = q × r

o
180
O2N Cl O2N Cl
R 2 =P2 + Q2 + 2PQ cos θ

=P2 + Q2 + 2PQ cos180 =P2 + Q2 − 2PQ ;
(P + Q )
2
2
R= ; R
= (P + Q ) ∴ R= 3.95 − 1.55
= 2.4D
4. CHEMICAL REACTIONS OF ALKYL HALIDES
(a) Nucleophilic substitution reaction

(i) Nucleophilic substitution in primary haloalkanes
Nucleophiles: A nucleophile is a species (an ion or a molecule) which is strongly attracted to a region
of positive charge.
-: O H -: C N - : O + + - +
:
: :
H H N
+H H
+
Nucleophiles are either fully negative ions, or have a strong –ve charge. Common nucleophiles are hydroxide ions,
cyanide ions, water and ammonia. Notice that each of these contains at least one lone pair of electrons either on
an atom carrying a full negative charge, or on a very electronegative atom carrying a substantial-charge.
The nucleophilic substitution reaction –an SN2 reaction: We’ll discuss this mechanism by using an ion as a
nucleophile because it’s slightly easier. The water and ammonia mechanisms involve an extra step which you
can read about on the pages describing those particular mechanisms. We’ll take bromoethane as a typical
primary halogenoalkane. The bromoethane has a polar bond between the carbon and the bromine. We’ll
look at its reaction with a general purpose nucleophilic ion which we’ll call Nu-. This will have at least one
lone pair of electrons. Nu- could, for example, be OH- or CN-. The lone pair on the Nu- ion will be strongly
attracted to the +carbon, and will move towards it and begin making a co-ordinate (dative covalent) bond.
In the process, the electrons in the C-Br bond will be pushed even closer towards the bromine, making it
increasingly negative.
-
Br Br
+ Nu
Nu
The movement goes on until the –Nu is firmly attached to the carbon, and the bromine has been expelled as
a Br‒ ion.
Note: We haven’t shown all the lone pairs on the bromine here. These other lone pairs aren’t involved in the
reaction, and including them simply clutters the diagram to no purpose.
Things to notice: The Nu- ion approaches the carbon from the far side of the bromine atom. The large
bromine atom hinders attack from the side nearest to it and, being –ve would repel the incoming Nu- anyway.
This attack from the back is important if you need to understand why tertiary haloalkanes have a different
mechanism. There is obviously a point in which the Nu- is half attached to the carbon, and the C-Br bond is
half way to being broken. This is called a transition state. It isn’t an intermediate. You can’t isolate it - even for
a short time. It’s just the mid-point of a smooth attack by one group and the departure of another.
+
CH3 + : Nu → H3C − Nu
PLANCESS CONCEPTS
In exam, you must show the lone pair of electrons on the nucleophile (in this case, the Nu- ion). It
probably doesn’t matter whether you show them on the departing Br-ion or not.
CH3 CH3 H Aman Gour (JEE 2012, AIR 230)
Nu: C Br Nu C Br
Technically, this is known as Han SN2+reaction.
- S stands for substitution, N for nucleophilic, and the 2 refers to the
initial stage of the reaction thatHinvolves two species –the bromoethane
H and the Nu- ion.
Transition state
Mechanism: The step-wise mechanism needs to be drawn as shown with very clear details as it gives one a picture
of the molecule’s arrangement in space.
CH3 CH3 H
CH CH3 CH
H 3
3
Nu: C Br Nu:
Nu C
C Br NuNu C C Br + : Br
H + - H + - H
H H H HH
Transition state Transition state
Notice that the molecule has been inverted during the reaction-rather like an umbrella being blown inside-out.
(ii) Nucleophilic substitution in tertiary

CH3haloalkanes: RememberCH that
3 a tertiary haloalkane has
CH3
three alkyl groups attached to the carbon with the halogen on it. These alkyl groups can be the CH C CH
Nu C + : Br Nu C + : Br
same or different. Consider a simple Hone, (CH3)3CBr - 2 - bromo-2-methylpropane.
3 3
H
Br
H H
Chem i str y | 12.7
The nucleophilic substitution reaction-an SN1 reaction

Why is a different mechanism necessary?
You will remember that when a nucleophile attacks a primary haloalkane, it approaches the +ve C from the side
away from the halogen atom. With a tertiary haloalkane, this is impossible. The back of the molecule is completely
cluttered with CH3 groups.
The alternative mechanism: The reaction happens in two stages. In the first, a small proportion of the haloalkane
ionizes to give a carbocation and a bromide ion.
CH3 CH3
slow
CH3 C Br CH3 C+ + : Br
CH3 CH3
This reaction is possible because tertiary carbocations are relatively stable compared to secondary or primary ones.
Even so, the reaction is slow. However, once the carbocation is formed,, it will react immediately when it comes into
contact with a nucleophile like Nu-. The lone pair on the nucleophile is strongly attracted towards the +ve C, and
moves towards it to create a new bond.
CH3 CH3
+ : Nu fast
CH3 C CH3 C Nu
CH3 CH3
The speed of the reaction is governed by the ionization of haloalkane. Because this initial slow step only involves
one species, the mechanism is described as SN1 -substitution, nucleophilic, one species taking part in the initial
slow step.
Why don’t primary halogenoalkanes use the SN1 mechanism?

If a primary haloalkane uses this mechanism, the first step would be, for example:
slow +
CH3 CH2 Br CH3 CH2 + : Br
A primary carbocation would be formed, and this is much more energetically unstable than the tertiary one formed
from tertiary haloalkanes-and therefore, much more difficult to produce.
This instability brings in a very high activation energy for the reaction involving a primary haloalkane. The activation
energy is much less if it undergoes an SN2 reaction.
(iii) Nucleophilic substitution in secondary haloalkanes: There isn’t anything new in this. Secondary haloalkanes
will use both mechanisms-some molecules will react using the SN2 mechanism and other, the SN1. The SN2
mechanism is possible because the back of the molecule isn’t completely cluttered by alkyl groups and so,
the approaching nucleophile can still reach the carbon atom. The SN1 mechanism is possible because the
secondary carbocation formed in the slow step is more stable than a primary one. It isn’t as stable as a tertiary
one though, and so the SN1 route isn’t as effective as it is with tertiary haloalkanes.
SNi mechanism
(i) Reaction of SOCl2 with Secondary Alcohols: The SNi Mechanism: Walden noted that CH3 CH CH3
when (+)-malic acid treated with PCl5 , the product was (-) chlorosuccinic acid –a process
that proceeded with inversion of stereochemistry. When (+) malic acid was treated with Br
a secondary
thionyl chloride (SOCl2), the product was (+)-chlorosuccinic acid. This proceeds with
haloalkane
retention of stereochemistry.
How can we understand this?
O H Cl O HO H O Cl H
OH PCl5 OH SOCl2 OH
HO HO HO
O O O
(-)-chlorosuccinic acid (+)-malic acid (+)-chlorosuccinic acid

Inversion Retention
(ii) Why Adding SOCl2 And Pyridine Leads To Inversion (via SN2): As it turns out, the stereochemistry of
this reaction can change to inversion if we add a mild base- such as pyridine.
O
Cl
O
: :
S O
: :
Cl Cl
Cl S Cl
Cl H S
:
O HO : H O HO H O O H
OH OH OH
HO HO HO
O O O
Attack of OH upon SOCl2 Expulsion of Cl- to form Formation of ‘’chlorosulfite’’

protonated chlorosulfite (can be Isolated)
O
O O
S
S S O
: :
O : :
: :
Cl O Cl Cl
O O
:
H H
O OH OH
HO HO
OH
HO O O
O
Departure of leaving group Chloride attacks cabocation Loss of SO2

to form ‘’intimate ion pair’’ on same face of ‘’Intimate’’ ion
Both reactions form the “chlorosulfite” intermediate. But, when pyridine (a decent nucleophile) is present,
it can attack the chlorosulfite, displacing chloride ion and forming a charged intermediate. Now, if the
leaving group departs, forming a carbocation, there’s no lone pair nearby on the same face that can
attack. In other words, by displacing chloride ion, pyridine shuts down the SNi mechanism.
Chem i str y | 12.9
PLANCESS CONCEPTS
SOCl2 plus alcohol gives retention of configuration, SOCl2 plus alcohol plus pyridine give inversion
of configuration (SN2)
O HO H O H Cl
OH SOCl2 OH
HO HO
Pyridine
O O
(+)-malic acid (+)-chlorosuccinic acid
inversion
(iv) Factors affecting nucleophilic substitution reactions:

•• Steric Nature of the Substrate. Steric accessibility of the electrophilic center in the substrate is probably
the most important factor that determines if a nucleophilic substitution will follow a SN1 or an SN2
mechanism.
Examples of SN2 (sterically accessible) substrates
H3C CH Br
CH3 Br CH3 CH2 Cl H3C CH CH33 Br Br
CH3 Br CH3 CH2 Cl CH Br
Cl
Primary substrates Cl
Primary substrates primary allylic halides
Unhindered secondary substrates primary allylic halides
Unhindered secondary substrates
Examples of SN1(sterically hindered) substrates
H C Br CH3
CH3 H33C Br CH3
CH3 H3C C CH2 Cl
H C C Br H3C C CH2 Cl
H33C C Br
CH3 Cl CH3
CH3 Cl CH3
Tertiary halides Hindered secondary halides Hindered primary halides
Tertiary halides Hindered secondary halides Hindered primary halides
PLANCESS CONCEPTS
Some substrates, whether they are sterically hindered or not, may prefer to undergo SN1 reactions if they
can dissociate into very stable carbocations in the presence of the solvent. In most cases, this involves
resonance-stabilized cations.
Examples of SN1 substrates that form stable carbocations
Br
Polar solvent + -
CH2 + Br
Cl
+

1 2 . 1 0 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
•• Nature of the nucleophile: Both SN1 and SN2 reactions prefer small nucleophiles. Large nucleophiles
have more difficulty accessing the electrophilic center in the substrate. They also have an increased
tendency to act as Bronsted bases, seeking acidic protons rather than electrophilic centers. This is due to
the lower activation energy of acid-base reactions compared to nucleophilic substitutions.
- - - - - - - -
OH CH3O CH3 CH2 O CN RS R C C Br l
Small, strong nucleophiles that favor SN2 reactions are shown below. Most of them have a localized
negative charge. It is also better if they are weak bases, such as bromide and iodide ions, but they can
be strong bases such as hydroxide and alkoxide ions (conjugate bases of alcohols).
Weak, small nucleophiles that favor SN1 reactions are shown below. Notice that several of them are the
conjugate acids of strong nucleophiles. They are also typically neutral, but some have a delocalized
negative charge.
O
-
H2O CH3OH CH3 CH2 OH RSH NH3 F C -
H3 C O
Large nucleophiles, especially if they are strong, have a tendency

CH3 to act as Bronsted bases rather than as
-
nucleophiles. They should be avoided if a nucleophilic H
N reaction
3C C isOdesired.
•• Solvent used: It has already been mentioned that SN2 mechanisms

CH3 are favored by low to moderate
polarity solvents such as acetone and N, N-dimethylformamide(DMF). SN1 mechanisms are favored by
moderate to high polarity solvents such as water and alcohols. In SN1 reactions, quite frequently, the
solvent also doubles as the nucleophile. Water and alcohols are prime examples of this practice.
O
O C CH3
H N H2O CH3OH CH3CH2
C
H3C CH3 CH3 Water Methanol Ethanol
Acetone DMF
SN2 Solvents SN1 Solvents
•• Leaving group: The nature of the leaving group has more of an effect on the reaction rate (faster or
slower) than it does on whether the reaction will follow an SN1 or SN2 mechanism. The most important
thing to remember in this regard is that good leaving groups are weak bases.
o Except for fluorine, all halogens are good leaving groups
o Groups that leave as resonance stabilized ions are also weak bases and therefore, good leaving
groups.
o Water is a good leaving group frequently used to prepare alkyl chlorides and bromides from alcohols.
The OH group in alcohols is not a good leaving group because it leaves as a hydroxide ion, which is a
strong base. However, if the hydroxyl group is protonated first with a strong acid, it can leave as a water
molecule, which is a good leaving group.
Illustration 4: Prepare the following ethers via Williamson’s synthesis.

I. Di-n-propyl ether (A) II. Benzyl methyl ether (B)
III. Phenylethyl ether (C) IV.t-Butyl ethyl ether (D) (JEE MAIN)
Sol: Reaction of alcohol with alkyl halide in the presence of base yields ether. This reaction is known as Williamson’s
Synthesis.
Na
I. n − Pr OH  n−Pr Br
→ n − PrOΘ  → Pr OPr ( A )
Na
II. MeOH  → MeOΘ  ( )
PhCH Br
2 → PhCH OMe B
2
NaOH
III. PhOH   EtBr
→ PhOΘ  → PhOEt ( C )
Chem i str y | 12.11
Na
IV. t − BuOH 
EtBr
→ t − BuOΘ  → t − Bu − OEt (D )
This reaction gives a poor yield because of the bulkiness of t-BuO-
Illustration 5: An aromatic compound ( A )( C7H8 O ) on reaction with Br2+H2O gives a white ppt. of compound
(B )( C7H5OBr3 ) . Compound ( A ) is soluble in NaOH. Compound ( C ) , an isomer of ( A ) , also gives the same
reaction and gives a white ppt. of compound (D )( C7H5OBr3 ) . Compound ( C ) is insoluble in NaOH. Identify
( A ) , (B ) , ( C ) and (D ) . (JEE ADVANCED)
Sol: OH OH
Br Br
Br2/H2O
CH3 CH3
(A)
Br
(B)
OCH3 OCH3
Br Br
Br2/H2O
(C)
Br
(D)
Illustration 6: Starting from C6H6 and C6H5OH, synthesize phenyl-2,4-dinitrophyneyl ether (B) (JEE ADVANCED)
Sol:
Cl Cl
NO2
Cl2
Path I : C6H6
FeCl3 Fuming
HNO2
NO2 -
PhO
(A)
-
OH O O
- NO2
OH
Path II :
Cl
NO2
(B)
O Nitration
(b) Elimination reactions: We have seen that alkyl halides may react with basic nucleophiles such as NaOH via
substitution reactions.
H H
H
-O : : : :-
: :
: :
: :
: :
: :
: :
:
H + C Br H O C Br H O C + Br
H
H HH H
H
transition state
When a 2° or 3° alkyl halide is treated with a strong base such as NaOH, dehydrohalogenation occurs producing
an alkene-an elimination (E2) reaction.
KOH in ethanol
Br + KBr + H2O
-HBr
There are 2 kinds of elimination reactions, E1 and E2.

E2 = Elimination, Bimolecular (2nd order). Rate = K RX  Nu :− 
 
E2 reactions occur when a 2 or 3 alkyl halide is treated with a strong base such as OH, OR, NH− , H− , etc.
ο
2
H

OH- + C C C=C + Br + HO-H

Br
The Nu: removes an H+ from a β-carbon, the halogen leaves forming an alkene
All strong bases, like OH, are good nucleophiles. In 2° and 3º alkyl halides, the α-carbon in the alkyl halide is
hindered. In such cases, a strong base will ‘abstract’ (remove) a hydrogen ion (H+) from a β-carbon, before it hits
the α-carbon. Thus, strong bases cause elimination (E2) in 2° and 3 alkyl halides and cause substitution (SN2) in
unhindered methyl° and 1° alkyl halides.
In E2 reactions, the Base to H σ bond formation, the C to H σ bond breaking, the C to C π bond formation, and
the C to Br σ bond breaking all occur simultaneously. There are no intermediate forms of carbocation. Reactions in
which several steps occur simultaneously are called ‘concerted’ reactions.
(i) Zaitsev’s Rule: Recall that, in elimination of HX from alkenes, the more highly substituted (more stable)
alkene product predominates.
Br
CH3CH2O- Na+
CH3CH2CHCH3 CH3CH=CHCH3 + CH3CH2CH=CH2
EtOH
2-butene 1-butene
major product minor product
(>80%) (<20%)
•• E2 reactions, do not always follow Zaitsev’s rule.

•• E2 eliminations occur with anti-periplanar geometry, i.e. periplanar means that all 4 reacting atoms-
H, C, C, & X- all lie in the same plane. Anti means that H and X (the eliminated atoms) are on opposite
sides of the molecules.
•• Look at the mechanism again and note the opposite side and same plane orientation of the
mechanism:
•• When E2 reactions occur in open chain alkyl halides, the Zaitsev product is actually the major product.
Single bonds can rotate to the proper alignment to allow the antiperiplanar elimination.
•• B- +
H R B R
H R R
C C R C C C C +B-H+X-
R
R R
R X R X- R R

•• In cyclic structures, however, single bonds cannot rotate, in regards with the stereochemistry. See the
following example.
E.g. Trans-1-chloro-2-methylcyclopentane undergoes E2 elimination with NaOH. Draw and name the
major product.
H H3 C
H3 C H H
Na+ OH- + NaCl
H H3C
+ HOH H
H H E2 H
H H
Cl Non zaitsev product Little or no zaitsev (more stable)
is major product product is formed
3-methylcyclopentene 1-methylcyclopentene
(ii) Substitution vs Elimination:

•• As with E2 reactions, E1 reactions also produce the more highly substituted alkene (Zaitsev’s rule).
However, unlike E2 reactions where no C+ is produced, C+ arrangements can occur in E1 reactions.
•• E.g. t-butyl chloride + H2O (in EtOH) at 65ºC
•• CH3 CH3 CH3 H
H2O, EtOH
CH3 C Cl o
CH3 C OH + C=C
65 C
CH3 CH3 H Br-
CH3
64% 36%
SN1 E1
product product
•• In most unimolecular reactions, SN1 is preferred to E1, especially at low temperatures.

•• If the E1 product is desired, it is better to use a strong base and force the E2 reaction.
•• Note that increasing the strength of the nucleophile favors SN1 over E1. Can you postulate an
explanation?
Mixtures of products are usually obtained.
PLANCESS CONCEPTS
Predicting Reaction Mechanisms
•• Non basic, good nucleophiles, like Br − and l− will cause substitution not elimination. In 3° substrates,
only SN1 is possible. In Me and 1° substrates, SN2 is faster. For 2° substrates, the mechanism of
substitution depends upon the solvent.
•• Strong bases, like OH- and OR-, are also good nucleophiles. Substitution and elimination compete. In
3° and 2° alkyl halides, E2 is faster. In 1° and Me alkyl halides, SN2 occurs.
•• Weakly basic, weak nucleophiles, like H2O , EtOH, CH3COOH , etc., cannot react unless a C+ forms.
This only occurs with 2° or 3° substrates. Once the C+ forms, both SN1 and E1 occur in competition.
The substitution product is usually predominant
•• High temperatures increases the yield of elimination product over substitution product.
( ∆G =∆H − T∆S ) Elimination produces more products than substitution, hence creates greater
entropy (disorder).
•• Polar solvents, both protic and aprotic, like H2O and CH3CN, respectively, favor unimolecular
reactions (SN1 and E1) by stabilizing the C+ intermediate. Polar aprotic solvent enhance bimolecular
reactions (SN2 and E2) by activating the nucleophile.
(iii) E1CB elimination: In any E1CB reaction, a base first removes a proton from the α carbon of the substrate
to give an intermediate carbanion (a species with a negatively charged carbon). This carbanion then
( )
loses the leaving group − : L to form alkene products (s). The E1CB mechanism usually occurs with
strong bases and with substrates where groups directly attached to the carbanion center can stabilize that
center’s negative charge.
- -
B: H C C L B H :C C L
- -
:C C L C = C :L
(iv) Elimination of X-X: Alkenes also form from the loss of both X’s of a 1,2-dihaloalkane.
X X Elimination
of
C C C=C
Both
X’s
These dehalogenation reactions do not involve bases. They use metals such as Mg or Zn that react with
the halogens (Cl, Br, and/or I) to form metal salts such as MgX2 or ZnX2 .Their mechanisms probably
involve formation of intermediate organometallic compounds on the metal surface that then eliminate
as +Mg ‒ X or +Zn ‒ X and X‒
Mg
BrCH2 CH2Br CH2=CH2+MgBr2
Ether
Zn
(CH3)3 C CHBr2 CH2Br (CH3)3 C CH2 CH=CH2+ZnBr2
Br
Zn
+ ZnBr2
Br
Reaction with organometallic compounds:

(a) Grignard reagent:
(i) Reaction of RX with Mg in ether of THF
(ii) Product is RMgX-an organometallic compound (alkyl-metal bond) Carbanions (CH3-Mg+) are very strong

1ooalkyl
2oalkyl Cl
3 alkyl R X Br
alkenyl l
aryl
Mg Ether
or THF
R Mg x
l +Mgl
Mg
C - C Basic and nucleophilic
H H Ether H H
H H
Iodomethane Methylmagnesium iodide
Mg 2 → CH CH CH CH CH CH H O
CH3CH2CH2CH2CH2CH2Br  → CH3CH2CH2CH2CH2CH2MgBr  3 2 2 2 2 3
Ether
1-Bromohexane 1-Hexylmagnesium bromide Hexane (85%)

(iii) Alkylithium (RLi) forms from RBr and Li metal

(iv) RLi reacts with copper iodide to give lithium dialkylcopper (Gilman reagents)
(v) Lithium dialkylcopper reagents react with alkyl halides to give alkanes
Basic and
nucleophilic
2Li
CH3CH2 CH2CH2Br CH3CH2 CH2CH2Li + LiBr
Pentane
1-Bromobutane Butyllithium
Ether
2 CH3Br + Cul (CH3)2Cu- Li+ + Lil
Methyllithium Lithium dimethylcopper
(a Gilman reagent)
Ether
(CH3)3CuLi + CH3(CH2)8CH2l o
CH3(CH3)8CH2CH3 + Lil + CH3Cu
0C
Lithium 1-lododecane Undecane (90%)
dimethylcopper
(b) Miscellaneous reactions:

Dry ether
(i) Wurtz Reaction: 2R − X + 2Na → 2NaX + R − R
ether
(ii) Formation of Grignard’s Reagent R − X + Mg  → RMgX
Dry ether
(iii) Corey House Reaction R 2CuLi + R ' X → R − R '+ RCu + LiX
R 2CuLi is prepared as follows:

Dry ether
•• (i) R − Br + 2Li → LiBr + RLi
Dry ether
•• (ii) 2RLi + CuI → R 2CuLi + LiI
(iv) Friedel Crafts Reaction

R

Anhy.AlCl3
+R X + HX

(v) Reduction Reactions

Ni
•• R − CI + H2 
Pt or Pd
→ R − H + HCI
Re dP
•• R − I + HI →
∆
R − H + I2
•• Zn−Cu/alc
R − CI + 2 H  → R − H + HCl
•• R − CI + LiAlH4 → R − H + LiCl + AlCl3

Illustration 7: Identify all the possible alkenes that would be formed on the dehydrohalogenation of the following
organic halides with alcoholic KOH. Also, identify the major alkene.
i. 1-Chloropentane ii. 2-Chloropentane (JEE MAIN)
Sol: 4 2 4 2
4 Cl Alc. KOH
5 2 5 4
i. Cl Alc. KOH
2
1 + Me
5Me 3 1 Me
5 3 Me
Me 3 1 Me 3 1 + Me Me
Pent-1-ene Pent-2-ene
Pent-1-ene
(Minor) Pent-2-ene
(Major)
(Minor) (Major)
ii. Cl
Cl
5 4 2 Alc. KOH
Me Me + Me
5Me 4 3 2 1 Alc. KOH Me
Me Me + Me
Me 3 1 Me Pent-2-ene Pent-1-ene
Pent-2-ene
(Major) Pent-1-ene
(Minor)
(Major) (Minor)
Illustration 8: Predict the order of reactivity of the following compounds in dehydrohalogenation. (JEE MAIN)
Me
I. Me Cl II.
Cl
Me
Me
Me
III. Br IV. Me
Me Br
Br
V.
Me Me
Me
Sol: Stability of carbocation has the influence on reactivity towards dehydrohalogenation. The more stable the
carbocation, greater is the reactivity towards dehydrohalogenation.
Order of the Stability of carbocation: tert>sec>primary.
Find out the carbocation formed during each reaction and predict the order of reactivity accordingly.
Order of reactivity: (V) > ( III ) > ( II ) > ( IV ) > ( I )
+
I. Me Cl Me
o +
1C
Me
Me
+ +
o
2C
o + o
+
(1 C 2C )
(Ease of formation: 3ο > 2ο > 1ο carbocation).

