II Sem. B.Sc. Organic halogen compounds notes prepared by Dr.

Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

Organic halogen compounds 4 hours Marks Mark: 08

Alkyl halides: Nomenclature. Nucleophilic substitution reactions - SN1 and SN2
mechanisms with energy profile diagrams. Effect of (i) nature of alkyl groups,(ii)
nature of leaving groups, (iii) nucleophiles and (iv) solvents on SN1 and SN2
mechanisms. Elimination reactions - E1 and E2 mechanisms; Hofmann and Saytzeff
eliminations with mechanism. Aryl halides: Preparation by halogenation. Relative
reactivity of alkyl, allyl, vinyl, aryl and aralkyl halides towards nucleophilic
substitution.

Organic halogen compounds: Those organic compounds which contain one or

more halogen groups are directly attached to the alkyl or aryl group called organic
halogen compounds.

Examples-

CH3Cl (methyl chloride), C6H5Br (Bromobenzene) ClCH2CH2Cl (1, 2-

Dichloroethane)

Classification of organic halides: Based on the structure of organic halides are

classified into two types.

1) Alkyl halides: Those organic compounds in which a halogen group is directly

attached to the aliphatic carbon atom (alkyl group) called alkyl halides.

Alkyl halides are mono, di, tri and poly alkyl halides depending on one, two, tree
and more than three respective halogen groups are present.

The general formula for mono alkyl halides can be written as R-X Where R= alkyl
group X= halogen groups (-F,-Cl,-Br,-I)

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

Ex. R= -CH3, X= -Cl Then, CH3-Cl (Methyl chloride)

R= - CH3CH2CH2- X = -Br Then, CH3CH2CH2- Br (Propyl bromide)

Nomenclature of alkyl halides: In IUPAC system, alkyl halides are named as

haloalkanes. Their systematic name is obtained by prefixing fluoro, chloro, bromo
or iodo to the name of the parent hydrocarbon. In complex derivatives, the numeral
indicating the position of the halogen atom is prefixed by the conventions of the
IUPAC system.

Formula Common name IUPAC name

CH3-Cl Methyl chloride Chloromethane
CH3-CH2-Br Ethyl bromide Bromoethane
CH3 –CH2-CH2-Cl Propyl chloride Chloropropane
H3C CH CH3 Isopropyl chloride 2 - chloropropane
Cl

H3C CH CH2 CH3 Sec – butyl chloride 2 –chlorobutane

Cl
H3C CH CH2 Cl Iso-butyl chloride 1 –chloro2-
CH3 methylpropane
CH3 Tert – butyl chloride 2 –chloro-2-
H3C C Cl
methylpropane
CH3

Classification of alkyl halides: Alkyl halides are classified into three categories.

1) Primary (1o) alkyl halides: Those alkyl halides in which a halogen group is
directly attached to the primary carbon atom called primary (1 o) alkyl halide.

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

OR

Those alkyl halides in which a halogen group, a alkyl group and two hydrogen
groups are directly attached to the same carbon atom called primary (1o) alkyl
halide.

General formula for primary alkyl halides can be written as R –CH2-X Where,
R = H or alkyl group and X = -F, -Cl, -Br, I

Ex. CH3Cl, CH3CH2Br, CH3CH2CH2I

2) Secondary (2o) alkyl halides: Those alkyl halides in which a halogen group is
directly attached to the secondary carbon atom called secondary (2 o) alkyl halide.

OR

Those alkyl halides in which a halogen group, two alkyl groups and one hydrogen
groups are directly attached to the same carbon atom called secondary(2o) alkyl
halide.

General formula for secondary alkyl halides can be written as R 2CH-X Where,
R = Alkyl group and X = -F, -Cl, -Br, I

Ex. (CH3)2CHCl, (CH3CH2)2CHBr, (CH3CH2CH2)2CHI

3) Tertiary (3o) alkyl halides: Those alkyl halides in which a halogen group is
directly attached to the tertiary carbon atom called tertiary (3 o) alkyl halide.

OR

Those alkyl halides in which a halogen group and three alkyl groups are directly
attached to the same carbon atom called tertiary (3o) alkyl halide.