Me Me Me
Me +
II. Cl +
Me Me Me
o + o
+
1C 3C
+ +
(1oC 3oC )
Me
Me + Me Me
Br +
III.
Me Me Me
+
3 C+
o o
1C
o
+ o
+
(1 C 3C )
IV. Me Me +
(only 2oC )
Me Me
+
2 C+
o
Br
Me
Me
+ o +
(only 3 C )
V. Br
Me
Me Me Me
o
3C
Illustration 9: Me Me (JEE ADVANCED)

H
1 H
2 -
EtO + EtOH
Cl Only one product
trans-1-Isopropyl-2-chloro
cyclohexane
Sol: Bulky group at equatorial position imparts stability to the ring. In order to undergo dehydrohalogenation
reaction the basic condition to be followed is that the two leaving group has to be in anti periplanar geometry. By
using this condition answer the question.
•• Here Bulky group has to be in equatorial position (down the plane) as to impart stability and Cl group should
also be at equatorial position (up the plane) for trans-configuration.
•• In Dehydrohalogenation reaction one important requirement is the orientation of the two leaving atom.
•• The two leaving atom has to be in Anti periplanar position.
•• Here there are two possibilities, H can be eliminated from C1 or it can be eliminated from C3.
•• On talking about H at C1, The H atom occupies axial position and Cl is in equatorial position. Thus the orientation
is Syn periplanar (Both upward) so the reaction is not feasible. Thus we only get one product.

Me
(Cl) and group in trans-position
Me
Axial H at C-1 and equatorial Cl Equatorial H at C-3

at C-2 are in syn-periplanar (down the plane) and equatorial
position (both upward) Cl at C-2(up the plane) are in
No reaction anti-periplanar position
H Me Me Me Me
1a 1 1
e Me 2
H Me
Cl
2 e 2 3
3 3
H a
H
•• H atom at C3 occupies equatorial position and Cl is also in equatorial position thus the orientation is anti, thus
we get the product.
Illustration 10: Explain the stereochemistry of the products from E2 dehalogenation with IΘ of the following.
E2-dehydrobromination of (a) R, R-2, 3-dibromobutane and (b) meso-(R,S)-2, 3-dibromobutane. ( JEE ADVANCED)
Sol: Draw the structure of the compound (a) and (b).In order to undergo dehydrohalogenation reaction the two
leaving group has to be in anti periplanar. In order to get this condition interchange the group accordingly. Br-
attacks the compound from the bottom side.
(a)
Br
(b)
Me Me
Me H H H
Me
Me
Br Br + Me
Br Br
H
cis or E-2-Bromo-2
butene (Note: cis or E)
:
B
(R,S)
5. PREPARATION OF ALKYL HALIDES

Numerous ways to make alkyl halides.
1. Free Radical Halogenation
(a) Alkane +Cl2 or Br2, heat or light replaces C-H with C-X but gives mixtures
i) Hard to control ii) Via free radical mechanism
(b) It is usually not a good idea to plan a synthesis that uses this method-multiple products
CH4 + Cl2 h CH3Cl + HCl

Cl2
CH2Cl2 + HCl
Cl2
CHCl3 + HCl
Cl2
CCl4 + HCl
Radical Chain Mechanism

h
Initiation step Cl Cl 2 Cl

H3 C H H Cl
Step 1
+ +

Propagation steps H3 C
Cl
(a repeating cycle)
+ Step 2 +
H3C Cl Cl Cl

H3 C + CH3 H3C CH3
Termination steps Cl + CH3 Cl CH3
Cl + Cl Cl Cl
Overall reaction CH4 + Cl2 CH3Cl + HCl
Radical Halogenation: Selectivity

If there is more than one type of hydrogen in an alkane, reactions favor replacing the hydrogen at the most highly
substituted carbons
Cl
h
CH3 CH2 CH2 CH3 + Cl2 CH3 CH2 CH2 CH3Cl + CH3CH2 CH CH3
Butane 1-Chlorobutane 2-Chlorobutane

30 : 70
( )
30% 1ο Product
= 5%per(1ο )H
70%(2ο )Product
= 17.5%per(2ο )H
6 (1 ) H's
ο
4(2ο )H's
17.5%per(2ο )H
∴ = 3.5 : 1 relative Reactivity
5%per(1ο )H
CH3 CH3 Dichloro-,

CH3
h tricholoro-,
CH3 CH CH3 + Cl2 CH3 CCH3 + CH3 CHCH2Cl +
tetrachloro-,
Cl and so on
2-Chloro-2- 1-Chloro-2-
methylpropane methylpropane

35 : 65
( )
65% 1ο Product
7.2%per(1
= ο
)H
35%(3ο )Product
35%per(3ο )H
9 (1 ) H's
ο
1(1ο )H's
35%per(3ο )H
∴ =5:1 relative reactivity
7.2%per(1ο )H
Relative Reactivity
1. Based on quantitative analysis of reaction products,
relative reactivity is estimated for RCH3
( )
R2CH2
Cl2 : 5 : 3.5 : 1for 3ο : 2ο : 1ο R3CH
R’ H + .Cl
2. Order parallels stability of radicals
3. Reaction distinction is more selective with bromine than Energy R’. + HCl
chlorine (1700:80:1 for 3ο : 2ο : 1ο )
H H H H R H R’ Cl
H H R
C C C
R H R R R R C C C Reaction progress
R H R R R R
Primary < Secondary < Tertiary Primary < Secondary < Tertiary Figure 12.1: Energy profile diagram of different
1.0 3.5 5.0
alkyl halide
Reactivity Stability
2. Allylic Bromination: (Allylic means adjacent to a C=C double bond)

The bromination of cyclohexene produces a high yield of 3-bromocyclohexene.
Allylic positions Allylic hydrogens
H H H Br
h
+ Br2 + HBr
cyclohexene H H 3-bromocyclohexene
(80%)
An allylic hydrogen has been substituted for a bromine.
The bromine atom abstracts an allylic hydrogen because the allylic radical is resonance stabilized.
The radical then reacts with a bromine molecule to continue the chain.
abstraction of allylic H
H
H H
. H H Br
Br. . Br - H +
H
.
H
Br - Br
+ Br .
H H H
Cyclohexene allylic radical allylic bromide
3. From Alcohols
anhydrous
(a) Preparation of alkyl chloride: R − OH + HCl 
ZnCl ∆
→ R − Cl + H2O
2,
anhydrous ZnCl
(i) 2 → CH CH − Cl + H O
CH3CH2 − OH + HCl( g)  3 2 2
(ii) CH3 anhydrous CH3

CH OH + HCl(g) CH Cl + H2O
CH3 ZnCl2 CH3
(iii) CH3 CH3

CH3 C OH + HCl(g) CH3 C Cl + H2O
CH3 CH3
Note: Tertiary alcohols react with HCl(g) even in the absence of anhydrous ZnCl2.
conc.H SO
(b) Preparation of alkyl bromides: R − OH + HBr →2 4
reflux
R − Br + H2O
conc.H SO
(i) CH3CH2 − OH + HBr →2 4
reflux
CH3CH2 − Br + H2O
reflux
(c) Preparations of alkyl iodides: R − OH + HI → R − I + H2O
reflux
CH3CH2 − OH + HI → CH3CH2 − I + H2O
From alcohols using PX3 or PX5
3R − OH + PCl3 → 3R − Cl + H3PO3
R − OH + PCl5 → R − Cl + POCl3 + HCl
From alcohols using SOCl2 (Thionyl chloride) [Darzen’s Procedure]
Pyridine
R − OH + SOCl 
reflux
→ R − Cl + SO + HCl
CCl
4. Borodine Hunsdiecker Reaction: RCOOAg + Br2 → 4
reflux
R − Br + CO2 + AgBr
Mechanism
RCOOAg R C O + Ag
O
Step 1 : R C O+Br Br R C O Br + Br
O O
Step 2 : Initiation
R C OBr R C O + Br
O O
Step 3 : Propagation
R C O R + CO2
O
Step 4 : Propagation
R + R C O Br R Br + R COO
O
Step 5: (a) R − COO + R  → R − COOR (side product)

(b) If ethyl free radical then

CH3CH2 → CH2 = CH2 + H

H + CH3CH2 → CH3CH3
H + Br  → HBr
5. Finkelstein Reaction
3 CH OH or
R − Cl + NaI → R − I + NaCI
NaCl
acetone
acetone
R − Cl + NaBr  → R − Br + NaCl.
The reverse reactions, is not possible because NaCl and NaBr are insoluble in CH3OH or acetone.
Illustration 11: Identify all the possible products. Give the major products and rank the products in decreasing
order of reactivity with NBS.
Me Me
NBS + h
Products
(
Sol: Reactivity order: 3ο allylic > 2ο allylic > 1ο allylic )
(I) > (II) = (III) > (IV) o
2 allylic
Me Me Me Me
NBS + h
o
1 allylic Allylic
bromination Br
o
3 allylic
(I)
o
2 allylic Major
Br
+
Me Me Me Me
+
(III) Br (II)
Br
+ Me
(IV)
Illustration 12: Identify all the possible products. Give the major products and list them in decreasing order of
reactivity with Me3COCl.
Me
Me3COCl
Products
Me Me h
Me3COCl
Me
Products
Me h
( )
Me
Sol: Reactivity order: 3ο allylic > 2ο allylic > 1ο allylic Me Me3COCl
Me Me +h
Me Me3COCl
Allylic
Me
o
2 allylic +h chlorination
Me
Allylic
o
o
2 allylic
1 allylic Cl chlorination
Me
Me
o
1 allylic Cl + Cl Me
Me Me Me Me
(I) + Cl (II)
Me Major Me Minor
Me
(I) (II)
Major Minor
Illustration 13: which of the following will solvolyse faster in SN1 and why?
CH3 H
H CH3
H and Br
Br H
(A) (B)
Sol: Compound with Substituents on equatorial position are more stable than Diaxial compound. Less stable
compound undergoes the reaction faster.
•• The rate of SN1 reaction depends on the difference in energy of the ground state and the transition state.
•• In compound (A) both H occupies equatorial position whereas in compound (B) both H occupies axial position
•• Compound (A) will solvolyses faster than (B).
•• Diaxial compound (A) is less stable than diequatorial compound (B) and thus (A) solvolyses faster.
Illustration 14: Indicate whether the following are SN1, SN2, E1, or E2.
60ο C
1. ( CH3 ) CBr + C2H5OH → ( CH3 ) C− OC2H5 + ( CH3 ) C = CH2
3 3 2
(Major ) (Major )
2. CH3CH2CH2Br + LiAlH4 →
3. CH3CH2CH2Cl + IΘ →
4. ( CH3 ) CBr + CNΘ (Ethanol) →

3
Θ
5. CH3CHBr − CH3 + OH (H2O ) →
Θ
6. CH3CHBr − CH3 + OH (Ethanol) →
7. ( CH3 ) CBr + H2O → (JEE ADVANCED)

3
Sol: 1. SN1, 3° halide.
2. CH3CH2CH3 + HBr,SN 2 ,1ο halide. Nucleophile is HΘ (hydride ion).
3. I − CH2CH2CH3 ,SN 2,1ο halide, IΘ good nucleophile and poor base.
4. ( CH3 )2 C = CH2 ,E2,3 halide, and CN- is a strong base, so elimination is predominant over SN1.
ο
5. CH3CHOHCH3 ,SN 2 , polar solvent favours substitution.
CH2 ,E2, less polar solvent favours E2

6. CH3 − CH =
7. ( CH3 )3 C − OH,SN1, H2O is not basic enough to remove a proton to give elimination reaction.
Illustration 15: The order of leaving group ability for the following is: 1. −OAc 2. −OMe 3. −OSO2Me 4. −OSO2CF3
Sol: Acidic and leaving group order: CF3SO3 − > MeSO3 − > AcO− > MeO − .
Illustration 16: Identify:
Base
A. (A)
Me
OH Br Base A. Me
A. (A) + OH
Cl
OH Br
Me
Br C2H5O
B. (B) B. Me
S 1 + OH
Br C2NH2O F
B. 1
(B)
SN Me
O Me C. Me
+ OH
A. (A) B. (B)
O Me Me
Sol: A. O (A) B. (B) F Me
A. Me
+ OH
O Cl
D. + OH
Me
Illustration 17: Give the major products of
B. the
Mefollowing elimination reactions. Br
+ OH
F
Me
Me Me
C. Me E. Me Cl + CH3O
A. Me
+ OH + OH
Cl
F Me
Me
Me
Me
B. Me
+ OH D. + OH
F F. Me O + CH3X
Me Br
C. Me Me
+ OH Me Me
F Me Me E2
E. Me Cl + CH3O G. N Me + OH
Me
O
Me O O
S O Ph + OH
I. S Ph + OH
I.
F. Me O + CH3X
Me Me Chem i str y | 12.25
Me Me
Me
Me Ph Ph
Ph Ph
H H CH3
Me J. H H CH3
E2 J. E1
G. N Me + OH H3 C N
N
E1
H3 C
Me O CH3
Me O CH3
OH + Me
H / Me
H. Me
E1 Me CH3OH
Me Me CH3OH
K. Ph
K. Ph E1
Cl E1
Cl
Me
O Me
O
I. S Ph + OH
Me Me
Sol: E2
Ph elimination
Ph follows Hofmann rule and produces Hoffmann product (less substituted alkene-less stable)
H H CH3
E1
J.
elimination follows Zaitsev’s rule
E1 and produces Zaitsev’s product (more substituted alkene –more stable)
H3C N
O Me
CH (E2, Saytzeff)
A. Me
3
B. Me Me (E2, Hofmann, with F)

Me CH3OH
Me
K.
C. Ph Me
Cl E1
Me + OH Me
Me
FMe
Me
(E2, Hofmann)
D. (Conjugated double bond) not
E. CH3OΘ (nucleophilic cannot attack) 3ο C having high e‒ density, hence elimination takes place giving alkene.
Me
Me
Me Cl + OCH3 Me
Me
Me Me
Me Cl + OCH3 Me
Me
Me
Me
( )
F. Williamson synthesis ( CH3 ) CΘ NuΘ attacks on 1ο C atom. (SN2)
3
Me O + CH3 X Me O Me
Me Me
Me Me
Me O + CH3 X Me O Me
Me Me
G. Hofmann elimination, less-substituted alkene because the leaving group ( CH3 ) N⊕ departs as uncharged
3
species.
Me
Me Me
N
+ (CH3)3N
Me H Me
OH
OH +
H /
H. +
Me Me E1
Major Minor
Saytzeff Alkene
O O
O O
I. S Ph + OH Ph
S
Me
Me Me Me
Ph Ph Ph Ph
H H CH3
J.
E1 H3C H
H3C N
O CH3
Me Me
Me CH3OH CH3
K. Ph Ph CH
Cl E1 CH3
Me OCH3
ARYL HALIDES
1. INTRODUCTION
Aryl halides are compounds where halogen is directly attached to an aromatic ring. They have the general formula
ArX, where Ar is phenyl substituted phenyl or a group derived from some other aromatic system e.g.
Br Cl l COOH
Cl
NO2
CH3
An aryl halide is not just any halogen compound containing an aromatic ring C6H5 − CH2 − Cl is not an aryl halide
for the halogen is not attached to the benzene ring.
The properties of aryl halides are entirely different from that of Alkyl halides.
2. METHODS OF PREPARATION OF ARYL HALIDES

+ -
(a) From Diazonium Salts NO2 NH2 NNX
Reduction HNO2/HX
o
0C
diazonium salt
(i) Sandmeyer Reaction + -
NNX Cl
Cu2Cl2 + N2
+
(ii) Gattermann Reaction
-
N NCl Cl
Cu/HCl + N2
The Gatternann reaction is a modification of Sandmeyer reaction. In Sandmeyer reaction, cuprous halides are used which
are unstable and difficult to handle, however in Gattermann reaction copper power and hydrogen halide are used.
(b) By Direct Halogenation of Aromatic Hydrocarbon
Cl Cl Br Br
FeCl3;Dark
FeCl ;Dark FeCl3;Dark
FeCl3;Dark
(i)
(a) (a) + Cl2 + Cl2 3 (ii)
(b)
+ HCl + HCl (b) + Br2 + Br2 + HBr + HBr
310-320
310-320 K K Room Room
Temp Temp
l
(iii) + l2 + Hl
This reaction is reversible due to the formation of HI which is a strong reducing agent. To get iodobenzene, HI must
be removed from the reaction mixture. To achieve this some oxidising agent like HIO3,HNO3 or HgO is used.
Illustration 18: Starting from C6H6 and C6H5OH , synthesize phenyl-2, 4-dinitrophenyl ether (B). (JEE ADVANCED)
Sol: The Cl of (A) undergoes aromatic nucleophilic displacement because it is activated by two ( −NO2 ) groups.
Cl Cl
NO2
Cl2
Path I : C6H6
FeCl3 Fuming
HNO3
NO2 PhO
(A)
OH O O
NO2
OH
Path II :
Cl
NO2
(B)
O Nitration
3. PHYSICAL PROPERTIES OF ARYL HALIDES
(a) Aryl halides are colourless liquids and colourless solids with a characteristic odour.
(b) The boiling point of aryl halide follows the order ArI > ArBr > ArCl > ArF
(c) The melting point of p-isomer is more than o- and m-isomer.
Structure and Reactivity of Aryl Halide and Vinyl Halides: Chlorobenzene is a resonance hybrid of 5 resonating
structures.
:
:
: : : : : : :
Cl +Cl +Cl +Cl Cl
- -
-
I II III IV V
Contribution by II, III and IV give a double bond character to the carbon-chlorine bond. Hence C-Cl bond in
chlorobenzene is strong. As a result, aryl halides are less reactive compared to the corresponding alkyl halide
towards nucleophilic substitution reaction.
Similar is the case with vinyl halides.
+
:
: :
CH2 = CH Cl CH2 CH = Cl
(a) Therefore attempts to convert aryl halides into phenols, ethers, amines with the usual nucleophilic reagents
and conditions are unsuccessful. e.g R-Cl+aq.NaOH → ROH+NaCl
Cl
+ aq NaOH No reaction
(This could however be achieved under vigorous conditions)
(b) The carbon-halogen bonds of aryl halides and vinyl halides are usually short.
(c) Dipole moments of aryl and vinyl halides are usually small
:
:
Cl Cl
3
2
Cl sp Center
sp
Center(d) In chlorobenzene, the chlorine atom is attached to a sp2hybridized carbon atom whereas in alkyl chloride, the
chlorineCH
atomCH
is attached
Cl to a sp3 hydridized carbon atom.
3 2
The sp2 hybridized carbon atom is more electronegative than the sp3 hybridized carbon atom, thereby the
release of electrons to chlorine atoms is less in chlorobenzene and more in alkyl chloride.
:
:
Cl Cl
3
Cl resonatingspstructure
Center
2
sp (e) The of chlorobenzene indicate that the benzene ring carries a –ve charge at o- and
Center p-positions w.r.t. chlorine atom. Thus the benzene ring definitely takes part in electrophilic substitution
reactions.
CH3 CH2 Cl
4. CHEMICAL REACTIONS OF ARYL HALIDES

Reaction of Aryl halides can be grouped as:
1. Nucleophillic substitution reactions
2. Electrophillic substitution reactions
3. Miscellaneous reactions
1. Nucleophilic substitution reactions

(a) Dow’s Process: The presence of a nitro group at ortho or para to chlorine increases its reactivity. Further as
the number of such NO2 groups increases the reactivity is increased.
-+
Cl OK
+ aq KOH 573 to 673 K + KCl + H2O

200-300 atms
-+
OK OH
+ dil. HCl + KCl
Pot. phenoxide Phenol
Like NO2, certain other groups have been found to increase the reactivity of chloro benzene if present at ortho or
para to chlorine atom. These groups are,
⊕
− N(CH ) , − CN, − SO H, H− COOH, − CHO, − C − R
33 3 ||
O
Cl ONa OH
15% NaOH dil.HCl

o
160 C
NO2 NO2 NO2
Cl OH
NO2 NO2
(i) Na2CO3
o
130 C
(ii) dil.HCl
NO2 NO2
Cl OH
NO2 NO2 NO2 NO2
H2O; warm
NO2 NO2
A nitro group at meta position of chlorine has practically no effect on reactivity

Cl NH2
NH3, Cu2O
o + HCl
200 C
20-30 atm
Aniline
Here again the presence of NO2 groups at ortho or para position w.r.t. Cl group increases the reactivity.
Cl NH2
NO2 o
NO2
NH3; 170 C
NO2 NO2
Cl CN
+ CuCN + CuCN
475 K
Cl OCH3
Cu Salt
+ CH3ONa o + NaCl
220 C
Mechanism: The nucleophilic aromatic substitution reaction can be well explained by a bimolecular mechanism.
Cl : Nu-
Cl Nu
slow -
Step 1 (Intermediate)
Cl NO2
Nu
-
: :
+ : Cl
:
-
Step 2
Product
The intermediate carbonium ion is stabilized due to resonance.

The stability of such carbonium ion can be further increased by –R or –M groups at ortho or para positions.
Equivalent to
Cl Nu Cl Nu Cl Nu Cl Nu
- -
(b) Elimination - Addition Reaction: Reaction with sodamide

NH2
Cl
NaNH2/NH3
196 K
H
Benzyne
This reaction is an elimination- addition mechanism for nucleophilic substitution.
X X X
NH2
+ NH3
H Benzyne
Addition
-
NH2 NH2
-
NH2 NH2
+ H - NH2 + NH-
2
-
2.
Electrophilic Substitution Reaction: Halogens are unusual in their effect on electrophilic substitution
reactions: They are electron withdrawing yet ortho and para-directing.
To understand the influence of halogens, let us consider the intermediate formed when an electrophile attacks
the halobenzene at ortho, meta and para positions.
X X X
Y Y Y
Ortho attack
H H H (A)
X X X X
+Y para attack (B)
Y H H Y H Y
X X X
meta attack H H (C)

H
Y Y Y
In A, B and C if one considers the inductive effect i.e. (-I effect) of X then A and B would be unstable because the
(+) charge comes on the carbon atom carrying the halogen atom X. The structure C will be most stable and the (+)
charge does not come on the carbon atoms carrying the halogen atom X.
We should therefore expect that halogen atoms attached to the benzene ring would be meta. While directing for
electrophilic substitution reactions, the existence of halonium ions have shown that halogen can share a pair of
electrons and can accommodate a positive charge. When this idea is applied to the present problem the carbocations
formed when an electrophile attacks at ortho or para position i.e. (A) and (B) would be stabilized as below. Whereas
the carbocation formed when the electrophile attacks the meta position on halo benzene i.e. C would be destabilized.
:
: :
X : :
X
Y Y
(A)
H H Charge delocalized
: :
X
:
: :
X
Charge delocalized
(B)
H Y
H Y
1 21.
. 3 2Halogenation
| Alkyl Halides, Ar yl Halides and Aromatic Compounds
Cl Cl 1. Cl
Halogenation
Cl
The inductive effect causes electrons withdrawing deactivation-Clthe resonance effect tends Cl to oppose theClinductive
FeCl2;Dark
effect for attack at 2ortho and para position, and hence
+ Cl + makes the deactivation less for orthoCland para than for
Cl2
FeCl2;Dark
meta. This shows reactivity is controlled by the inductive effect, and+orientation is controlled by resonance
+ effect.

Reactions Cl Cl
1.
1. Halogenation 2.
Halogenation
2. Nitration Nitration
2. Nitration
Cl Cl Cl ClCl Cl Cl Cl Cl
Cl NO2
FeCl2;Dark NO2 + H2SO4
+ Cl2 + H2SO4 + + HNO3 +
+ HNO 3 + 60oC
o
60 C
Cl NO2
3. Sulphonation (C)
3. Sulphonation
2. Nitration Cl NO2 Cl Cl
3. Sulphonation
Cl
Cl
Cl
Cl
Cl
Cl
SO3H

NO2 + H2SO4 +
+ H2SO4 SO H
+ HNO3
o + 3
+ H2SO60
4
C + SO3H
NO2
3. Sulphonation
Cl Cl Cl SO3H
SO3H
4. Friedel Crafts Reaction

+ H2SO4 +
(a)
(A) Alkylation
SO3H
Cl Cl Cl
anhyd
R
AlCl3
+R-X +
(b)
(B) Acylation R
O
Cl Cl Cl
anhyd
C-CH3
AlCl3 +
+ CH3COCl or CH3C-O-C CH3

O O
C=O
(c)
(C) Benzoylation CH3
O
Cl Cl Cl
anhyd
C-C6H5
AlCl3 +
+ C6H5COCl or C6H5-C-O-C-C6H5

O O
C=O
C6H5
5. Miscellaneous Reactions
(a) Fittig reaction

Ether
2 Cl + 2Na + 2NaCl
(b) Wurtz-Fittig reaction

Ether
Cl + R-Cl + 2Na R + 2NaCl
Here side products like R - R and are also formed
(c ) Ullmann's reaction
l
Cu powder

Biphenyl
Chlorobenzene does not undergo Ullmann’s reaction but if a deactivating group is attached to chlorobenzene then
the substituted chloro benzene can take part in Ullmann’s reaction.
Cl NO2
NO2
Cu powder
NO2 NO2

NO2
NO2
Nucleophilic Substitution Mechanism

Table 12.1: Difference between SN1 and SN2
SN2 SN1
Reaction RX + Nu ‒‒ > RNu + X Same
Mechanism Concerted Two steps
Intermediate None Carbocation
Kinetics Second-order First order
Stereochemistry Complete inversion Nonspecific
Nucleophile Important Unimportant
Leaving Group Important Important
Alkyl Group CH3 > 1° > 2° > 3° 3° > 2° > 1° > CH3
(steric hindrance) (carbocation stability)
Occurrence CH3, 1°, some 2° 3°, some 2°
Solvent Effects Variable (Poloreproteic) Polar, protic
PLANCESS CONCEPTS
Elimination Mechanisms
Table 12.2: Difference between E1 and E2
E2 E1
Reaction RX + Base-->C=C Same
Mechanism Concerted Two steps
Intermediate None Carbocation
Kinetics Second-order First order
Stereochemistry Anti periplanar Nonspecific
Base Important Unimportant
Leaving Group Important Important
Alkene Produced Zaitsev Rule Same
Substitution vs. Elimination

Table 12.3: Difference between substitution reaction and elimination reaction
SN1 SN2 E1 E2
CH3X No Good nucl. No No
1° (RCH2X) No Good nucl., weak base No Strong base, weak nucl.
2° (R2CHX) No Good nucl., weak base No Strong base

3° (R3CX) Good nucl., weak base No Polar solvent, Strong base
no base or nucl.
Good nucl., Good nucl., Poor nucl., Poor nucl.,

strong base, weak base, strong base, weak base,
e.g., OH- e.g., l- e.g., tBuO- e.g., H2O
CH3X S N2 S N2 S N2 No reaction
S N2 S N2 E2 No reaction
1ο (RCH2 X )
E2 SN2 E2 No reaction
2ο (R 2CHX )
E2 SN1 E2 S N2
3ο (R 3CX )
Aishwarya Karnawat (JEE 2012, AIR 839)

Illustration 19: Write the structure of carbocation produced on treatment of a compound (A)(Ph2CHC(OH)Me2)
with SbF5/SO2. (JEE MAIN)
Sol: It is formed by protonation and subsequent elimination of H2O, followed by H+ ion transfer to form a more
stable carbonium ion.
H OH H
H
Ph C C Me Ph C C Me
-H2O
Ph Me Ph Me
H
Ph C C Me
Ph Me
Illustration 20: Which of the following has the greater Ka value (JEE Advanced)
OH OH
D D
I. II.
Sol: Deuterium is more e- donating than H atom. Hence K a of (i)>(ii).
Illustration 21: Which of the carbonyl groups in (A) and (B) protonate more readily in acid solution and why?
(JEE Advanced)
A. H3CO COCH3
B. O2N COCH3
Sol: Protonation of (A) takes place more readily than (B), since protonated (A) is more resonance stabilised than
protonated (B).

OH
MeO C COCH3
(A) More stable
OH
Illustration 22: (JEE MAIN)
O2N C COCH3
Cl
(B) Less stable
O2N NO2
I. + NaOH (A)
NO2
NO2
NO2
MeONa
II. (B)
MeOH,
I. + NaOH (A)

NO2
NO2
NO2
MeONa
II. (B)
MeOH,
CF3
III. NaNH3
(C)
Liq. NH3
Cl
Br
Me OMe KNH2
IV. (D)
Liq. NH3
Sol: (I) [due to three e‒ -withdrawing (NO2) groups (C ‒ Cl) bond is weakened.
(II) OMe CF3

NO2 NH2
(III) [Due to e‒ -withdrawing (‒CF3) groups, (C ‒ Cl) bond is weakened, so SN reaction takes place.]
(IV) No. reaction since there is no H at o-position that can form benzyne.
Illustration 23: Br (JEE MAIN)

Li/Hg O
I. (F) (G)
F
NO2
KCN,
II. (H)
C2H5OH
Br
CN
Sol: I. (F) O
O (G) II. (H)
Diels-Alder
Br
Me
Me
Illustration 24: Br
Br
NaCN,
NaCN,
I.I. (J)(J)
CC2H
H5OH
2
OH 5
NO
NO22
NO22
NO
Br
Br22,Fe
,Fe (i)(i)KCN
KCN
II.II. (K)
(K) (L)(L)
(ii)
(ii)HH
2OO
2
Me
Me
(JEE ADVANCED)
Me NO2
Br CN COOH
Sol: I. (J) II. (K) H2O

(L)
CN Br Br Br
Me Me Me
Illustration 25: When a trace of KNH2 is added to a solution of chlorobenzene and potassium triphenyl methide
((Ph)3 CΘK ⊕ ) in liquid NH3, a rapid reaction takes place to yield a product of formula C25 H20. What is the product?
What is the role of KNH2 and why is it needed? (JEE ADVANCED)
Sol: C25H20 suggests that the product is tetraphenylmethane, Ph4C. KNH2 is used to produce benzyne which
combines with Ph3 C‒K+ to give the final product.
Cl
CPh3
CPH3
KNH2 Ph3C NH3
NH3 + NH2
+H +
OTHER AROMATIC COMPOUNDS
1. PHENOL
This process (to derive phenol) is carried out by the aerial oxidation of cumene to hydroperoxide, which is then
decomposed by acid into phenol and acetone (by product).
Me Me
Me +H2SO4 O2
or o
OH 130 C
Cl (100% yield)
+ Anhyd, AlCl3
Me Me
Me
or Me O - OH
OH
+ BF3
Me Me Cumene
hydroperoxide
Electrophile in all is Me Me
Attacking point OH
Me
H2SO4
100oC
+ O
Me
Phenol Acetone
2. INTRAMOLECULAR FRIEDAL CRAFT REACTION

When both (Ar) group and (R–X) are present within the same molecule, then the intramolecular friedal craft reaction
takes place, e.g.,
Anhyd.
(I) + HCl
AlCl3
Cl
Anhyd.
(II) + HCl
AlCl3
Cl Me
Me
3. LIMITATIONS OF FRIEDAL CRAFT REACTION

(a) As aryl and vinyl halide (CH2 = CHX) do not form carbocation easily, they are not suitable to be used as the
halide component.
(b) Polyalkylation takes place quite often. After the introduction of one alkyl group (an activating group) the ring
gets activated for further substitution. Friedal craft acylation does not suffer from this defect since the alkyl or
aryl group, being a deactivating group, does not facilitate further substitution.
(c) Carbocations formed during the reaction rearrange to yield more stable carbocation.
(d) It is often accompanied by the rearrangement of alkyl group attached to the nucleus e.g., 1, 2, 4-trimethyl
benzene rearranges to give mesitylene in friedal craft reaction.
Me Me
Me
AlCl3 + HCl
+ AlCl3 + HCl
or HAlCl4
Me Me
Me
(e) The presence of e¯-withdrawing groups (m-directing group) in the ring hinders the Friedal craft reaction,
e.g., nitrobenzene and acetophenone do not undergo this reaction. On the other hand, if a strong activating
group (e¯-donating group) is present in either of the above two compounds, reaction takes place, e.g., o-nitro
anisole can undergo this reaction.
(f) The presence of (NH2), (NHR) and (NR2) groups also inhibits the reaction. This is because these groups
become powerful e¯-withdrawing groups reacting with Lewis acid or with protoic acid when the compounds
containing these are placed in friedal craft reaction mixtures.
NH2 NH2 -AlCl3
+ AlCl3
(I)
Lewis acid
NH2 NH2
(II) +H
(g) Friedal craft reaction reactivity order of the following compounds is:
Me
Me Me Me Me Me Me
Toluene Ethyl benzene Isopropyl benzene t-Butyl benzene

(Three H.C. (Two H.C. (One H.C. (No H.C.
Structure) Structure) Structure) Structure)
The above reactivity in friedal craft reaction is due to hyperconjugation (H.C.)

But friedal craft reaction reactivity order of the benzene deuterated or other isotopic label compound is:
CH3 CH3 CH3

D D T T
D D T T
D T
Here, again no. (C–H), (C–D), or (C–T) bond break in the first R.D.S. (See mechanism), so primary isotope effect does
not take place. So the rate of reaction of the above is almost same.
4. BLOCKING OF P-POSITION BY FRIEDAL CRAFT ALKYLATION

p-position in benzene derivatives can be blocked either by sulphonation and then desulphonation, or by friedal
craft alkylation, by the use of bulky t-butyl group. In the dealkylation, benzene or toluene or m-xylene or HF may
be used as an acceptor; for example,
Me Me Me
Me3C-Cl+AlCl3 COPh
PhCOCl+AlCl3
Me3C-OH+AlCl3
(o-, directing) CMe3 CMe3

Me or
=CH2+ H3SO4
Me
(SE at p- at o- , steric hindrance)

Me
Electrophile in all is Me Me Dealkylation

with
Attacking point
+ AlCl3
Sulphonation : conc. H2SO4
Me Me
COPh CMe3 Me
PhCl+ AlCl3 COPh
+
SO3H SO3H
t-Butyl o-Benzoyl
benzene toluene
Me
COPh
Desulphonation
o-Benzoyl H2SO4+steam+H2O
toluene or
o
HCl/H2O at 150 C
To avoid the oxidation of aniline and phenol by nitration, the amino and (–OH) groups are protected by acetylation
or benzoylation. The acetyl or benzoyl group is finally removed by hydrolysis to give o-and p-isomers.
Acetylation can be done by any of the following three acetylating reagents.
(a) (CH3CO)2O + Glacial acetic acid
(b) (CH3CO)2O + Conc. H2SO4
(c) CH3COCl + Pyridine
The benzoylation of alcohol, phenol, aromatic or aliphatic amine with benzoyl chloride (C6H5COCl) and NaOH is
called Schotten-Baumann reaction.
Example:
Py.
(i) ROH + ClCOCH3 ROCOCH3 + HCl
PhCOCl
+NaOH ROCOPh + NaCl + H2O
(ii)
(ii) NH - CO - Ph NH2 NH2 - CO - CH3
Benzoylation Acetylation
(CH3CO)2O + CH3COOH
Benzanilide Aniline Acetanilide
(N-Phenyl benzamide)
NHCOCH3 NHCOCH3
Conc. HNO3
NO2
+ Conc. H2SO4
+
Nitration, 288 K
NO2 o-Nitro acetanalide

(Minor)
p-Nitro acetanalide (Due to steric hindrance)
(Major)
NH2 NH2
NO2
H / H2O +
-AcOH
NO2 (Minor)
(Major)
Illustration 26: Complete the following reactions: [JEE ADVANCED]
SOCl2 Anhyd. Zn + Hg S or Se
o-HOOC – C6 H4 – CH2 – Ph (B) (C) (D) (E)
(A) AlCl3 + HCl 600ºC
Sol:
O
COOH H
SOCl2 Cl
(A) (B)
Anhycl. AlCl3 Intramolecular
F.C.
O
Zn-Hg+HCl
Clemmensen
n
(D) recl (C)
( > C=O - CH2-)
o
S or Se, 600 c
Aromatisation
(A) (B)
1 2 . 4 2 | Alkyl Halides, Ar yl Halides andAnhycl.

Aromatic
AlCl3Compounds
Intramolecular
F.C.
O
Zn-Hg+HCl
Clemmensen
(D) reduction (C)
( > C=O - CH2-)
o
S or Se, 600 c
Aromatisation
Anthracene
5. DIRECTIVE/INFLUENCE
Standandard for comparison ⇒ –H in benzene
Class I (o- , p-directing) Class II (m-directing)
i. Very strong activating groups i. Very strong deactivating groups

. . . . . . .. ⊕ ⊕ ⊕
− : O :Θ > − NR 2 > − N HR > − OH − O3 > − NHR 2 > − NH3 > −NO2
..
> −CF3 > −SO3H > −C ≡ N
ii. Moderately activating groups ii. Moderately activating groups
O O – C – H > – C – R > – C > – OH > – C – X >

|| || || || || ||
O O O O
−OR => −NH − C − R > −O − C − R
Aldehyde Ketone Acid Acid halide

: :
: :
: :
> C> O R> C> O C R> C> NH2
O O O O
Ester Anhydride Amide
iii. Weakly activating group iii. Deactivating groups
−R > −Ar > −CH =CH2 −F > −Cl > −Br > −I (Due to − I effect)
..
−CH2 X > −SR > N= O − S
. .− R
||
O
PLANCESS CONCEPTS
All o¯, p-directing groups except halogens and groups in (iv) are activating groups.
All those substituents which are more reactive than benzene (standard for comparison) are activating.
Vaibhav Krishnan (JEE 2009 AIR 22)
5.1 Directive Influence on Second, Third and Fourth Group
Second group
CH3
CH3 CH3
NO2
Nitration
+
Toulene
NO2
CHO CHO
Nitration
-CHO is
m-directing NO2
Third group: The position of a third group entering the benzene ring is determined by the nature of two groups
already present there.
Case I: When both the groups belong to Class I, the directive influence of each group is in the order as given in
Table. (When both the groups belong to Class I): Reactivity of (–CH3) > (–Cl).
i. CH3
CH3 CH3
Cl Cl O2N Cl
Nitration
+
NO2
Case II: When both the groups belong to Class II, the third group is introduced only with difficulty. The directive
influence of each group is in the order as given in Table. (When both groups are of Class II): Reactivity of (–CN)
> (–CHO)
i. CN CN CN
CHO CHO CHO
Nitration
+
NO2 NO2
o-Compound Two isomers

CN CN
Nitration
CHO O2N CHO

CHO CHO CHO
Nitration
+
NO NO2
1 2 . 4 4 | Alkyl Halides, Ar yl Halides and Aromatic2 Compounds
o-Compound Two isomers

ii.
CN CN
Nitration
CHO O2N CHO
Case III: When groups belongs to Class I and Class II, the directive influence of the group belonging to Class I takes
precedence. (When both groups are of Class I and Class II):
(– CH3) group of Class I directs the substitution.
i.
CH3 CH3 CH3
CH3 CH3 CH3
NO2 Cl NO2 NO2
NO2 Halogenation Cl NO2 NO2
Halogenation +
+
Cl
o-Compound Cl
o-Compound
Two isomers
Two isomers
CH3
ii. CH3 CH3 CH3
CH3 CH3
Cl
Halogenation Cl
Halogenation +
+
NO2 NO2 NO2
NO2 NO2 NO2
Cl
m-Compound Cl
m-Compound
CH3
CH3
Cl
Cl
+
+
NO2
NO2
Three isomers
Three isomers
Fourth Group: When a trisubstituted substance is converted to a tetrasubstituted product, adjacent compound
(i.e., 1, 2, 3-derivative) gives two, the unsymmetric compound (i.e., 1, 2, 4-derivative) gives three, and the symmetric
compound (i.e., 1, 3, 5-derivative) gives only one tetrasubtituted product.
For Example:
CH3 CH3 CH3
CH3 Cl CH3 CH3
A. Chlorination
+
CH3 CH3 Cl CH3
1, 2, 3-Trimethyl benzene
(Adjacent) Two isomers
6. RELATIVE REACTIVITIES
All the activating groups render the benzene ring more reactive and the deactivating groups less reactive than
benzene towards SE reaction. If a substituent contains a pair of non-bonded e¯’s on the atom directly attached
to the benzene ring, and these e¯s being in conjugation with the π e¯s of the benzene ring are delocalized into
the
.. ring
.. through
.. π - orbital overlap, then it is called electron donation by resonance or π donation, for example,
OH,
..
− NH
.. 2
, − Br
..
: , etc. They also withdraw e¯s inductively due to the greater electronegativity (EN) of the atom
attached to the benzene ring than the EN of H. This is called σ -withdrawing or inductive electron withdrawing.
:
NH3 Me NH3
donation donation withdrawing

and withdrawing (or) (or)
(or) (Inductive e- donation) (Inductive e- withdrawing)
e- donation by
resonance and inductive
e- withdrawing
: NH2 NH2 NH2 NH2 NH2