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

General formula for tertiary alkyl halides can be written as R 3C-X Where, R =
Alkyl group and X = -F, -Cl, -Br, I

Ex. (CH3)3CCl, (CH3CH2)3CBr, (CH3CH2CH2)3CI

Nucleophilic substitution reaction in alkyl halides: In alkyl halides carbon-

halogen bond is polar and carbon atom bears partial positive charge. Hence alkyl
halides easily undergo nucleophilic substitution reaction. A reaction in which
halogen group of alkyl halide is replaced by a nucleophile is called nucleophilic
substitution reaction.

i. e. R-X + Nu- R – Nu + X-

Types of nucleophilic substitution reaction: There are two types of nucleophilic

substitution reaction

1) SN1 reaction: SN1 reaction stands for unimolecular nucleophilic substitution

reaction where rate of a reaction depends on the concentration of substrate (alkyl
halide) only and it is first order rate reaction.

i. e. Rate α [alkyl halide]

For example: When tertiary alkyl halide (30-butyl bromide) react with sodium
hydroxide in water medium to form a recemic mixture of tertiary alcohol (3 0-butyl
alcohol)

H3C CH3
H3C

H3C
C Br + NaOH
H3C
C OH + HO C CH3

H3C H3C CH3

2 -Bromo -2 -methylpropane Recemic mixture of
o
(3 Butyl bromide)
2 - hydroxy 2 -methylpropane
o
(3 Butyl methyl ether)

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

Mechanism: Mechanism of this reaction takes place in two steps

Step 1- The ionization of a C-Br of bond 30-butyl bromide gives a 30- carbocation
intermediate.

CH3
H3C
slow step -
H3C
C Br C
+
+ Br

H3C H3C CH3

2 -Bromo -2 -methylpropane Carbocation
o
(3 Butyl bromide)

This step is slow hence it is rate determining step

Step 2- Attack of nucleophile (OH-) which is come from NaOH from either face of
the planar carbocation to form recemic mixture of tertiary butyl alcohol. This step
is fast

CH3 CH3 H3C

- Fast
OH
-
C
+ OH HO C + H3C
C OH
CH3
H3C CH3
CH3 H3C
Carbocation Recemic mixture of
0
3 butyl alcohol

Energy profile diagram for SN1 mechanism (reaction):

The following figure shows an energy diagram for the SN1 reaction of ter-butyl
bromide (2-bromo-2-methylpropane) and base (NaOH). There is one transition
state leading to formation of the carbocation intermediate in step 1 and a second
transition state for the carbocation intermediate with base (OH-) in step 2 to give
tertiary butyl alcohol. The reaction leading to formation of the carbocation
intermediate crosses the higher energy barrier and it is slow, hence step is called
the rate determining step.
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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

Where R = -CH3, X = -Br and Nu = OH-

2) SN2 reaction: SN2 reaction stands for bimolecular nucleophilic substitution

reaction where the rate of a reaction depends on the both concentrations of
substrate (alkyl halide) and reagent (nucleophile). It is second order rate reaction.
And its mechanism takes single step

i. e. Rate α [alkyl halide] [nucleophile]

Order of the reaction = 2

For example: When primary alkyl halide (methyl chloride) reacts with sodium
hydroxide in water medium to form primary alcohol (methyl chloride)

H H
H2 O
H
C Cl + NaOH
H
C OH + NaCl
H H
methyl chloride methyl alcohol
0 0
(1 -alkyl halides) (1 - alcohol)

Mechanism: When 10-alkyl halide (methyl chloride) is approaches the nucleophile

(OH-) which is comes from NaOH in the aqueous solution a transition state form in
which a partial bond between carbon-OH- is formed and partial bond between
carbon-Cl broken. But transition state is highly unstable which is immediately

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

bond between C-OH completely formed and C –Cl bond completely broken to
form the final inversion product of primary alcohol (methyl alcohol)

Energy profile diagram for SN2 mechanism (reaction):

The following figure shows an energy diagram for the SN2 reaction of methyl
chloride and OH- come from NaOH. There is single transition state is formed
where partial bond between carbon-OH- is formed and partial bond between
carbon-Cl broken. This transition state is highly unstable, to form final product of
inversion methyl alcohol

Factors affecting on mechanism of SN1 and SN2 reaction:

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
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There are four factors affecting on mechanism of SN1 and SN2 reaction.