:
:
-donation
Donate e ’s into the ring by resonance ( π donation) and withdraw e ’s from the ring inductive ( σ withdrawing).
But they donate e ’s into the ring less effectively than the very strong activating groups. It means that they are less
effective e¯ donors by resonance, since they can donate e ’s by resonance in two opposite competitive directions,
i.e., into the ring and away from the ring (cross conjugation) and this net resonance effect is decreased. Despite this,
e donation by resonance is more than e withdrawal by inductive effect ( σ withdrawal). That is why these groups
are moderately activating. (–CH=CH2), (–CH=CH–R), (–CH=CR2), and aryl (Ar¯) groups are weakly activating groups.
They can donate and withdraw e s by resonance but are slightly more e¯ donating than e¯ withdrawing. In case of
three isolated rings, the central ring (A) acts as e¯ donating by resonance, since it is bonded to two activating Ph
group and it can donate e¯s on either side of the ring.
A A
Benzene
(e donation by resonance by ring A on either side)
Alkyls [(–CH3), (–C2H5), and –CH (CH3)2] are weakly activating groups. An alkyl group is a weak e¯ donor inductively
( σ donation) and simultaneously e¯ donor by hyper conjugation.
The halogens are weakly deactivating groups because they donate e¯’s to the ring by resonance ( π donation) and
withdraw e¯’s inductively ( σ withdrawal). The deactivating characteristic is due to the high EN of halogens, yet they
are o¯, p-directing due to e¯ donation by resonance (X =–F, –Cl, –Br, –I).
Illustration 27: Given the decreasing order of the relative reactivity towards SE reaction of the following compounds.
(a) I. Benzene, II. Phenol, III. Aniline, IV. Chlorobenzene
(b) I. Acetanilide, II. Aniline, III. Acetophenone, IV. Benzene
(c) I, 1,3-Dimethyl benzene, II. 1, 4-Dimethyl-benzene, III. Toluene, IV. Benzene,
V. 1,3, 5-Trimethyl benzene (JEE ADVANCED)
Sol: (A) (III) > (II) > (I) > (IV) (PhNH2> PhOH > PhH > Ph-Cl)
Reactivating of –NH2 > – OH > – H > – Cl
(B) (II) > (I) > (IV) > (III)
O O
:
Ph NH2 > Ph NH C CH3 > Ph > Ph C CH3

EDG (Cross conjugation) (Standard) (EWG)
(C) (V) > (II) > (I) > (III) > (IV)

(C) (V) > (II) > (I) > (III) > (IV)
Me Me Me Me
Me Me Me
Me
(H.C. Effect)
Illustration 28: Indicate by an arrow the position(s) where SE reaction takes place in the following:
(JEE ADVANCED)
O
(A) (B) ||
Ph − NH − C − Ph
O (I) NO2
|| (H) COOH
(C) (D) (E)
Ph − NH − C − CH3 OH O2N

Sol: Electrophilic Substitution takes place at position where electron density is maximum. Depending upon the
group present and their influence (ortho,meta,para) predict the site of SE
(A) 2
3
1
4
6 5
1, 4-diphenyl benzene
or
p-terphenyl
SE reaction takes place at the place indicated by the arrows in the central ring, since it is joined to two activating
phenyl rings.
(B) O
:
NH C B
Benzanilide
Ring (A) bonded to (–NH–) is activated. So SE reaction takes place at o¯ and p-position of ring (A) but p-product is
major, since o-positions will be sterically hindered. Ring (B) is bonded to group and is deactivated.
(C) : O
NH C CH3
Acetanilide
Same explanation as in (b), p-product is major.
(D) COOH
OH
(o- and p-w.r.t.-OH)
The (–COOH) group is deactivating and m-directing, (–OH) is activating, and o-and p-directing class I (–OH) decides
orientation.
(E) NO2
NO2
No reaction because of two strongly deactivating (–NO2) groups.
However, the (–NO2) group is m-director; if suitable conditions are employed then (–NO2) directs at m-position.
7. AROMATIC SUBSTITUTION REACTION IN BENZENE

Ar-SN: SN reaction is benzene under ordinary conditions is not possible, since the displacement of H⊕ , a very
strong base and poor leaving group, is very difficult. This can occur only if an oxidant can convert H⊕ to H2O. The
oxidant O2 or K3 [Fe(CN)6] can convert H⊕ to H2O.
H H OMe H OMe H OMe H OMe

:
+ OMe Slow
R.D.S.
(Na )
Arenanion O2 or K3[Fe(CN)6]
OMe OMe
:
+H + H2O
ArSN reactions are possble with ArX and ArOTs, aromatic halides and tosylate (-Ts = p-Toluene sulphonyl group
O
Me S ). Both –X and (–OTs) are good leaving groups, especially when EWG (e¯-withdrawing groups),
O
such as (–NO2) and (–C ≡ N), are present at ortho and/or para to the reacting C atom e.g.,
Cl OH
Aq. NaOH
(I)
Aq. NaOH. 623K
300 atm
Cl OH
O2N NO2 O2N NO2
Aq. NaOH
(II)
or H3O ,
NO2 NO2
PLANCESS CONCEPTS
Greater the number of these EWG at o-and/or p-position, faster is the reaction and lesser vigorous are
required. This is also called addition-elimination reaction (since Nu⊕ adds and –X eliminates)
NH2 Br OH
NO2 NO2 NO2
NH3 Aq. Na2CO3
475 K, 60 atm 373 K
NO2 NO2 NO2

2, 4-Dinitrobromo benzene
SCH2Ph OC2H5
PhCH2SNa C2H5ONa
NO2 NO2
NHEt
NO2 EtNH2
NO2 NO2
NO2
Nikhil Khandelwal (JEE 2009, AIR 94)
7.1 Aromatic Nucleophilic Substitution

ArX undergoes nucleophilic substitution reaction in the presence of a very strong base such as NaNH2 or KNH2 in
liquid NH3 at –33ºC (140 K). The reaction occurs through the formation of an intermediate called benzyne.
Two important features are :
(i) There is no necessity of an e¯-withdrawing group in the ArX.
(ii) The entering group does not always occupy the vacated position. This is called cine substitution.
NH2
Cl NH2
* NaNH2, liq. NH3 Addition of NH3 * *
+
H 140 K (-NH3,-NaCl) Step 2
(Elimination) Benzyne
Step 1 Equal amounts
slow R.D.S
Step 1: Slow R.D.S: In this reaction, first the elimination of HCl occurs and then the addition of NH2 takes place, so,
this ArSN reaction is called elimination-addition reaction.
14
When chlorobenzyne (I) with C is treated with NaNH2 in liquid NH3, half of the product has an (–NH2) group
14 14
attached to C (C*) as expected, but the other half has an (– NH2) groups attached to the carbon adjacent to C
(C*). This observation proves the formation of a benzyne intermediate which has two equivalent C atoms to which
the (–NH2) group can be attached. Benzyne has an additional π -bond formed by sideway overlap of sp2 orbitals
alongside the ring. These orbital’s that form π - bond cannot overlap with the aromatic π -system because they are
not coplanar. The new π -bond is weak because of the poor overlap and hence benzyne is very reactive.
NH3
:
Cl Cl * *
:
* NH2 * -Cl * NH2
+
-H
H NH3
Benzyne
* * NH3
+ Redistribution
NH3 of H atoms
Illustration 29: Complete/Convert the following

Me Me
I
??
(A) 2 + Cu B+C (C)
NO2
(A)
I

(B) 2 + Cu B
NO2
(A)
Sol: (A) It is Ullmann reaction.
Me NO2 2' 3'

5 6
1 1' B = (+) form
4 4'
2 C = (+) form
3 6' 5'
NO2 Me
(±) 6.6'-Dimethyl-2.2'-dinitro biphenyl
The diphenyl is sterically hindered because of bulky ortho substituents, therefore phenyl rings cannot be coplanar,
and the energy barrier for rotation of (C1 – C1) σ -bond is very high for inter-conversion of enantiomers. The
enantiomers are isolable at room temperature. This type of stereoisomerism is due to restricted rotation about a
single bond. Such a process in which stereoisomers can be isolated is called atropisomerism and the isomers so
formed are called atropisomers.
(B) It is also Ullmann reaction.
O2N
(B) 2.2' Dinitrobiphenyl
NO2
Me
In this case, free rotation about the single bond is possible and each ring has vertical plane of symmetry. Hence, it
does not show optical isomerism. (A) + CBrCl3
h
(C) Me COOH
Cl
[O] Soda lime
NaNH2
KMnO4/OH and (B) ? ?
Liq. NH3
Et
Me
Illustration 30: Complete the following reactions: (JEE ADVANCED)
O
NO2
Me
h (i) OH
(A) + CBrCl3 (C)
(ii) K3[Fe(CN6)],
NO2
Cl
NaNH2
(B) ? ?
Liq. NH3
Et
Me
O
NO2
Sol: (A) Reaction proceeds by free radical mechanism because in the presence of light, radicals are formed. (C – Br)
bond is weaker than (C – Cl) bond and hence (C – Br) bond breaks to give Br–.
(i) OH
(C)
(ii) K [Fe(CN6)],
CBrCl3 h Br 2+ CCl3 3
NO
Attack by
CCl3 on toluene occurs at the Me side chain and not in the ring because (C – H) bond of Me is weaker
than (C – H) bond of the ring. Moreover, benzyl radical is more stable than aryl radical.
CH3
Path (b) Path (a)
Br CCl3
CHCl3 CH2
CH2+ HBr
CBrCl3
CCl3 + CH2Br
h
(Br)
Path (A) is favourable because the formation of CHCl3 is more stable than the formation of HBr. It is because (C – H)
bond in CHCl3 is stronger than (H – Br) bond.
(B) It is an example of ArSN (elimination-addition) reaction via benzyne.
Cl
NaNH2
Me
:
Et
O
(Nucleophile)
Me Me
Et Et
NH3
O : O
(C) It is an example of ArSN (addition-elimination) reaction due to the presence of strongly EWG [two (–NO2)
 Θ 
groups]. H atom at o- and p- to (–NO2) group will be most activated and is attacked by nucleophile  OH  at these
 
 
positions. K3 [Fe(CN)6] is an oxidising agent to remove proton from the complex
NO2 NO2
OH
Na
NO2 NO2
H OH
NO2
K3[Fe(CN6)]
NO2 H -H Cr2O3 or V2O5

(B) (C)
OH or Mo2O3
Me
773K. 10-20 atm
Illustration 31: (JEE ADVANCED)
Cl
NaNH2 H Cr2O3 or V2O5

(i) Liq.NH3
? (B) ?
or Mo2O3
(C)
Me Et Me 773K. 10-20 atm
O
Cl
OMe 2
(ii) NaNH
?
1. Excess of NaOH2.NH3
+ ? (G)
Liq.NHO3 2. H3O
Br Et Me
O
OMe 1. Excess of NaOH2.NH3

+ (G)
O 2. H3O
Br
Sol: These reaction are example of intermolecular friedal craft alkylation reaction.
(i) 1 1
2 H 2 1, 2-H
3 3 shift
4 4
Me Me
5 Me
6
1 1
H 2
Cr3O3 2
Aromatisation Intramolecular 4 3
4 3
F.C. reaction
Me Me
Me Me
(B)
o
3C
(More stable)
Me Et
1-Ethyl-1-Methyl
napthalene
(C)
3 3
2 2
NH2 4
(ii) 4
Strong base -H 5 5
Br H 1 Br -Br
:
1
H 6
6
O OMe O OMe COOMe
(F)
(G)
Illustration 32: Indicate the position where ArSN reaction will take place and explain why. (JEE ADVANCED)
PhONa
O2N I Br (B)
(i)
(A)
PhONa
O2N I Br (D)
(ii)
(A) NO2
PhONa
O2N I Br (D)
( iii )
(E) OMe
PhONa
HO3S I NO2 Br (H)
(iv)
(G)
O2N I
(ii)
NO2
(-NO2 at p) (NO2 at m) Chem i str y | 12.53
Sol: ArSN (addition-elimination) reaction takes place in the ring which contains
PhO strong EWG
NOat
2 +o- or
I / and p to the
eliminating group.
NO2
OPh OPh
:
O2N I MeO I
(i)
:
( iii )
OMe

I + PhO NO2
p-OMe = -I m-OMe
and +R and = only -I
OPh + R > -I Net Net e- with
e- donating drawing
O2N I
(ii)
PhO + I OMe
NO2
(-NO2 at p) (NO2 at m)
MeO
PhO NO2 + I
NO2
OPh
OPh
O
:
MeO I
HO S I NO2
:
( iii )

(iv)
O OMe

o-SO3H = -I o-NO2-, -R, -I of NO2
net e- = -I
and -R,p-OMe > -Im-OMe
of SO3H
withdrawing
and +R and (EN of=Nonly
> S)-Ibut
is greater
+ R > -I Net
-R of SO3H >with
Net e- - R of
e- donating drawing
NO2 (more resonance
st. of SO3H); net e-
withdrawing
PhO is
+ less
I OMe
than -SO3H
MeO
PhO SO3H + O2N I
OH
CH2Br CH2MgBr Me
Mg H3O
Illustration 33: ether + Me - CHO + Compound (B)
(A)
Compound (B) is an isomer of (A). Compound (B) shows positive iodoform test and gives o-toluic acid. What is (B)?
Explain its formation. (JEE ADVANCED)
Sol: (B) is an isomer of (A) and shows iodoform reaction, therefore, the side chain must contain either
O
C CH3
or
CH
OH
CH3
group.
Compound (B) may be:

Me O Me OH Me
COO
Me or Me NaOH + I2
+ CHI3
(I) (II)
But (I) is not an isomer of (A) (molecular formula C9H10O), (II) is an isomer of (A). Hence, compound (B) is (II).
Formation of (II): It involves the rearrangement. The (CH3CHO) group is attached to o-position of the ring, due to the
polarisation of (Me-HC=O Me-CH-O) in which o-position of the ring behaves as the nucleophilic centre.
CH2MgBr CH2-MgBr CH2 CH3
H H
+ CH = O CH = O CHOMgBr CH OMgBr
Me Me Me Me
Me OH
H3 O Me
B (II)
POINTS TO REMEMBER
1. Electrophilic substitution reaction:

(a) Halogenation – Addition of Cl or Br : need a Lewis acid catalyst (Fe or FeCl3)
H X
X2(Cl2 or Br2)
HFe or FeCl X
X2(Cl23or Br2)
H HFe or FeCl NO2 X
HNO 3
X2(Cl23or Br2)
NO2
(b) Nitration H H SO Fe or FeCl
2 HNO
4
3
3
H H H SO SO3H NO2
SO3/H2SO2 4 4HNO3
Hor H SO , H2SO4 SO3H
2 SO43/H2SO4
SO3H
(c) Sulfonation Hor H SO ,
2 SO43/H2SO4
or H2SO4,
(d) Friedel – Crafts Alkylation – Substitution of methyl (Me) or ethyl (Et) need Lewis acid catalyst.
H R
RX (R = Me, Et)
AlCl3
Why does R have to be Me or Br ? Longer alkyl chains attach at most substituted carbon.

H X
AlCl3
Rearranged Not formed
(e) Friedel-Craft Acylation – Substitution of acyl group (RC = O) for H : Need Lewis acid catalyst.
O
O (Acyl halide)
H CR
RCX ketone
AlCl3
CR CH2R
2. Clemmensen reduction Zn(Hg)
HCl
O
3. Wolf-Kishner reduction
CR CH2R
N2H4
OH/
(Mg or Fe) / HCl

4. NO2 NH2
or H2, catalyst (e.g. Pt)
O O
O O
R 1. KMnO4, OH- COH
5. Carboxylic acid
R - COH
1. H+ 4, OH
2. KMnO
Carboxylic acid
2. H+
O
R O
COH
K2Cr2O7
R COH Dicarboxylic acid
KH2Cr2O
2SO
6. R 47 COH Dicarboxylic acid
H2SO4 O
R COH
O
Flow Chart:
Preparation of Aryl Halide:

(1)diazonium
(1) From From diazonium
salt : salt
+ -
N NX
(a) Sandmeyer reaction :

N2X Cl
CuCl2
+N2
(b) Gattermann reaction :

N2 X Cl
Cu/HCl
+N2
(2) Direct halogenation of aromatic hydrocarbon
Cl
FeCl3, Dark
+Cl2 +HCl
310-320 K
Elimination reaction
E1 E2 E1CB
Unimolecular Bimolecular Elimination unimolecular

elimination elimination conjugate base
Two step process Single transition state Poor leaving group and
Ionization Takes place with acidic hydrogen
Deprotonation primary and eliminate to form
Take place with secondary alkyl halide addition bond
tert. Alkyl halide Competes with SN2 Two step process
In competition reaction mechanism Compounds must have a
with SN1 reaction Antiperiplanar acidic hydrogen on its -
because they requirement carbon and poor leaving
share a common Requires strong base group on -carbon
carborcationic Carbanion intermediate
intermediate
Occurs in
Absence of base
No antiperiplanar
requirement

Reactivity of Aryl Halide:
Halogenation
Nitration
Electrophilic Takes place at

substitution ortho and para
reaction Sulphonation position to
chloro group
Fridal craft
Alkylation/
Acylation /
Benzylation
Presence of groups like

Nucleophillic
NO2, -CN, -SO3H, -CHO at
substitution
o-or para position increases
reaction
the activity of chlorobenzene
Table for Ortho Meta and Para directing group:
Substituent Character relative to H Activating / deactivating Directing

-O- Strongly activate Ortho/para
-NR2 Electron donating Strongly activate Ortho/para
-NH2 Strongly activate Ortho/para
-OH Strongly activate Ortho/para
-OR Strongly activate Ortho/para
-NHC(O)R Moderately activate Ortho/para
-OC(O)R Moderately activate Ortho/para
-R Weakly activate Ortho/para
-Ph Weakly activate Ortho/para
-CH=CR2 Weakly activate Ortho/para
-H Reference Neutral Ortho/para
-X(X=halo) Weakly activate Ortho/para
-C(O)H Electron withdrawing Moderately activate Meta
-C(O)R Moderately activate Meta
-C(O)OR Moderately activate Meta
-C(O)OH Moderately activate Meta
-CF3 Strongly deactivate Meta
-CN Strongly deactivate Meta
Solved Examples
JEE Main/Boards As the number of electron donating group increases

more stable is the complex, and more basic is the
Example 1: Benzene, toluene, xylene, (o,m,p) and compound.
mesitylene dissolve in HBF4 to from salts. Explain the Me
order of basicity: H Me H Me H Me H Me
+ HBF4 +
BF4
Sol: The more stable the σ -complex greater would be

the basicity.
Because of + I effect of (Me), the positive charge is
Mesitylene>m-Xylene>o-and p-Xylene> partially neutralized and (Me) group acquires+ δ charge
Toluene> Benzene i.e., there is charge spreading which increases the
H H stability of the σ -complex and thus increases the basic
character of toluene w.r.t. benzene.
+ HBF4 + BF4
Mesitylene has three (Me) groups. So it must be the
-Complex strongest base accordingly.
Since the reaction is reversible; as more stable the Resonating structures of m-, o-, and p-xylenes are.
σ -complex more will be the equilibrium on the right,
i.e., the more basic is the arene.
Me
H Me H Me H Me H Me
+ HBF4 +
Me Me Me Me Me
m-Xylene
(I) (II) (III) (IV)
Me
H Me H Me H Me H Me
Me Me Me Me Me
+ HBF4 +
o-Xylene
(V) (VI) (VII) (VIII)
Me
H Me H Me H Me H Me
+ HBF4 +
Me Me Me Me Me
p-Xylene (IX) (X) (XI) (XII)
In o-and p-xylenes, the resonance-contributing (B) O

structures (VII) and (X) are slightly less stable than other Cl
resonating structures. C6H6
?
So one can conclude that resonating structures of Cl

m-xylene are more stable than o-and p-xylenes, which
increases the basic character of m-xylene than o-and Sol: Generally Aryl halides are less reactive towards
p-xylenes. So the order of basic character is: Nucleophilic substitution reaction. However when a
strong Electron withdrawing group are present in o-or/
Me
and p-positions they undergo such reaction.
(A) (-Br) can be replaced by (-CN) group under high

Me Me pressure and at high-temperature conditions (Dow’s
Mesitylene process).
Me Me Me Me
Me Br CN COOH
= 1 mol of 475 K H3O

+
Me CuCN Pyridine
Toluene Benzene
Me
m- o- p- Br Br Br
Xylene Second 1 mol of
method Mg/ether
Example 2:
(i) CO2
Br MgBr Br COOH
(ii) H3O
Br COOH
(A)
? (B) This involves friedal craft acylation of chlorobenzene.
Chloro groups directs acyl group at para position which
on chlorination in presence of light gives the product.
Br Br
Cl Wurtz reaction.
FeCl3 MeCOCl+ AlCl3 Therefore, 1° and 2° RX undergo Wurtz reaction, while

+ Cl2
F.C. acylation 3° RX undergo dehydrohalogenation to give alkenes.
Me
Cl Cl
Me3C H CH2 C Br
Cl2+h -NaBr
Acidic Me Me
H atom
Cl
Me3CH +CH2 = C Me
O O Me
p-isomer Isobutane Isobutene
(Major)
Example 6: Give the decreasing order of ArSN reaction in:

Example 3: The treatment of RX with aqueous KOH
leads to the formation of alcohols but in the presence of (A) PhCl
alcoholic KOH or NaOH, Alkenes are the major products.
(B) p ‒ NO2 ‒ C6H4 ‒ Cl
Explain why.
(C) 2, 4, 6-Trinitro Chlorobenzene
Sol: NaOH or KOH is completely ionised in aqueous (D) 2, 4-Dinitro Chlorobenzene
solution to give OH- ions, which acts as a strong
nucleophile, so SN reaction takes place with RX to give Sol: ArSN reactions are favored by Electron withdrawing
alcohols. group at o-and p-positions; more the EWG presents at
these positions, faster is the ArSN reaction.
Moreover OH- ions are hydrated or solvated in aqueous
The decreasing order of ArSN reaction:
solution which reduces the basic character of OH- that
cannot abstract acidic β − H atom of RX to form alkene. (C) > (D) > (B) > (A)
In case of alcoholic solution of NaOH or KOH, OH- reacts (C) ⇒ Three (N2) groups at o-and p-,
with ROH to form ROΘ (alkoxide ion) which is a stronger (D) ⇒ Two NO2, groups at o-and p-,
base than OH-, and ROΘ can abstract acidic β − H atom
(B) ⇒ One (NO2) group at p-,
of RX easily to form alkanes.
(A) ⇒ (CI) group.
Example 4: CHF3 is less acidic than CHCI3.Explain.
Example 7: Distinguish between the following
Sol: By considering the stability of conjugate base, compounds:
acidity of the two species can be explained. (I) m-Iodotoluene and (II) Benzyl iodide,
Negative inductive effect of F> CI. According to –I effect,
CHF3 should be more acidic than CHCl3. But this is not Sol: (II) Gives a yellow precipitate of Agl with AgNO3,
observed. whereas (I) Does not.
The reason is the stability of conjugate base.
The conjugate base ‒CCl3 is resonance stabilized due to Example 8:
:
+ HN ?
the presence of d-orbital in Cl [2p(C) -3d(Cl)] overlap.
Θ Piperidine
Conjugate base CF3 is not resonance stabilized due to
the absence of d-orbitals in F. Sol:
H
Example 5: Wurtz reaction in case of tert-alkyl halide N

fails. Explian.
:
+ HN
Θ ⊕
:
Sol: Me3C − X + 2Na → Me3 C− Na+ NaX

t −Butylsodium
t-Alkyl halides undergo dehydrohalogenation in the N

presence of strong base such as Na metal rather than -H
JEE Advanced/Boards Since the benezene ring does not contain any EDG
(activiting group) and vinyl ( −C = CH2 ) group is a
Example 1: weakly activating (and o, p-directing), SE reaction with
Me Br‒ is very slow. Hence, Br2 first adds to the double bond
Me ONa to form major contributing stable structure (I) (due to
the retention of aromaticity), leading to the product (II).
PhCHBr2
Me
?
Ph Ph
CH = CH2 + Br Br
HBr Me3CONa
? ? ? Br + CH CH2Br
Sol: (I)
Br
H
:
H 2Na/Hg in ether
Me3CO Ph3C Cl Ph3CNa CH CH2Br
: :

Ph C Cl Me3CO PhCCl -NaCl
Cl -Elimination
Deep red colour

Ph C PhCCl Ph
Carbene
Ph
(II)
Cl -Elimination
-HCl Ph Ph HOH
Carbene ROH
Cl -Hcl Ph3CH + RONa
Example 3: Ph3CH + NaOH
Ph Ph Ph Ph
Ph Ph Ph Ph
Me3CO Ph3C Cl
Me3CO 2Na/Hg in ether
Chlorotriphenyl Deep red colour
Ph OCMe3 Ph Cl methane
Ph OCMe3 Ph Cl Colour is H2O
discharged or
HBr ROH
HBr
Ph Ph Ph Ph
Ph Ph Ph Ph
+ Sol: Strong reducing agent, such as Na/Hg amalgam,
Br
Br + converts Ph3C-Cl to the sodium salt, very stable
Br
Br
Ph3 CΘ (triphenyl methyl or trityl anion) because of
Ph Ph
delocalisation of negative charge to three Ph rings. The
(( ((
Ph Ph
Three-membered ring Triphenylcyclo
Three-membered ring
attains aromaticity Triphenylcyclo
propenium bromide strongly basic carbanion accepts H+ from either weakly
attains aromaticity propenium bromide acidic H2O or ROH giving colorless Ph3CH.
:
2Na/Hg in ether
The absence of β − H atom suggests α -elimination via Ph3C Cl Ph3CNa
-NaCl
the formation of carbine intermediate which forms ring Deep red colour
with ( C ≡ C )
OMe HOH
ROH
Ph3CH + RONa
LiNMe2
(A) Ph3CH + NaOH ?+?
Ether
Example 2:
Ph3C Cl
2Na/Hg in ether Cl
Example 4:
Chlorotriphenyl Deep red colour
methane
OMe
Br2 + FeBr3 Colour is H2O KOH
(B)+(C)+(B) (B) ?
(A) LiNMe2
(B) Ph or
Br2 + FeBr3 (A) ? + discharged
?
Styrene Ether ROH
(B)+(C)+(B)
Styrene Cl
Sol: Br Br Br
Br Br Br
Br Br Br Br Sol:
(B) It is an example
KOH of ArSN (elimination-addition)
?
Br2 Br Br Br Ph via benzyneintermediate, since strong Electron
reaction
+ +
FeBr3
Br2
Br withdrawing group o or/and p-to the eliminating group
+ + is not present. Thus, ArSN (addition-elimination) is not
FeBr3 Br Br possible.
Br Br
 Θ  Example 5:
 : NMe2  Group in (LiNMe2) acts as a base to remove
 
1
H SN Cr2O3 or V2O5
Me CH2 O CH2
ortho-H atom to the eliminating group.
(B) (C)
(A) or Mo2O3
Me
: :
:
:
O N O 773 K, 10-20 atm
Since the rearranged product has increased conjugation
with the ring, it is a thermodynamically controlled Me CH2 O CH2 ON O
product (T.C.P) and is the result of an equilibrium- Sol: Nitrite
controlled Reaction. 1 1
2 2
Hence, the starting material is the kinetically controlled H 1, 2-H shift
product (K.C.P). 4
3
4
3
Me Me
The conversion of K.C.P. to T.C.P is due to the removal of 5 Me
α -H atom by base, and α -H atom is acidic due to the 6
1
1
2
-I effect of (Ph-) group. Cr2O3
2 H
Intramole- 4 3
(A) Aromati- 4 3 Me
cular F.C. Me
sation
OMe OMe Me reaction
(B) Me
o
3 C
LiNMe2 Li
Me2NH+ (More stable)
Me Et
:
Cl Cl 1-Ethyl-1-methyl
naphthalene
OMe (C)
OMe
Me2NH -LiCl Example 6: (A) Account of the rapid of ethanolysis of

Li
(Me O Cl)
Cl
OMe OMe Although is 1° halide.
+ Sol: (A) This is due to the stability of carbocation

NMe2
bonded to by resonance.
NMe2 The NO2 is an ambident nucleophile (two nucleophilic
(B) centers N and O).
KOH More is the positive charge on the carbocation

CH = CH CH3
formed, it will attack at the more electronegative (EN)
Ph [Extended conjugation
with (C=C) of (Ph-) group] nucleophilic center and vice versa. (Since EN of O>N)
SN1
Steps involved are: Me O Cl Cl +
CH2 CH2
OH
: :
Ph CH2 CH=CH2 -H O Me O Me O
:
( (
2
EtO -H
CH CH=CH2
Me O OEt
CH CH=CH2
Example 7: Catalytic dehydrogenation of methyl
cyclohexane, obtained from petroleum, gives a liquid
H2O
Ph CH=CH2 CH2 which on treatment with chlorosulphonic acid at 370 K
+H yields a mixture of two isomers (A) and (B), C7H7SO2Cl. The
major isomer (A) reacts with ammonia to form (C), which
Ph CH=CH CH3 on oxidation with permanganate gives compound (D). On
heating, compound (D) gives a well-known sweetening
(E). The minor isomer (B) also reacts with ammonia to give
a compound (F) which on treatment with NaClO/NaOH CH3 CH3 COOH

gives an antiseptic (G): Identify (A) to (G).
NaOCl
Sol:
Excess of Cl2
CH33 CH3 3
CH
Pt at
at 500 oo
500 CC ClSO2OH SO2NH2 Cl Cl
Pt ClSO 2OH SO2 N SO2 N
or
or 370KK
370 Cl Cl
Cr22O
Cr O33-Al
-Al22OO33 (Halozone) (Used
oo
at 600
at 600 CC CH3 3
CH CH
CH 33 for sterilising drinking water)
SO
SO2Cl
2Cl
++
Example 8: A Grignard reagent (A) and a halo alkene
(A)
(A)
(B)
SO
SO2Cl
2Cl (B) react together to give (C). compound (C) on heating
(B)
with KOH yields a mixture of two geometrical isomers.
CH CH
(D) And (E), of which (D) predominates. (C) Gives
CH33 CH3 3
SO
SO22Cl SO
SO2NH
Cl NH 2NH
1-bromo-3-phenyl propane on reaction with HBr in the
2 [O]
2 [O]
NH33
presence of a peroxide. Give the structure of (A), (B),
(A) O (C
(C) )
(A) O COOH
COOH and (C) and the configurations of (D) and (E).
-H SO2NH
NH
NH -H2O
2O
SO NH
2
2 2
Sol:
SO2
SO2
(E) (Sweetening agent) (D)
(E) (Sweetening agent) (D)
o-Sulphobenzoic imide
o-Sulphobenzoic imide
PhMgX + XCH2 CH CH2
CH3 CH3 CH3
CH3 CH3 CH3 (A) (B)
NH3 NaClO/NaOH Ph CH2 CH CH2 + MgX2
NH3 NaClO/NaOH
HBr, peroxide ; (C)
Na anti-
SO2Cl SO2NH2 SO2 N Na Markovnikov
SO2 N Cl KOH
(( ((
SO2Cl
(B) (F)SO2NH2
(B) (F) Chloramine-T
Cl Shifting of
3 2 1
Chloramine-T
An antiseptic Ph CH2 CH2 CH2 double bond
An antiseptic
1.2% soln for
1.2% soln for
mouthwash) Br
mouthwash)
1-Bromo-3-phenyl propane
Ph H Ph CH3
C C + C C
H trans CH3 H cis H
(D) (E)
(More stable)
JEE Main/Boards
Exercise 1 (v) CH3 CH(CH3)CH(Br) CH3

(vi) CH3C(C2H5)2 CH2 Br
Q.1 Name the following halides according to IUPAC
system and classify them as alkyl, allyl, banzyl (primary, (vii) CH3C(Cl) (C2H5) CH2CH3
secondary, tertiary), vinyl or aryl halides:
(Viii) CH3 CH=C(Cl)CH2(CH3)2
(i) (CH3)2 CHCH(Cl)CH3
(ix) CH3 CH=CHC(Br) (CH3)2
(ii) CH3 CH2 CH(CH3)CH(C2H5) Cl
(x) p-ClC6H4CH2CH(CH3)2
(iii) CH3 CH2 C(CH3)2CH2 I
(iv) (CH3)2CCH2 CH(Br)C6H5

Q.2 Which one of the following has the highest dipole Q.13 Write the mechanism of the following reaction:
moment why? BOH−H O
2 → nBuCN
nBuBr + KCN 
(i) CH2Cl2 (ii) CHCl3 (iii) CCl4
Q.3 What are ambident nucleophiles? Explain with an Q.14 Out of C6H5CH2Cl and C6H5CHClC6H5, which is
example. more easily hydrolyzed by aqueous KOH?
Q.4 Write the equation Wurtz-fittig reaction. Q.15 The treatment of alkyl chlorides with aqueous KOH
leads to the formation of alcohols but in the presence
of alcoholic KOH, alkenes are major products. Explain.
Q.5 p-Dichlorobenzene has higher m.p. and solubility
than those of o-and m-isomers. Discuss.
Q.16 Identify and indicate the presence of chirality,
if any in the following molecule. How many stereo
Q.6 An alkyl halide, (X) of formula C6H13 Cl on treatment
isomers are possible for those containing chiral center?
with potassium tertiary butoxide gives two isomeric
alkenes (Y) and (Z). (C6H12). Both alkenes on hydrogenation
give 2, 3-dimethybutane. Predict the structures of (X), (Y) Q.17 Give two example of molecules which contain
and (Z). chirality centers but process a chiral structure?
Q.7 What happens when and complete equation? Q.18 Write the equation of elimination with mechanism?
(i) n-butyl chloride is treated with alcoholic KOH. Q.19 (i) Why are haloalkanes more reactive towards
(ii) Bromobenzene is treated with Mg in the presence nucleophilic substitution reaction than haloarenes?
of dry ether. (ii) Which of the following two substance undergo SN1
(iii) Chlorobezene is subjected to hydrolysis. reaction faster and why?
(iv) Ethyl chloride is treated with aqueous KOH. Q.20 Identify and indicate the presence of center of
(v) Methyl bromide is treated with sodium in the chirality, if any in the following molecules. How many
presence of dry ether. stereoisomers are possible for those containing chiral
center?
(vi) Methyl chloride is treated with KCN.
(i) 1, 2-dichloropropane
Q.8 What is meant by chiral or asymmetric carbon (ii) 3-bromo-pent-1-ene
atom?
Q.21 Does the presence of two chiral carbon atoms

Q.9 Write the equations for the preparation of
always make the molecule optically active? Explain
1-iodobutane from
giving an example.
(i) 1-butanol (ii) 1-Chlorobutane (iii) But-1-ene.
Q.22 How can iodoform be prepared from ethanol?
Q.10 Which compound in each of the following pairs (Give equation)
will react faster in SN 2 reaction with –OH?
Q.23 How can methyl bromide preferentially converted
(i) CH3 Br or CH3I (ii) (CH3)3 CCl or CH3 Cl
to methyl isocynaide?
Q.11 Predict all the alkenes that would be formed by Q.24 Write the difference between SN1 and SN2
dehydrohalogenation of the following halides with reaction?
sodium ethoxide in ethanol and identify the major alkene:
(i) 1-Bromo-1-methylcyclohexane Q.25 Explain nucleophilic substitution reaction in aryl
halides?
(ii) 2-chloro-2- methylbutane
(iii) 2,2,3-Trimethyl-3-bromopentane. Q.26 How will you bring about the following
conversions?
Q.12 Gives the uses of Freon 12,DDT, carbon
(i) Bromoethane to cis-hex-3-ene
tetrachloride and iodoform.
(ii) Benzyl alcohol to phenylethanenitrile Exercise 2

(iii) Cyclopentene to cyclopenta-1, 3-diene
Single Correct Choice Type
Q.27 Write the equation of Swarts reaction.
Q.1 Consider the following halo alkanes:
Q.28 Although chlorine is an electron withdrawing 1. CH3F 2. CH3Cl 3. CH3Br 4. CH3I

group, yet it is ortho-para directing in electrophilic The increasing order of reactivity in nucleophilic
acromatic substitution reactions. Why? substitution reaction is
(A) 1<2<4<3 (B) 1<2<3<4
Q.29 Explain why (i) The dipole moment of
chlorobenzene is lower than that cyclohexyl chloride. (C) 1<3<2<4 (D) 4<3<2<1
(ii) Alkyl halides, though polar, are immiscible with
water. Q.2 Which of the following haloalkane is hydrolyzed by
SN1 mechanism?
(iii) Grignard reagents should be prepared under
anhydrous conditions. (A) CH3Br (B) CH3CH2Br
(C) CH3CH2CH2Br (D) (CH3)3 CBr
Q.30 Write the method formation of halo arenes.
Q.3 The reaction of t-butyl chloride and sodium
Q.31 Write the chemical properties of halo arenes.
exthoxide gives mainly
Q.32 Explain SN1 Mechanism with example. (A) t-butyl ethyl ether (B) 2, 2-dimethylbutane
(C) 2-methylprop-1-ene (D) Isopropyl n-propyl ether
Q.33 What are arenes? How are they classified? Discuss
briefly the isomerism and nomenclature of arenes.
Q.4 The fire extinguisher ‘pyrene’ contains.
(A) Carbon dioxide (B) Carbon disulphide
Q.34 Discuss of structure of benzene laying emphasis
on resonance and orbital structure. (C) Carbon Tetrachloride (D) Chloroform
Q.35 CH3 HCO3H Q.5 The final product (Z) is the following sequence of
X reactions
KMnO2,
Y HNO
2 →(X) 
CH3CH2 NH2 
SOCl
3 → (Z) is
2 →(Y)  NH
O3, H2O Z (mix)

(A) Methanamine (B) Ethanamide
Identify X, Y and Z (C) Ethanamine (D) Propan-1-amine
Q.36 Justify the Statement: Benzene is highly Q.6 Consider the following reactions:
unsaturated compound but behaves like a saturated
compound. 1. CH3CH2CH2Cl+I‒ →
2. (CH3)3 C-Br+ ethanolic KCN →
Q.37 Discuss briefly the mechanism of electrophilic 3. CH3CHBrCH3+aqueous KOH →
substitution reactions in benzene.
4. CH3CHBrCH3+alcoholic KOH →
Q.38 Explain the directive influence of various The most likely products is these reactions would be
substituent and their effect on reactivity of arenes.
(A) 1. CH3CH2CH2l 2. (CH3 )3 C− CN
Q.39 Complete the following sequences 3. CH3 − C H− CH3 4. CH3 − C H− CH3

| |
OH OH
AlCl
+ CH3—CH2—CH2—Cl →
3
CH3 (C) Both equal rates (SN1 and SN2)

|
(B) 1. CH3CH2CH2Cl 2. CH
= C − CH3 (D) None of these
2
3. CH3 − C H− CH3 4. CH3 − CH =

CH2
| Q.10 The correct order of nucleophilicity is
OH
(A) Me3CO‒ > Me2CHO‒ > O-
(C)
= 1. CH3 − CH CH2 2. (CH3 )3 C − CN
3. CH3 − C H− CH3 4. CH3 − CH =

CH2 (B) O- > Me2CHO‒ > Me3CO‒
|
OH (C) Me2CHO‒ > O- > Me3CO‒
(D) 1. CH3 − CHCH2 l 2. (CH3 )3 C − CN (D) None of these

3. CH3 − CH =
CH2 4. CH3 − C H− CH3
|
Q.11 Arrange the following in order of decreasing
OH
reactivity towards SN2 reaction.
Q.7 Aryl halides are less reactive towards nucleophilic (i) CH3CH2CH2Cl (ii) CH3CH2 CHClCH3
substitution reaction as compared to alkyl halides due to (iii) (CH3)2CHCH2Cl (iv) (CH3)3CCl
(A) The formation of less stable carbonium ion
(A) (i)>(ii)>(iii)>(iv) (B) (iii)>(iv)>(ii)>(i)
(B) Resonance stabilization
(C) (i)>(iii)>(ii)>(iv) (D) (iv)>(iii)>(ii)>(i)
(C) Longer carbon-halogen bond
(D) sp2-hybridized C attached to the H Q.12 In the reaction:
KCN [H]
Q.8 In the following reaction: A  → B  → C2H5NH2
Br (A) A is CH3I (B) B is CH3 NC

l
( )
CH
3 2
CHC
Step I
= CH →(CH ) CHC − =
32
C CH
2
(C) A is C2H5 I (D) B is C2H5NC
Br
AgNO
l 2→
StepII Q.13 C2H5I  X . Here X is
→(CH ) C H − CH− CH Br (Major product)
32 2
O
Which of the following sets of reagents can be used for
step I and step II? (A) C2H5-O-N=O (B) C2H5 - N
O
Step I Step II
1. HBr HBr and peroxide (C) C2H5-N=O (D) C2H5-N=N-C2H5
2. HBr and peroxide HBr Ni− Al/NaOH

Q.14 C6H5Cl → X The compound X is
3. Br2 HBr
(A) Phenol
4. Br2 HBr and peroxide
(B) Benzene
Select the correct answer using the codes given below
(C) o-and p-Chlorophenol
(A) 1, 2 and 4 (B) 2 and 4
(D) Benzol
(C) 3 and 4 (D) 1 Alone
Q.15 Which of the following is least reactive towards
Q.9 Cl-CH2-O-CH2CH3 will undergo rapid nucleophilic displacement reaction when treated with
(A) SN1 substitution aqueous KOH?
(B) SN2 substitution (A) 2, 4, 6-Trinitrochlorobenzene

(B) 2, 4-Dinitrochlorobenzene o
600 C
Q.22 Z .Z may be
(C) 4-Nitrochlorobenzene
(D) 3- Nitrochlorobenzene
(A)
(A)
Q.16 o-Chlorotoluene reacts with sodamide in liquid
NH3 to give o-toluidine, and m-toluidine. This proceeds
through an Intermediate (B)
(B)
CH3 CH3 CH3 CH3

Cl (C)
(C)
(A) (B) (C) (D)
(D) None of these
Q.17 The final product D in the above sequence of Q.23 Which of the following is used for aromatization
reactions is of n-hexane?
(A) AlCl3
2 NBS Alc.KOH Pd/C
+ A B C D
-H2
(B) Na in liquid NH2
(A) Benzene (B) Tetralin (C) Cr2O3/Al2O3 with heat
(C) Decalin (D) Naphthalene (D) Wilkinson’s catalyst
OH
Q.18 1, 3-Dichloropropane reacts with Zn and NaI and Q.24 CH=CH CH3 CHCH3CH3
gives (major product)
+
(A) Propane (B) Propane H2O/H
(C) Cyclopropane (D) n-Proyl iodine

The stereochemistry of product is
Q.19 SN2 reactions are (A) Dextro (B) Laevo
(A) Stereospecific but not stereo selective (C) Meso (D) Racemic
(B) Stereo selective but not Stereospecific
(C) Stereo selective as well as Stereospecific Previous Years’ Questions
(D) Neither stereo selective nor Stereospecific
Q.1 Among the following, the molecule with the highest
Q.20 Benzyl Chloride (C6H5CH2Cl) can be prepared from dipole moment is (2003)
toluene by chlorination with (A) CH3Cl (B) CH2Cl2
(A) SO2 Cl2 (B) SOCl2 (C) HCl (D) NaOCl (C) CHCl3 (D) CCl4
Q.21 Which xylene gives only one monobromo Q.2 What would be the product formed when 1-Bromo-
derivative? 3-chloro cyclobutane reacts with two equivalents of
metallic sodium in ether (2005)
(A) Ortho (B) Para
Cl
(C) Meta (D) None of these (A) (B)
Br
(D)
(C)
Q.3 Aryl halide are less reactive towards nucleophilic Q.9 The synthesis of alkyl fluorides is best accomplished
substitution reaction as compared to alkyl halide due by: (2015)
to (1990)
(A) Free radical fluorination (B) Sandmeyer’s reaction
(A) The formation of less stable carbonium ion
(C) Finkelstein reaction (D) Swarts reaction
(C) Longer carbon-halogen bond Q.10 In the reaction (2015)
(D) The inductive effect NH2

(E) sp2-hybridized carbon attached to the halogen NaNO2/HCl CuCN/KCN
D E + N2
o
0-5 C
Q.4 The compounds used as refrigerant are (1990)
CH3
(A) NH3 (B) CCl4
The product E is:
(C) CF4 (D) CF2Cl2 (E) CH2F2
COOH
Q.5 The products of reaction of alcoholic silver nitrite (B)
(A)
(A) (B) H3C CH3
with ethyl bromide are (1991)
(A) Ethane (B) Ethene CH3
(C) Nitro ethane (D) Ethyl alcohol CN CH3
(E) Ethyl nitrite
(C)
(C) (D)
(D)
Q.6 A new carbon-carbon bond formation is possible in

CH3
(1998)
(A) Cannizzaro reaction
(B) Friedel-Craft’s alkylation Q. 11 The product of the reaction given below is:
(C) Clemmensen reduction 1. NBS / h

X (2016)
2. H2O / K2CO3
(D) Riemer- Tiemann reaction
Q.7 Which of the following compounds does not OH

disslove in conc.H2SO4 even on warming? (1983) (A) (B)
(A) Ethylene (B) Benzene
(C) Hexane (D) Aniline
O CO2H
Q.8 Compound (A), C8H9Br, gives a white precipitate (C) (D)
when warmed with alcoholic AgNO3. Oxidation of (A)
gives an acid (B), C8H6O4 . (B) easily forms anhydride on
heating. Identify thecompound (A). (2013)
CH3Br C2H5
Q.12 2- Chloro -2 – methyl pentane on reaction with
sodium methoxide in methanol yields : (2016)
(A) (B)
Br CH3
C2H5CH2C CH2 C2H5CH2 C CH3
CH3 C2H5CH2C OCH3
CH3 CH3
CH3
CH2Br (i)
(A) (ii)
(B) (iii)
(C)
CH2Br
(A) All of these (B) (i) and (iii)
(C) (D)
CH3 (C) (iii) only (D) (i) and (ii)
CH3
JEE Advanced/Boards
Exercise 1 Q.4 Explain electrophilic substitution reactions of aryl

halide.
Q.1 Account for the observation that the hydrolysis
(solvolysis in water) of (I) occurs much faster than other Q.5 Write the structure of the major organic product in
primary chlorides, and gives mainly (II). each of the following reactions:
H3 C Ethanol
H2C CH3 (A) (CH3)3 CBr+KOH 
→
H2 O Heat
Cl H2 C
Water
H3C
CH3
OH (B) CH3CH(Br)CH2CH3+NaOH 
→
(I) (II) Liq.NH
(C) CH2=CHCH2Br+CH3C ≡ CNa+ 
3
→
OH
Q.2 Vinyl chloride does not give SN reaction but allyl Red P/Br2
chloride gives. Explain. (D)
Q.3 Suggest a mechanism for each transformation

below. Show all steps in each of your mechanisms.
OH
Br Br + HBr
O (E) HO
H2 O
(A) + 2HBr
Q.6 Explain miscellaneous reactions of aryl halide.
CH3
CH3 H3 C CH3 Q.7 Propose a mechanism for the following reaction
(B) H3C CH3Li C
H3C CH3 OH
Br H3 C CH3
Br
CH3
CH3 CH3 H2O
H3C AlBr3
(C) H3 C Br
H3C
Br Br
Br
OH Q.8 What products would be formed when each of the
(D) Ag+ following compounds reacts with N-bromosuccinimide
Br H2 O in CCl4 in the presence of light.
Br
CH3
CH3
CH3 OH H3C CH3 (A) (B)
(E) H3C CH3 H+ CH3 CH3
OH CH3 O CH3
CH3
H H H H (C)
CH3 (D)
H-
(F) H
Br H3C CH3
H3C H3 C CH3
Q.9 (a) p-Methoxylbenzyl bromide reacts faster than CCl4; all three are soluble in cold conc. H2SO4. Compound
p-nitrobenzyl with ethanol to from an ether product. a gives a precipitate when treated with AgNO3 in NH3
Explain why. (aq), but compound B and C do not. Compound A and
B both yield hexane when they are treated with excess
(b) In the following reaction the relative rate is 3,300
H2 in the presence of platinum catalyst, under these
faster when X = F than I. explain.
conditions C absorbs only one molar equivalent of H2
and gives a product with the formula C6 H12. When A is
X
NO2 N
oxidized with basic KMnO4 and the resulting solution
NO2
acidified, the only organic product that can be isolated
+
N is CH3(CH2)3CO2H. Similar oxidation only CH3CH2CO2H
+ X- and C gives only HO2C(CH2)COH. What are structures
NO2 H of A, B and C.
NO2
Q.13 The alkyl halide C4H4Br (A) reacts alcoholic KOH

Q.10 (a) Complete the following transformations: and gives an alkene (B), which reacts with bromine to
CH3 give dibromide (C). (C) is transformed with sodamide
to a gas (D) which forms a precipitate when passed
Cl2 SOCl2
(a) A
(i) KCN
B C D through an ammonical silver nitrate solution. Give the
sunlight (ii) H3O+ AlCl3 structural formulae of the compounds (A), (B),and (D)
Pb(NO3)2, boil and explain reactions involved.
H3O+
E HCN F G
Q.14 An optically active compound A (assume that it
KCN NaBH4 is dextrorotatory) has the molecular formula C7H11Br.
H l
(alcoholic) A reacts with HBr, in the absence of peroxide to yield
isomeric products, B and C, with molecular formula
(b) Identify A, B, C, D and E in the following C7H12Br2. Compound B is optically active C is not.
Cl2, CCl4 Treating B with 1 mol of potassium tert-butoxide
yields ( ± A ) . Treating A with potassium tert-butoxide
(b) (C6H12) (C6H12Cl2)
(A) (B)
yields D(C7H10). Subjecting 1 mol of D to ozonolysis
O3/H2O/Zn
(i) Alcoholic KOH followed by treatment with zinc and water yield 2 mol
D + CH3CHO (ii) NaNH2
of formaldehyde and 1 mol of 1, 3-cyclopentandione.
Propose strereo-chemical formulae for A, B, C and D and
(C6H10) outline the reaction involved in these transformations
H3C CH3
(C) H2/Pt
(c) Identify A, B, C, D and E in the following Q.15 Explain elimination reaction in halo arene.
Br
Q.16 Compound A (C8H12Cl) exists as a racemic form.
Compound A does not decolorise either Br2/CCl4 or
(CH3)3COK+ Cold dil. KMnO4
A B dilute aqueousKMnO4. When A is treated with Zn/
HCO3H
C CH3COOH, two fractions B and C both with molecular
O, H2O BaO, formula C8 H16 are obtained fraction B consists of a
racemic form and can be resolved. Fraction C can’t be
D E
resolved. Treating A with sodium ethoxide in ethanol

converts A into D(C8H14). Hydrogenation of D using
Q.11 Identify A, B, C and D in the following: platinum catalyst yields C. Ozonolysis of D, followed by
Also select pair of isomers if any treatment with zinc and water yields.
O
HBr i) H+ BH3/THF HBr CH3
D C A B
ii) H2O H2O2/OH-
H3C
O
Q.12 Three compounds A, B and C all have the formula Assign structure to A, B, C and D.
C6 H10. All three compounds rapidly decolorise Br2 in
Q.17 For each reaction below, fill in the structure of Q.19 Convert with equation.
the expected product, showing stereochemistry where
(i) Benzene to p-nitrochlorobenzene
appropriate. Then indicate the type of reaction and/or
mechanism involved. (ii) Benzene to aniline
(iii) Benzene to m- nitrochlorobenzene
Br
(A)
H2CO [H] (iv) Benzene to dipehnyl
H 25
o
CH3 (v) Benzene to p-chlorotoluene

(vi) chlorobenzene to DDT
H (vii) chlorobenzene to phenyl cyanide
(B) base+CHBr3
(viii) Benzene diazonium chloride to aniline.
H
(ix) Aniline to phenyl isocyanide.
OH- Q.20 An organic compound A, C6H10O, on reaction with

(C) CH3Mg Br followed by acid treatment gives compound
N+ CH3 B. The compound B on ozonolysis gives compound C,
H3C CH3 which in presence of a base gives 1-acetyl cyclopentene
D. The compound B on reaction with HBr gives
CH3 compound E. Write the structures of A, B, C and E. Show
how D is formed from C.
H3C (CH3CO3H)
(D) (C7H14)
CH3 70o Q.21 Explain briefly the formation of the products
RSO2O CH3
giving the structures of the intermediates.
H H HCl
Ph + + etc.
(E) H2 C
CH3
OH H2C
CH3
OH Cl
H3C
Ph N+ HCl
only
OH H2 C Cl
H3C CH3
O-
H3C CH3 Q.22 Explain why

(F) (i) Vinyl chloride is unreactive in nucleophilic substitution
+ CH2N2
reaction?
H H
(ii) Neo-pentyl bromide undergoes nucleophilic
substitution reaction very slowly?
Q.18 What would be the major product in each of the (iii) 3- bromocyclohexene is more reactive than
following reactions? 4-bromocyclhexene in hydrolysis with aqueous NaOH ?
CH3 (iv) Tert-butyl chloride reacts with aqueous sodium
C2H5OH hydroxide by SN1 mechanism while n-buty chloride
(I) H3C
reacts with by SN 2 mechanism?
CH3 Br
F
Q.23 Write down the intermediate steps in the followed
NaOCH3 reaction
(II) O
H3C
O O O
NO2
O Br C2H5 H 3C
NaOEt CH3
C2H5
Ph HO
base O
(III) O C2H5
O
O
Br
Q.24 Optically active 2-iodobutane on treatment with Q.31 The freezing point constant of C6H6 is 4.90 and
Nal in acetone gives a product which does not show its melting point 5.51ºC. A solution of 0.810 g of a
optical activity. Explain why? compound (A) when dissolved in 7.5 gms of benzene
freezes at 1.59ºC. The compound (A) has C = 70.58%.
Q.25 An organic compound ‘A’ having molecular Compound (A) on heating with sodalime gives another
formula C4H8 on treatment H2SO4 gives ‘B’. ’B’ on compound (B) which on oxidation and subsequent
treatment with conc. HCl and anhydrous ZnCl2 gives acidifications gives an acid (C) of equivalent weight 122.
‘C’; and on treatment with sodium ethoxide gives back (C) on heating with sodalime gives benzene. Identify
‘A’ identify the compounds ‘A’, ‘B’ and ‘C’ and write the (A), (B) and (C) and explain the reactions involved.
equations involved.
Q.32 When bromo benzene is mono chlorinated,
two isomeric compounds (A) and (B) are obtained.
Q.26 (W) and (X) are optically active isomers of C6H9Cl.
Monobromination of (A) gives several isomeric products
(W) on treatment with one mole of H2 is converted
of formula C6H3ClBr2. While monobromination of (B) yields
to an optically inactive compound (Y), but (X) gives
only two isomeric (C) and (D). Compound (C) is identical
an optically active compound (Z) under the same
with one of the compound obtained from the bromination
conditions. Give structure of (Y) and configuration
of (A). However (D) is totally different from any of the
of(W), (X) and (Z) in Fischer projections.
isomeric compounds obtained from bromination of (A).
Give structures of (A), (B) and (D) with explanation.
Q.27 A white precipitate was formed slowly when
Br
AgNO3 was added to a compound (A) with molecular
formula C6H13Cl. Compound (A) on treatment with hot C2H5
Cu Powder
alcoholic KOH gave a mixture of two isomeric alkenes Q.33 (A)

(B) and (C) having formula C6 H12. The mixture of (B) and
(C) on ozonolysis furnished four compounds.
Write the structure of A and explain its stereochemistry
(i) CH3CHO; (ii) C2H5CHO;
(iii) CH3COCH3; (iv) (CH3)2CHCHO. Q.34 + CH3COCl
AlCl3
A
What are (A), (B) and C? NO2

Q.28 Primary alkyl halide C4H9Br (a) reacted with alcoholic Zn-Hg Br2/Fe
B C
KOH to give compound (b). Compound (b) is reacted HCl
with HBr to give (c) which is an isomer of (a). When (a) is
reacted with sodium metal it gives compound (d), C8H18 Me
which is different form the compound formed when Q.35 Nitration of with HNO3 in acetic acid
n-butyl bromide is reacted with sodium. Give the structural
formula of (a) and write the equations for all the reactions. solvent at 45ºC occurs 25 times faster than nitration
of under same condition and the percentage are

Q.29 Cyclobutyl bromide on treatment with magnesium
in dry ether forms an organometallic (A). The ortho = 56.5 meta = 3.5 and para 40.0. What is the
organometallic react with ethanol to give an alcohol (B) partial rate factor. Can these values be taken for other
after mild acidification. Prolonged treatment of alcohol electrophilic substitution reactions of toluene.
(B) with an equivalent amount of HBr gives 1-bromo-1-
methyl-cyclopentane (C). Write the structures of (A), (B) Q.36 An aromatic hydrocarbon (A) (mol. wt.=92)
and explain how (C) is obtained from (B). containing C=91.3% and H=8.7% gave on treatment with
chlorine three isomeric compounds (B), (C) and (D) each
Q.30 An organic compound (X) on analysis gives containing 28% chlorine. On oxidation, each of three gave
24.24% C, 4.04% H. Further sodium extract of 1.0 g of monobasic acids X, Y and Z respectively. The acid (X) can
(X) gives 2.90 g of AgCl with acidified AgNO3 solution. also be obtained by the oxidation of (A) while (Y) and
The compound (X) may be represented by two isomeric (Z) contained chlorine also. The acid X on reaction with
structures (Y) and (Z). (Y) on treatment with aqueous soda lime gave benzene while acids (Y) and (Z) on similar
KOH solution gives a dihydroxy compound, while (Z) on treatment gave chlorobenzene. What are A, B, C, D, X, Y, Z.
similar treatment gives ethanol. Find out (X), (Y) and (Z).
Q.37 The values for nitration of t-butyl benzene are CH CH CH CH

o = 4.5, m= 3.0, p = 75. How much more reactive is 3 3 3 3
| | | |
t-butyl benzene than benzene.
(A) CH2 = C − CH - CH3 and CH3 − C = C - CH3
Q.38 Which of the following C6H6 structure gives only

one C6H5 Br isomer CH CH CH CH
3 3 3 3
CH2 | | | |
(B)
= CH2 − C CH - CH3 and
= CH3 − C C - CH3
(A)
(B)
CH2 CH2 CH CH CH CH
3 3 3 3
| | | |
CH2
(C)
= CH2 − C CH - CH3 and
= CH2 − C C - CH3
(C) (D) (D) None of these
Aq.NaOH
Q.4 CH − CH CH Br  →X
Q.39 Write the Mechanism of nitration of benzene and 3 2 2
toluene. Al O Cl / H O
2 3 Y 
X → 2 2 →
Heat
CH2CH2CH2Br
Exercise 2 (A) Identify ‘z’ in
Single Correct Choice Type (A) Mixture of CH3 − C H − C H2 and CH3 − C H − C H2

CH2CH2CH3 | | | |
Q.1 Propylbenzene reacts with
(B) bromine in presence of Cl Cl OH Cl
light or heat to give Br (B) CH3 − C H − C H2
| |
CH2CH2CH2Br CH2 CH CH3 OH Cl
(A) (C) Br
(C) CH3 − C H − C H2
| |
CH2CH2CH3
CH CH2CH3 Cl OH
(B)
(D) Br
Br (D) None of these
Q.2 Which CH one CHof CH

the following would undergo
Q.5 The correct order of leaving tendency of
hydrolysis most readily with aqueous sodium hydroxide
2 3
(C) Br
to form the corresponding hydroxide derivative? (i) OH- (ii) ArSO3- (iii) MeCOO- is
NO2 (A) i < ii < iii (B) i < iii < ii (C) iii < i < ii (D) iii < ii < i
CH CH2CH3
(D) O N
(A) 2
Br Cl (D) O2N Cl Q.6 List the hydrogen halide acids in decreasing
order of reactivity in the following reaction:
NO2 R-OH+HX → RX + H2O
(A) HI>HBr>HCI>HF (B) HBr>HI>HCI>HF
(B) Cl (C) (CH3)2N Cl (C) HI>HCI>HBr>HF (D) HI>HF>HBr>HI.
Q.7 In the mechanism for the reaction of HBr with

Q.3 An alkyl halide of formula C6H13Cl on treatment t-butyl alcohol, pick out the incorrect statement.
with potassium tertiary butoxide gives two isomeric
(A) Formation of protonated alcohol is a slow step
alkenes (C6H12). Both alkenes on hydrogenation give 2,
3-dimethybutane. Isomeric alkenes are (B) Formation of (CH3)3 C+ is a slow step
(C) Formation of (CH3)3 CBr from (CH3)3 C+ is a slow step Q.14 When propane is heated with excess of Cl2 at
(D) Formation of (CH3)3 C is a fast step
+ 573-673 K under 75-100 atm. Pressure, the products
obtained are
Q.8 SN1 reactions occur through the intermediate (A) CH3CH2CH2Cl + CH3CHClCH3
formation of (B) CCl4+C2Cl6
(A) Carbocations (B) Carbanions (C) CH3CH2CHCl + CH3CHClCH2Cl
(C) Free radicals (D) None of these (D) CHCl3 + CH3CH2Cl
Q.9 SN1 reactions are favored by Q.15 Which of the following is used as a camphor
substitute?
(A) None polar solvents
(B) Bulky groups on the carbon atom attached to the (A) C2Cl6 (B) CHCl3 (C) CCl4 (D) CF2Cl2
halogen atom
(C) Small groups on carbon atom attached to the Q.16 Freon used as a refrigerant is
halogen atom (A) Acetylene tetrachloride
(D) None of these
(B) Trichloroethylene
(C) Dichlorodifluoromethane
Q.10 The main product formed when ethylbenzene
reacts with chlorine in presence of UV light is (D) Ethylene dichloride
(A) 1-Chloro-1-phenylethane
(B) o-Chloroethylbenzene Q.17 n-Propyl bromide on treatment with ethanolic
potassium hydroxide produces
(C) 2-Chloro-1-phenylethane
(D) p-Chloroethylbenzene (A) Propane (B) Propene
(C) Propyne (D) Propanol
Q.11 + CH2Cl2
Anhyd.
AlCl3
A. A is Q.18 Chlorobenzene can be prepared by reacting
aniline with
Excess
(A) Hydrochloride acid
(B) Cuprous chloride
(A) CH2Cl (B) CHCl2
(C) Chlorine in presence of anhydrous aluminum
chloride
(C) (D) CH2 (D) Nitrous acid followed by heating with cuprous
chloride
Q.19 Carbylamine test is performed in alcoholic KOH

Q.12 A sample of chloroform before being used as an by heating a mixture of
anaesthetic agent is tested by
(A) Chloroform and silver powder
(A) Fehling’s solution
(B) Trihalogenated methane and a primary amine
(B) Ammoniacal cuprous chloride
(C) An alkyl halide and a primary amine
(C) Silver nitrate solution in the cold
(D) An alkyl cyanide and a primary amine
(D) Silver nitrate solution after boiling with alcoholic KOH
Q.20 Pick out the correct equations:

Q.13 One of the important constituents of tear gas is
(A) CH3CH=CH2+HCl → CH3CHClCH3
(A) COCl2 (B) CCl3 NO2
(B) CH3CH=CH2+HBr → CH3CH2CH2Br
(C) SOCl2 (D) CH3-N=C=O
peroxide
(C) CH3CH=CH2+HBr  CH33CH
→ CH CH22CH
CH22Br
Br
(D) CH3CH=CH2+HI → CH

peroxide
CH33CHlCH
CHlCH33 Q.26 Assertion: Chlorobanzene is easily hydrolysed as
compared to chloromethane.
Reason: Carbon chlorine bond in chlorobenzene is
OD
relatively shorter than that in chloroethane.
Q.21 +D2SO4
+D2O
Z. Z may be
Q.27 Assertion: Carbon tetrachloride is used as fire
extinguisher.
OD OD OD OD
D D Reason: Carbon tetrachloride is a non-polar substance.
D D D
(B)
(A)
(A)
(B) (C) or
D D Q.28 Assertion: Tertiary haloalkanes are more reactive
than 1° alkyl halides towards elimination. Positive
D D D
OD OD OD
Reason: Inductive effect of alkyl groups weakens
carbon halogen in 3° halides.
D D D
(C)
(C) or (D) None of these
D D Q.29 Assertion: In comparison to ethyl chloride, it is
D
difficult to carry out nucleophilic substitution on vinyl
D
chloride.
Reason: Vinyl group is electron donating group.
Assertion Reasoning Type
Q.30 Assertion: Free radical chlorination of n-butane
Each of other questions given below consists of two
gives 72% 2-chlorobutane and 28% 1-chlorobutane
statements, an assertion (A) and reason (R). Select the
though it has six primary and four secondary hydrogen’s.
number corresponding to the appropriate alternative
as follows Reason: A secondary hydrogen is abstracted more
easily than the primary hydrogen.
(A) If both assertion and reason are true and R is the
correct explanation of assertion, then mark (A)
Q.31 Assertion: Benzyl chloride is more reactive than
(B) If both assertion and reason are true but reason is p-chlorotoluene towards aqueous NaOH.
not the correct explanation of assertion, then mark (B)
Reason: The C-Cl bond in benzyl chloride is more polar
(C) If assertion is true but reason is false, then mark (C) than C-Cl bond in p-chlorotouene.
(D) If both assertion and reason are false, then mark (D)
Q.32 Assertion: Nucleophilic substitution reaction
on an optically active alkyl halide gives a mixture of
Q.22 Assertion: Alkyl halides are not soluble in water.
enantiomers
Reason: Although polar in nature, yet alkyl halides are
Reason: The reaction occurs by SNi mechanism.
not able to from H-bonds with water molecules.
Q.33 Assertion: Ethyl bromide reacts with alcoholic

Q.23 Assertion: Chloral is not alkyl halide. silver cyanide solution to give ethyl carbylamine as
Reason: Although molecules contains two OH groups the major product along with a small amount of ethyl
linked to same C atom. cyanide.
Reason: CN- is an ambident nucleophile.
Q.24 Assertion: The reaction of vinyl chloride and
hydroiodic acid produces 1-chloro-2-iodoethane. Q.34 Assertion: CH3 − = 2
CH CH2 →
Cl ,773K
Reason: HI adds on vinyl chloride against Markovnikov's ClCH2 − CH = CH2 + HCl

rule.
Reason: At high temperature Cl2 dissociates into
Q.25 Assertion: Chloroform is generally stored in chlorine atoms which bring about the allylic substitution.
brown bottles which are filled up to brim.
Reason: Chloroform reacts with glass in the presence
of sunlight.
Q.35 Assertion: Tertiary haloalkanes are more reactive CH CH

3 3
than primary haloalkanes towards elimination reactions. | |
Reason: The +I-effect of the alkyl groups weakens the (C) CH3 − CH =CH − CH3 (D) CH3 − CH − C H2 − CH3
|
C-X bond.
OH
Comprehension Type
Multiple Correct Choice Type
There are several factors which decide the fate of
substrate in presence of nucleophile (or base). One of Q.39 When nitrobenzene is treated with Br2 in the
them is nature of solvent. presence of FeBr3, the major product formed is
In mildly basic, neutral or acidic solution primarily m-bromonitrobenzene. Statements which are related
substitution takes place. This will occur via SN2 to obtain the m-isomer are
mechanism for 1° alkyl halides and via SN1 mechanism (A) The electron density on meta carbon is more than
for 3° alkyl halides. When 2° alkyl halides react with that on ortho and para positions
(-) charge nucleophile in polar protic solvents, the SN2
mechanism is followed when 2° alkyl halides react with (B) The intermediate carbonium ion formed after initial
H2O or ROH as solvent SN1 mechanism is followed. attack of Br+ at the meta position is least destabilished
In strongly basic solutions primarily elimination takes (C) Loss of aromaticity when Br+ attacks at the ortho
place with 2° and 3° alkyl halides moderate or strong and para positions and not at meta position
basic solutions arise when followed are present NaOH, (D) Easier loss of H+ to regain aromaticity from the meta
KOH, NaOEt. When we use strong and sterically position than from ortho and para positions
hindered base, KOtBu, even 1° alkyl halides given
elimination products primarily.
Q.40 Benzene can undergo
Na+N− (A) Substitution (B) Addition
Q.36 CH3 − C H − CH3  3
Acetone
→ A; product A is
| (C) Elimination (D) Oxidation
Br
(A) CH3CH = CH2 (B) CH3‒CH2‒CH2‒N3
Q.41 C7H7Cl i) KMnO4 Cl
ii) Sodalime,
(C) CH3 − C H =
CH3 (D) CH2 CH2
| N
N CH2 N
3 (A) CH2Cl (B) Cl CH3
KOH Cl Cl
Q.37 CH3CH2CH2Br → B; product
product BB isis
t BuOH
(C) CH3 (D) CH3
(A) CH3CH = CH2 (B) CH3CH2CH2OH
In the above reactions, compound (A) is
(C) CH3 − C H −CH3 (D) CH3 − C H −CH3
| |
A
OH OtBu Q.42 Ph C CH3 → Ph–CH2–CH3
O
CH A could be:
3
| –
Na+N3− (A) NH2NH2, glycol/OH (B) Na(Hg)/conc. HCl
Q.38 CH3 − CH − C H − CH3 
H2O/Acetone
→
|
Br (C) Red P/HI (D) CH2 CH2 ; Raney Ni–H2
CH CH SH SH
3 3
| |
(A) CH3 − CH − C H − CH3 (B) CH3 − CH − CH =
CH2
|
N3
Previous Years’ Questions Q.4 The major product of the following reaction is
H3 C Br
Q.1 Identify the set of reagents/reaction conditions X
and Y in the following set of transformations (2002)
F
PhSNa
X Y
CH3 − CH2 − CH2Br → Pr oduct → dimethyl formamide
CH3 − C H − CH3
| NO2
Br
(A) X = dilute aqueous NaOH, 20°C,
H3C SPh H3 C SPh
Y = HBr/acetic acid, 20°C,
(B) X = concentrated alcoholic NaOH, 80°C, F F
(A) (B)
Y = HBr/ acetic acid, 20°C,
(C) X = dilute aqueous NaOH, 20°C, Y = Br2/CHCl3, 0°C
NO2 NO2
(D) X = concentrated aqueous NaOH, 80°C,
Y = Br2/CHCl3, 0°C H3 C Br H3C SPh
Q.2 The product of following reaction is SPh SPh

(C) (D)
OH
C2H5O-
+ C2H5l NO2 NO2
anhy. C2H5OH
(A) C6H5OC2H5 (B) C2H5OC2H5 Q.5 The compound used as refrigerant are (1990)
(C) C6H5OC6H5 (D) C6H5l (A) NH3 (B) CCl4
(C) CF4 (D) CF2Cl2 (E) CH2 F2
Q.3 The following compound on hydrolysis in aqueous
acetone will give: (2005)
Q.6 Match the following
CH3 CH3 CH3
MeO
CH3 CH3 CH3
NO2 Column I Column II
MeO NO2 (A) CH3-CHBr-CD3 on treatment (p) E1 reaction
H Cl CH3
with alc. KOH gives CH2=CH-CD3
H Cl CH3
It mainly gives as a major product.
CH3 CH3 CH3
(B) Ph-CHBr-CH3 reacts faster (q) E2 reaction
CH3 CH3 CH3
(K) MeO NO2 than Ph-CHBr-CD3
(K) MeO NO2
H OH CH3 (C) Ph-CH2-CH2Br on treatment (r) E1CB reaction
H OH CH with C2H5OD/C2H5O- gives Ph-
CH3 CH3 CH33 CD=CH2 as the major product.
CH3 CH3 CH3 (s) First order reaction
(L ) MeO NO2 (D) PhCH2 CH3CH2 Br and PhCD2
(L ) MeO NO2 CH2 Br react with same rate.
OH H CH3
OH H CH
CH3 CH3 CH33 Q.7 Which of the following is the correct method for
(M) MeO CH3 CH3 CH3 NO2 synthesizing methyl-t-butyl ether and why?
(M) MeO NO2 (CH3)3CBr+NaOMe →

H CH3 CH3
or
H CH3 CH3
CH3Br+NaO-t-Bu → (1997)
(A) K and L (B) Only K (C) L and M (D) Only M
Q.8 Write the

structures of the products: Q.15 The major product(s) of the following reaction
Alc.KOH
C6H5CH2CHClC6H5 →
(1998) is(are) (2013)
OH
Q.9 What would be the major product in each of the aqueous Br2 (3.0 equivalents)
following reactions? (2000)

CH3 SO3H
C2H5OH
CH3 C CH2Br OH OH OH OH
Br Br Br Br Br
CH3
Br Br Br Br Br
SO3H
Q.10 Identify X, Y and Z in the following synthetic
SO3H Br Br
scheme and write their structures P Q R S
2 →X (i) Na NH
CH3CH2C ≡ CH  (A) P (B) Q (C) R (D) S
(ii) CH3CH2Br
H2 /Pd−BaSO 4
X  Akaline
→ Y  →Z (2002) Q.16 The major product in the following reaction is
KMnO 4
(2014)
O 1. CH3MgBr, dry ether, 0oC
Q.11 The total number of alkenes possible by Cl
CH3 2. aq. acid
dehydrobromination of 3-bromo-3-cyclopentylhexane
using alcoholic KOH is (2011) O OH
(A)
(A) H3 C (B)
(B)
CH3 H2 C CH3
CH3
Q.12 The maximum number of isomers (including
stereoisomers) that are possible on monochlorination
(C)
(C) (D)
(D) CH3
of the following compound, is (2011) O CH2 O
CH3 CH3
C
CH3CH2
H
CH2CH3 Q.17 The acidic hydrolysis of ether(X) shown below is
fastest when (2014)
Q.13 Which of the following molecules, in pure form, is
(are) unstable at room temperature? (2012)
acid
OR OH + ROH
(A)
(A) (A) (B) (B)
(B)
(A) One phenyl group is replaced by a methyl group.

O O (B) One phenyl group is replaced by a para-
O O mehoxyphenyl group
(C) (C) Two phenyl groups are replaced by two para-
(C) (C) (D) (D)
(D)
methoxyphenyl group
(D) No structural change is made to X.
Q.14 KI in acetone, undergoes SN2 reaction with each of

P, Q, R and S. The rates of the reaction vary as (2013) Q.18 In the following reaction, the major product is
CH
(2015)
O 3
1 equivalent HBr
CH2
Cl H2C
H3C Cl Cl Cl
CH3 CH3
P Q R S
(A)
(A) H2C CH3 (B)
(B) H3C
(A) P>Q>R>S (B) S>P>R>Q Br Br
(C) P>R>Q>S (D) R>P>S>Q CH3 CH3
(C)
(C) (D)
(D)
H2C Br H3C Br
Q.19 The number of hydroxyl group(s) in Q is (2015) Q.21 Among the following, reaction(s) which gives(give)
tert-butyl benzene as the major product is(are) (2016)
+ aqueous dilute KMnO4(excess)
H H
P Q
HO heat o
0C Br
H3C CH3 Cl
(A) (B)
NaOC2H5 AlCl3
Q.20 In the following monobromination reaction, the

number of possible chiral products is (2016) OH
(C) (D)
CH2CH2CH3 H2SO4 BF3.OEt2
Br2 (1.0 mole)
H Br
CH3 300o C
(1.0 mole)
(Enantiomerically pure)
PlancEssential Questions
JEE Main/Boards JEE Advanced/Boards
Exercise 1 Exercise 1
Q.2 Q.4 Q.6 Q.7(iii, v) Q.3 (B, D, E) Q.5 (E) Q.8 (B, D) Q.10
Q.9(iii) Q.11 Q.16 Q.18 Q.14 Q.17 (C, E) Q.19 (vi, ix) Q.21
Q.19 Q.22 Q.24 Q.25 Q.24 Q.27 Q.29
Q.27 Q.32
Exercise 2
Exercise 2 Q.1 Q.3 Q.11 Q.14
Q.4 Q.5 Q.8 Q.10 Q.19 Q.25 Q.33 Q.38
Q.14 Q.16 Q.17 Q.22 Q.40
Q.24
Previous Years’ Questons
Previous Years’ Questions Q.3 Q.4 Q.6 Q.10
Q.3 Q.6
Answer Key
JEE Main/Boards
Exercise 1
Q.6
CH3CH3 CH3CH3 CH3CH3
CH3 C CH CH3 -HCl CH2 = C CH CH3+CH3 C=C CH3
(Y) (Z)
Cl
H2
CH3 CH CH CH3
CH3 CH3
Exercise 2
Q.1 B Q.2 D Q.3 C Q.4 C Q.5 C Q.6 B
Q.7 B Q.8 D Q.9 B Q.10 A Q.11 C Q.12 A
Q.13 B Q.14 B Q.15 D Q.16 B Q.17 D Q.18 C
Q.19 C Q.20 A Q.21 B Q.22 A Q.23 C Q.24 D
Previous Year’s Questions

Q.1 A Q.2 D Q.3 B, E Q.4 A, D Q.5 C, E Q.6 B, D
Q.7 C Q.8 D Q.9 D Q.10 C Q.11 B Q.12 A
JEE Advanced/Boards
Exercise 1
Q.5
CH3
OH
(A) H3C (C) H2C
(B) CH3
CH3 CH3
CH2
l
Br
(D) (E)
Q.8
Br Br Br CH3
Br CH
3
(A) (B) CH3 (C) (D)

H3 C
H3 C CH3
Q.10 (a)
O O
Cl
H Cl
(A) (B) (C)
(D) CN
(E) (F)
O O OH
O
OH OH OH
(H) (I)
(G)
OH O HO
(b) CH3 CH3 Cl CH3 CH3

O
(A) (B) (C) (D)
H3C CH3 H3 C CH3 H3 C CH3 H3C
Cl
(c)
OH
OH
(A) (B)
OH O
OH COOH
COOH
(C) (D) (E)
Q.11
OH
Br OH
(A) (B) (C)
D(=B)
Q.12
CH CH3
(A) H3C (B) H C (C)
3
Q.13 CH2
(A) H3C Br (B) H3 C
CH
(C) H3C Br (D) H3C
Br
Q.14
H2C CH3 Br CH3

(A) Br (B) H3C Br
Br Br H2C
(C) H 3 C CH3 (D) CH2
Cl CH3
CH3
A= B=
Q.16 CH3 CH3
Cl CH3 CH3 CH3

CH3
A= B= C= D=
CH3 CH3 CH3 CH3
Q.17 CH3 CH3

C= D=
CH3 CH3 H
Br (Carbenoid
(A) Racemic CH3 SN1 (B)
cyclopropanation)
Br
O
H3 C H
O
H3 C
CH3
(C) (Hofmann E2) (D) H
(Saytzeff E1)
H3 C
N CH2
H3C CH3 H CH3
H3C
Ph H
H
(E2) (Singlet carbene cycloaddition)
CH3
(C) (Hofmann E2) (D) H
(Saytzeff E1)
H3 C
N CH2
H3C CH3 H CH3 Chem i str y | 12.83
H3C
Ph H
H
(E2) (Singlet carbene cycloaddition)
(E) (F)
H
H3C Ph
H3 C
Q.18
CH3
O
H3C Ph
(I) (II) (III) O
H3C CH3
NO2
Q.20
OMgBr
O CH3
CH3MgBr CH3 HOH
+
[H ]
(A) O (B)
CH3 O
CH3 OC
Ozonolysis OH-
CH3
Intermolecular
aldol condensation
(B) (D)
CH3
Br
(E)
Q.23
O
O H3 C C2H5
O
- C2H5 O O
O
O
C2H5 O O
H5C2 H5 C 2
Q.26 The given statements suggest that (W) and (X) are as follows:
CH2CH3 CH2CH3 CH2CH3
H2
H Cl H Cl or CHCl
CH=CH2 CH2CH3 CH2CH3
(W) Optically (Y) (Structure of Y)

inactive
CH3 CH3
H2
H CH2Cl H CH2Cl or
CH=CH2 CH2CH3
(X) Optically inactive

(Z)
Q.29
OH
Br MgBr
Mg CH3CHO C CH3
Ether H
(A) (B)
HBr
OH
Br CH3
H HO C CH3
Br 2
CH3 CH3 H
Q.30 (1) The compound (X) has two isomers(Y) and (Z).
(2) The compound (X) has C, H and Cl atoms.
(3) % of Cl in (X) =71.72% ∴ Empiricial formula of (X) is CH2Cl
Exercise 2
Q.1 D Q.2 A Q.3 A Q.4 A Q.5 B Q.6 A

Q.7 B Q.8 A Q.9 B Q.10 A Q.11 D Q.12 C
Q.13 B Q.14 B Q.15 A Q.16 C Q.17 B Q.18 D
Q.19 B Q.20 B Q.21 B

Q.22 A Q.23 B Q.24 A Q.25 C Q.26 D Q.27 B
Q.28 A Q.29 C Q.30 A
Comprehension Type
Q.31 C Q.32 A Q.33 D Q.34 A Q.35 A Q.36 A
Q.37 A Q.38 B
Q.39 A,B Q.40 A, D Q.41 B, C, D Q.42 A,D
Previous Years’ Questions

Q.1 B Q.2 A Q.3 A Q.4 A Q.5 D, E
Q.6 A → q; B → q; C → r; D → p, s
Q.11 5 Q.12 8 Q.13 B, C Q.14 B Q.15 B Q.16 D
Q.17 C Q.18 D Q.19 4 Q.20 5 Q.21 B, C, D

Solutions
JEE Main/Boards
Exercise 1
2-chloro-3-methylbutane
Sol 1: (i)
Alkyl 2º
Cl
(ii) 3-chloro-4-methylhexane
Cl
Alkyl 2º
(iii) 1-Iodo-2,3-dimethylbutane
I
Alkyl 1º
Br
(iv) 3-Bromo-4-benzyl-2,2,-dimethyl butane

Benzyl 2º
2-Bromo-3-methyl butane
(v)
Alkyl 2º
Br
(vi) Br
1-Bromo-2-ethyl-3-methylbutane
Alkyl 1º
2-Chloro-2-ethyl butane
(vii)
Alkyl 3º
Cl
Cl
(viii) 3-Chloro-5-methyl hex-2-ene
Vinyl 2º
4-Bromo-4-methyl-pent-2-ene
(ix) Alkyl 3º
Br
P-Chloro-sec phenyl butane

(x)
Benzyl 2º
Cl
Sol 2:
vector addition in one direction

∴ Highest dipole addition
µ2 > µ1 > µ3
Sol 3: Ambident nucleophile have 2 or more than 2 sites to donate electron to the electrophile
−
O
Eg. C ≡ N : here C and N both are nucleophiles.
Sol 4: Wurtz-fittig reaction:

Sol 5: P-Dichlorobenzene
Sol 6:
Sol 7:
S N1
SSNN2
2
(iv) C2H5Cl + Aq.KOH C2H5OH
(v) CH3Br + Na + Et2O → CH3—CH3Free radical substitution
(vi)
SN2
Sol 8: sp3 hybridized carbon which have u different valency is a chiral or asymmetric carbon atom.
Sol 9:
S N2
Sol 10: (i) CH3Br < CH3I → better leaving group
(ii) < CH3Cl → sterically less hindered
Sol 11: Reagent: EtO– Na + EtOH
(i)
(ii)
(iii)
Sol 12: Freon 12 — refrigerant

DDT — insectiside, pesticide
CCl4 — fire extinguisher
CHI3 — disinfectant and in iodoform test
S N2
Sol 13:
Sol 14: C6H5CHClC6H5 because 2 e‒ withdrawing phenyl rings.
Sol 15:
Gives substitution reaction so, it will give

O
−
But Alc. KOH gives elimination reaction because O H is not polarized so it can directly attack. H2O is formed
Sol 16: Intermolecular substitution reaction is known as SN1 mechanism in which both nucleophile is in same
molecule.
E.g. Darzen Process
R—OH + SOCl2 R —Cl + SO2 + HCl
Sol 17: (a) (b)
Sol 18: Refer theory.
Sol 19: (i) Halo alkanes have σ -bond so it is easily cleared but in haloarenes π -bond electrons get resonates so
there will be π -bond character which requires high energy
Sol 20:
Sol 21: It is not necessary that a compound which have optically active carbon atom is wholely a optically active
compound.
Sol 22:
Sol 23:
Sol 26: (i)
(ii) (iii)
Sol 27: Swarts reactions: R—Cl / R—Br 

Hg F
→ R—F
22
Sol 28: In chlorobenzene, ortho-para is preferable position because when electrophile attacks on ortho or para
position, it forms a stable intermediate.
stable complex formation

Sol 29: (i)
In chlorobenzene due to resonance of e‒ s of Cl the C—Cl bond is getting less polarized while in cyclohexyl chloride
there is no such effect seen
(ii) Alkyl halides are not soluble in water because they are unable to form hydrogen bonds with water.
Sol 30:
H H

FeCl3 FeCl3
+ Cl2 + HCl + Cl2 + HCl
Br Br
Sol 31: Properties
1. They are
+ Clless reactive
FeBr3 than haloalkanes
+ HBr
FeBr3
2 + Cl2 + HBr
2. They can undergo replacement of halogen by hydroxyl group
H ONa OH
dil. HCl
+ NaOH
3. Replacement by group.
H NH2
2 + 2NH3 + Cu2O 2 + Cu2Cl2 + H2O
Sol 32: Intermolecular substitution reaction is known as SNi mechanism in which both nucleophile is in same
molecule.
Eg. Darzen Process
R—OH + SOCl2 → R —Cl + SO2 ↑ + HCl
Sol 33: Arenes: Compounds with pleasant smell and they are called aromatic compounds.
They contain benzene having ring of six carbon atoms. Later on, it was found that many compound having these
benzene rings do not have pleasant smell.
Arenes are benzene substituted compounds. So, the nomenclature is based on the position of group substituted
which are named as ortho, meta, para.
Sol 34: or
Resonance
hybrid
Each carbon atom is sp2 hybridised. Each carbon has 3 sp2 hybrid orbitals lying in 1 plane at angle. There is one
unhybridised p-orbital which participates in side ways overlapping to form pπ ‒ pp bond. 2 hybridised orbital do
axial overlapping with C atoms to form C – C σ bond and 1 to form C – H σ bond.
Sol 35:
Sol 36: Benzene is highly unsaturated because it is having 3C = C bond but because of its extra resonance stability, it
is inert toward addition reaction & nucleophilic substitution but undergoes electrophilic substitution, like saturated
alkanes.
Sol 37:
Y Y Y Y
H
+ + E + H +
+ E
E
E H
Ortho Meta Para
Sol 38: Substitution is influenced by the group already present in benzene ring. There are 2 types of groups
- Activators (O/P) directors - Deactivators (m-directors)
O
OH OH OH
NO2 COCH3 C CH3
HNO3
+
HNO3
H2SO4
NO2 NO2
AlCl3 CH2 CH2 CH3

Sol 39: + CH3 CH2 CH2 Cl
Exercise 2
Sol 1: (B) Good leaving group tendency is the driving force

∴ CH3I > CH3Br > CH3Cl > CH3F
Sol 2: (D) Hydrolysis of 3º alkane is preferable by SN1 mechanism because of the carbocation stability(D)
Sol 3: (C)
Sol 4: (C) Pyrene contains CCl4
Sol 5: (C)
Sol 6: (B) 1. I– is better leaving group so no reaction

2. E1
3. SN2
4. E1
Sol 7: (B)
Sol 8: (D) HBr will give step (I) while Br2 will give 2Br groups in step (I) only.
1º alkyl halide so SN2 substitution(B) peroxide will cause allyl substitution
Sol 9: (B) More electron density than high nucleophilicity. More electron density than high more +I effect, high
e‒ density.
Sol 10: (A)
Sol 11: (C) For SN2 1° > 2° > 3°

Thus order of decreasing reactivity towards SN2 reaction is
CH3CH2CH2Cl > ( CH3 ) CHCH2Cl > CH3CH2CHClCH3 > ( CH3 ) CCl

  2      3
1 2 3
Sol 12: (A)
Sol 13: (B) AgNO2 has a covalent bond
Sol 14: (B)
Sol 15: (D) Least electron deficient carbon site
Sol 16: (B)
Benzyne intermediate
Sol 17: (D)

Sol 18: (C)
Sol 19: (C) SN2 – seteroselective – Attack on specific site

Stereospecific – Only one configuration formed
Sol 20: (A)
Sol 21: (B)
Sol 22: (A) Dimerization of benzene.
Sol 23: (C)

Sol 24: (D)
Both optically active isomer so reacemic mixture. Planar carbocation attack can be from both up and down.
Sol 1: (A) CH3Cl have one Cl atom which is more electronegative so it will have highest dipole moment.
Sol 2: (D) It is the example of Wurtz reaction.
Sol 3: (B, E) Aryl halide are less reactive towards nucleophilic substitution reaction as compared to alkyl halide due
to following reasons
(E) sp2-hybridized carbon attached to the halogen.
Sol 4: (A D) NH3 and dichlorodifluoro methane are used as refrigerant.
Sol 5: (C E)
The main product of this reaction is nitroethane but ethylnitrite is also formed as a side product along with silver bromide.
Sol 6: (B, D) New carbon-carbon bond formation take place in Friedel Craft’s alkylation following mechanism
involve
Here new C—C bond formed between carbon of benzene ring and alkyl group.
Similarly, in Reimer-Tiemann reaction.
Sol 7: (C) Hexane is very unreactive with no non polar bond.
O
CH2 Br COOH C
[O]
Sol 8: (D)
O
CH3 COOH C
O
Sol 9: (D) R − I + agF → R − F + AgI (Swarts Reaction)
Sol 10: (C)
NH2 N2Cl CN
NaNO2/HCl CuCN/KCN
+ N2
0-5oC
CH3 CH3 CH3
OH
Sol 11: (B) 1. NBS/h OH-
2. H2O/K2CO3 +
Br
CH3 CH3
+
Sol 12: (A) CH3 CH2 CH2 C CH3
CH3ONa
CH3 C CH2 CH2 CH3
Cl OMe
C2H5 CH2 C CH2 + C2H5CH C CH3
CH3 CH3
JEE Advanced/Boards
Exercise 1
Sol 1:
Sol 2: Vinyl chlorides eg. have double bond character in C—Cl bond because
of which it requires high energy to cleave that bond and substitute the reset one but in alkyl chlorides gives SN AE
mechanism or S 1 because reaction they form stable carbocation.
N
Sol 3: (A)
(B)
(C)
(D)
(E)
(F)
Sol 4:
X X X
E
E+
+ + H+
H H H
NO2
HNO3
+
NO2
E2 elimination reaction
Sol 5: (a)
(b)
1 2 . 1 0 0 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
(c)
(d)
(e)
So substitution will be take place at site (1)
Sol 6: (a) Electrophie Aromatic Substitution

X X X
E
C+
+
(b) Addition Elimination

H OMe
+ - OMe
NO2 NO2
Sol 7:
SN1
Sol 8: Reagent - NBS

Reaction - Bromination of allylic and benzylic carbon
Sol 9: (a)
Carbon (1) has more eΘ density than (2) so bond of C1—Br is weaker than C2—Br so it get cleaned easily.
(b)
F creates make better nucleophile site due to its light electronegativity than I
Sol 10: (a)
(b) (C) C6H10 (≡ bond)

(C)
(CH3)3CO-K+
Sol 11:
S N1
Sol 12: A, B, C → C6H6

Br2/CCl4 decolorisation → –C = C– present
soluble in cold con.H2SO4 → –OH present
A → terminal alkyne
A,B simple chain compound
C → ring with double bond
∴ A →
B → gives symmetry cleavage during ozonolysis
C →
Sol 13:
Alc Br2 NaNH2

(A) (B) (C) (D)
KOH alkene
C4H9Br Alkene Dibromide AgNO3
Br Br PPt
Br
Terminal alkyne gives ppt. with amm. AgNO3
Sol 14:
- u
- u
(A)
(B)
Sol 15: (a) Addition Elimination
X X OMe OMe
-
+ OMe
NO2 NO2 NO2
(b) Elimination Addition

H
-
NH2
+ NH2-
NH2
Sol 16:
Cl CH3
CH3
A= B=
CH3 CH3
CH3 CH3
C= D=
CH3 CH3
Sol 17: (A) S N1
(B)
(C)
Elimination (E2) Hoffmann
(D)
(E)
E1
(F)
Sol 18: (i)

(ii)
(iii)
Sol 19: (i)
(ii)
(iii)

(iv) (v)
H
(vi) H H
H (vii)
H H
2 H2SO4
+ Cl3CHO
Chloral Cl DDT Cl
(viii) (ix)
Sol 20:
(C) → (D)

Intramolecular Aldol reaction
∴
Sol 21:
Sol 22: (i) Vinyl chloride do not undergo SN reaction because of double bond character due to resonance.
(ii)
can’t go SN2 because satirically hindered site and for SN1 also it is not a stable carbocation initially.
(iii)
Because intermediate of (I) is resonance stabilized while (II) there is only +I effect.
Ag. SN1
(iv) SN1 3º halides undergo SN1 mechn became SN2 is restricted till less satirically hindered
Cl NaOH
site And 3º carbocation is more stable than 1º.

Sol 23:
Sol 24:
It will go via SN1 mechanism
Sol 25:
A should be treat in with dil. H2SO4 via addn
S N2
E2
Sol 26:
Sol 27:
Sol 28:
Sol 29:
Sol 30:
Sol 31:
COOH
Sol 32:
Cl
Bromination product of (A) :
Sol 33:
Stereochemistry :
Both rings are in different planes so optically active.
Sol 34:
Sol 35:
o
45
+ HNO3
CH3COOH
56.5% 3.5%
40.0%
since –CH3 group is electron donating group it will activate the ring and rate of reaction will be more for toluene
than benzene –CH3 group show +I effect so it will be distance dependent and it is –o/–p director.
Ortho position will be more activated than para.
% product : (ortho > para) >> meta
Sol 36:

Sol 37: t-butyl benzene is very much reaction than benzene due to strong +I og t-butyl group. Value for nitration
at Para position is the withiest due to big size of butyl group which Coues stearic hindrance at or the position
Sol 38:
+
Sol 39: HNO3 + 2N2SO 4 → NO2 + 2NSO − 4 + H3O +
H NO2
+
+ NO2
Exercise 2
Sol 1: (D)
Sol 2: (A) Most electron deficient side will attract OH– towards it and –NO2 group show –M-effect (A)
Sol 3: (A)
Sol4: (A)
Sol 5: (B) Stable group have high livability tendency A <<< B (Resonance) (B)
Sol 6: (A) High polarizability will attributes to high nucleophilicity (A)
Sol 7: (B)
Sol 8: (A) R–OH + X– → R+ → R–X + OH–
Sol 9: (B) R should be large to avoid SN2
Sol 10: (A)
Sol 11: (D)
Sol 12: (C) Other alcohols are poisonous for our body. So, silver nitrate precipitate out them as nitrates.
Sol 13: (B) CCl3NO2 (Chloropicrin) because it forms phosgene (COCl2) after reaction phosgene is harmful for our body.
573−673 K
Sol 14: (B) + Cl2 
75 −100 atm
→ CCl4 + C2Cl6
At such high p & T , it cleaves the C—C bond and chlorinate all valency of carbon.
Sol 15: (A) Computer substitute is C2Cl6 because it has same odour (A)
Sol 16: (C) CF2Cl2(C)
Sol 17: (B)
Sol 18: (D)
Sol 19: (B)
Sol 20: (B) CH3–CH=CH 2 + HBr CH3–CH2–CH2–Br
⊖
more e deficient
(C)/(D) this are the minor products of Kharasch effect
Sol 21: (B)
o/p activator group.
Sol 22: (A) They do not form H-bonds because of electron donating alkyl group. and also because of very bond
blooding.
OH
Sol 23: (B) Chloral → CCl3–CHO CCl3—C
OH
It is a alkyl halide according to IUPAC nomenclature.
Sol 24: (A) Because chloride attached carbon has less electron density so it attaches to the other one against
markonikoff’s rule.
OH
⠤
Na N3–
+
H2O
Br N3
OH
Sol 25: (C) In presence of sunlight chloroform forms phosgene which is harmful for our body. (Poisonous gas).
⠤ ⊖ ⊖
Na N3–
+
H2O
⊕
Br N3 Better leaving group

1
so go via SN path
⊖ ⊖
⊕
Better leaving group
1
so go via SN path
Sol 26: (D) Chlorobenzene undergoes resonance so C–Cl bond have some double-bond character it will get hard
to hydrolysis it.
Sol 27: (B) It extinguishes five because it inhibits the chemical reactions not because of its non-polar nature solvent.
Sol 28: (A) Inductive effect increases electron density on carbon so it will be easy for Cl-atom to leave the site so
bond will get weakened.
Sol 29: (C) Vinyl group’s carbon area sp2 hybridised and thus are more electronegative than sp3 so they will not donate
electron and more important reason is resonance factor electron and more important reason is resonance factor.
⠤
H2C — C— Cl:
⠤
H
Cl
Sol 30: (A)
Cl2
+
hν Cl
78% 72%
more stable, Free radical
intermediate which overcome the number factor.
Comprehension Type
Sol 31: (C) Polar solvent so via SN2 reaction –N3 will get substitute on 2º alkyl halide Sol 32: (A) Strong sterecially
hindered base gives elimination products.
Sol 33: (D)
S N1
Sol 34: (A)
Sol 35: (A) SN1 mechanism:
Sol 36: (A)
⊖
CN– C ≡ N: two donating site
∴ ambident nucleophile
Sol 37: (A) CH3 – CH = CH2
Step 1: Cl2 → Cl• + •Cl
Step 2:
Sol 38: (B) Reason is incorrect.

Multiple Correct Choice Type
Sol 39: (A, B)
–NO2 is a deactivating group so it is meta director.
Sol 40: (A, D)
Sol 41: (B, C, D)
Sol 42: (A, D)
Clemenson reduction Na(Hg) /Con. Na Wolf-kishner NH2–NH2 glycol/OH–

Red P/HI

Alcoholic NaOH
Sol 1: (B) CH3–CH2–CH2Br → CH3–CH=CH2 
HBr
→ CH3—CH—CH3
80ºC
Br
Sol 2: (A)
S N2
Sol 3: (A) Reaction proceed through carbocation intermediate
Sol 4: (A) Nucleophile PhS– substitute the Br– through SN2 mechanism with inversion of configuration at α − C .
Sol 5: (D, E) The compound used as refrigerant are CF2Cl2 , CH2 F2.
Sol 6: A → q; B → q; C → r; D → p, s
Alc. KOH
(A) CH3–CHBr–CD3 
E2
→ CH =CH–CD
2 3
E2 reaction is a single-step reaction in which both deprotonation from β − C and loss of leaving group from α − C
occur simultaneously in the rate-determining step. C–D bond is stronger than C–H bond, C–H is preferably broken
in elimination.
(B) Ph–CHBr–CH3 reacts faster than Ph–CHBr–CD3 in E2 reaction because in later case, stronger C–D bond is to be
broken in the rate determining step.
C H OD
(C) Ph–CH2–CH2Br 
2 5
−
→ Ph–CD=CH2
C2H5O
Deuterium incorporation in the product indicates E1CB mechanism
C H O−
I 
2 5 →
(D) Both PhCH2CH2Br and PhCD2CH2Br will react at same rate in E1 reaction because C–H bond is broken in fast non
rate-determining step. Also E1 reaction follow first order kinetics.
Sol 7:
Alc. KOH
Sol 8: C6H5 CH2 CH C6H5  → C6H5—CH=CH—C6H5
E2
Sol 9: Unimolecular reaction occur
Sol 10:
Sol 11: (5)

Br CH2 CH2 CH3
CH3 CH2 C CH2 CH2 CH3 alc.KOH CH3 CH C
(cis & trans)
CH3 CH2 C CH CH2 CH3
(cis & trans)
+
CH3 CH2 C CH2 CH2 CH3
Sol 12: (8)

.
CH3 CH2 CH CH2 CH3
CH3
*
H2C CH2 CH CH2CH3 (d & l)
Cl CH3
+
* *
H3C CH CH CH2 CH3 (d & l)
Cl CH3
+ Cl
H3C CH2 C CH2 CH3
CH3
+
H3C CH2 CH CH2 CH3
CH2Cl
Sol 13: (B, C) -

O
+
(B) antiaromatic (C)
is antiaromatic
Sol 14: (B) SN2 reaction are through back attack of attacking Nu‒ and not on the basic of stability of carbocation.
Sol 15: (B) OH OH

Br Br
aq. Br2
SO3H Br
(Q)
OH OMgX
Sol 16: (D) Cl CH3MgX, dry ether, 0oC Cl aqueous acid
CH3 CH3 CH3
CH3 O CH3
Sol 17: (C) When two phenyl groups are replaced by two para methoxy group, carbocation formed will be more
stable.
Sol 18: (D)

CH3
+ + +
CH2 H
CH3 C CH2 = CH2 CH3 C = CH2 CH2
CH2
CH3 CH3
Br - Br -
Br
CH3 C CH = CH2 CH3 C = CH CH2 Br
CH3 CH3
(K.C.P) (K.C.P)
Sol 19: (4)
+
H H
H -H2O
HO +
H2O
CH3 CH3 + CH CH3 CH3
3 CH3
1,2 methyl shift
OH
CH3 Aq.dilute
o
KMnO4(excess)O C +
HO OH -H +
OH CH3 CH3
CH3 CH3 CH3
Sol 20: (5)

CH2 CH2 CH3 CH2 CH2 CH3 Et Et
H Br + Br2 H Br Br H
H Br + +
H Br H Br
CH3 CH2 Br CH3 CH3
CH3
Br Br CH2 CH2 CH2 Br AlCl3
(A) + Cl
CH2 + H Br
H Br CH3
CH3 H2SO4
(B) +
Sol 21: (B, C, D)

AlCl3 BF3.OEt2
(A) + Cl (C) + OH
H2SO4
(B) +
BF3.OEt2
(C) + OH

Alkylhalides Arylhalides Aromatic Compounds 1

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12.

Flowchart 12.1: Classification of haloalkanes

2. PHYSICAL PROPERTIES OF ALKYL HALIDES

•• The only methyl halide which is a liquid is iodomethane.

(c) Solubility of haloalkanes

3. CHEMICAL REACTIVITY OF HALOALKANES

C-F C-Cl C-Br C-l

has higher boiling point due to intermolecular H-bonding. O H

stronger acid than p-fluorobenzoic acid.

accept H⊕ from ( −COOH) and exists as a dipolar ion (zwitterion),

Illustration 3: Calculate the dipole moment of the following compound:

Sol: Dipole moment is given by μ = q × r

R 2 =P2 + Q2 + 2PQ cos θ

4. CHEMICAL REACTIONS OF ALKYL HALIDES

(a) Nucleophilic substitution reaction

CH3 CH3 H Aman Gour (JEE 2012, AIR 230)

(ii) Nucleophilic substitution in tertiary

The nucleophilic substitution reaction-an SN1 reaction

Why don’t primary halogenoalkanes use the SN1 mechanism?

(-)-chlorosuccinic acid (+)-malic acid (+)-chlorosuccinic acid

Attack of OH upon SOCl2 Expulsion of Cl- to form Formation of ‘’chlorosulfite’’

Departure of leaving group Chloride attacks cabocation Loss of SO2

Saurabh Gupta (JEE 2010, AIR 443)

(iv) Factors affecting nucleophilic substitution reactions:

Saurabh Gupta (JEE 2010, AIR 443)

Large nucleophiles, especially if they are strong, have a tendency

•• Solvent used: It has already been mentioned that SN2 mechanisms

SN2 Solvents SN1 Solvents

Illustration 4: Prepare the following ethers via Williamson’s synthesis.

There are 2 kinds of elimination reactions, E1 and E2.

•• E2 reactions, do not always follow Zaitsev’s rule.

(ii) Substitution vs Elimination:

•• In most unimolecular reactions, SN1 is preferred to E1, especially at low temperatures.

Predicting Reaction Mechanisms

Reaction with organometallic compounds:

1-Bromohexane 1-Hexylmagnesium bromide Hexane (85%)

(iii) Alkylithium (RLi) forms from RBr and Li metal

(b) Miscellaneous reactions:

R 2CuLi is prepared as follows:

(iv) Friedel Crafts Reaction

(v) Reduction Reactions

•• R − CI + LiAlH4 → R − H + LiCl + AlCl3

(Ease of formation: 3ο > 2ο > 1ο carbocation).

Illustration 9: Me Me  (JEE ADVANCED)

Axial H at C-1 and equatorial Cl Equatorial H at C-3

5. PREPARATION OF ALKYL HALIDES

1. Free Radical Halogenation

CH4 + Cl2 h CH3Cl + HCl

Radical Chain Mechanism

Overall reaction CH4 + Cl2 CH3Cl + HCl

Radical Halogenation: Selectivity

CH3 CH3 Dichloro-,

chlorine (1700:80:1 for 3ο : 2ο : 1ο )

2. Allylic Bromination: (Allylic means adjacent to a C=C double bond)

(ii) CH3 anhydrous CH3

(iii) CH3 CH3

From alcohols using PX3 or PX5

R − OH + PCl5 → R − Cl + POCl3 + HCl

From alcohols using SOCl2 (Thionyl chloride) [Darzen’s Procedure]

Step 5: (a) R − COO + R  → R − COOR (side product)

Illustration 9: Me Me (JEE ADVANCED)

CH4 + Cl2 h CH3Cl + HCl

7. ( CH3 ) CBr + H2O → (JEE ADVANCED)

Illustration 23: Br (JEE MAIN)

Sol: I. (J) II. (K) H2O

Illustration 26: Complete the following reactions: [JEE ADVANCED]

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