1) Nature of alkyl group (alkyl halide): SN1reactions are governed mainly by

electronic factors, the relative stabilities or carbocation intermediates. S N2 reactions
by contract are governed mainly by steric hindrance, and their transition states
are particularly sensitive or crowding about the site of reaction.

i) Relative stabilities of carbocations: We know that 3o carbocations are the most

stable carbocations, requiring the lowest activation energy for their formation,
whereas 1o carbocations are the least stable requiring the highest activation energy
for their formation. In fact, 1o carbocations are so unstable that they have never
been observed in solution. Therefore, 3o alkyl halides are most likely to react by
carbocation formation; 2o alkyl halides are less likely to react in this manner, and
methyl and 1o alkyl halides never react in that manner.

i.e. 3o alkyl halide > 2o alkyl halide >1o alkyl halide

Reactivity increases towards SN1 mechanism

ii) Steric hindrance: To complete a substitution reaction, the nucleophile must

approach the substitution center and begin to form a new covalent bond to it. If we
compare the ease of approach by the nucleophile to the substitution center of a 1o
alkyl halides with that of a 3o alkyl halides, we see that the approach in
considerably easier in the case of the 1 o alkyl halides. Two hydrogen atoms and
one alkyl group screen the backside of the substitution center of 1o alkyl halides.
In contrast, three alkyl groups screen the backside of the substitution center of 3o
alkyl halides. This center in bromoethane is easily accessible to a nucleophile,
while there is extreme crowding around it in 2-bromo-2-methyl propane.

i.e. 1o alkyl halide > 2o alkyl halide > 3o alkyl halide

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
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Reactivity increases towards SN2 mechanism

2) Nature of leaving group: In the transition state for nucleophilic substitution on

an alkyl halide, the leaving group develops a partial negative charge in both SN1
and SN2 reaction; therefore, the ability of a group to function as a leaving group is
related to how stable it is as an anion. The most stable anions. The most stable
anions and the best leaving groups are the conjugate bases of strong acids.

I- > Br- > Cl- > F- > CH3COO- > HO- > CH3O- > NH2-

Efficiency increases towards SN1 and SN2 mechanism.

3) Nature of nucleophile: Nucleophilicity is a kinetic property, which we measure

by relative rates of reaction. We can establish the relative nucleophilicities for a
series of nucleophiles by measuring the rate at which each displaces a leaving
group from alkyl halide.

Br-, I- CH3COO-, RCOO- H2O

CH3S- , RO- CH3SH, RSH, R2S CH3OH, ROH

HO-, CH3O-, RO- NH3, RNH2, R2NH, R3N CH3COOH,

RCOOH

GOOD MODERATE POOR

Effectiveness as nucleophile increases.

Because the nuclophile participates in the rate determining step in an SN2 reaction,
the better the nucleophile, the more likely it is the reaction will occur by the
mechanism. The nucleophile does not participate in the rate determining step for an
SN1 reaction. Thus, an SN1 reaction can in principle, occur at approximately the

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

same rate with any of the common nucleophile, regardless of their relative
nucleophilicities.

4) Nature of solvent: Solvent provides the medium in which reactants are

dissolved and in which nucleophilic substitution reactions takes place. Common
solvents for these reactions are divided into two groups.

i) Protic solvents: These solvent contains –OH groups and hydrogen –bond
donors. Common protic solvents for nucleophilic substitution reactions are water,
low molecular weight alcohols, and low molecular weight carboxylic acids. Each is
able to solvate both the anionic and cationic components of ionic compounds by
electrostatic interaction between its partially negatively charged oxygen(s) and the
cation and between its partially positively charged hydrogen and the anion. These
same properties aid in the ionization of C-X bonds to give an x- anion and a
carbocation; thus, protic solvents are good solvents in which to carry out SN 1
reactions.

i.e. H2O> HCOOH >CH3OH >CH3CH2OH >CH3COOH

Polarity (efficiency) increases towards SN1 reaction.

ii) Aprotic solvents: These solvents do not contain –OH groups and cannot
function as hydrogen –bond donors. The protic solvents most commonly used for
nucleophilic substitution reactions. Dimethyl sulfoxide and acetone are polar
aprotic solvents; dichloromethane and diethyl ether are non polar aprotic solvents.
The aprotic solvents are particularly good ones in which to carry out SN 2 reactions.
Polar aprotic solvents are able to solvate only cations; they are not able to solvate
anions; therefore, they allow for naked and highly reactive anions as nucleophiles.

i.e. CH3SOCH3 > CH3COCH3 > CH2Cl2 > CH3CH2OCH2CH3

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

Polarity (efficiency) increases towards SN2 reaction.

Differences between SN1 and SN2 reaction

SN1 mechanism SN2 mechanism

1. First order kinetics. 1.Second order kinetics
2. Two step reaction. 2. One step reaction.
3.Carbocations are intermediates 3. Carbocations are not intermediates,
reaction occurs through a transition
state.
4. Nucleophile attacks from both sides 4. Exclusive back side attack of
though back side attack predominates. nucleophile takes place.
5. Generally racemization with some 5. Complete inversion of configuration
inversion observed. occurs.
6. Rearrangements generally observed. 6. Rearrangements not observed.
7. Elimination is an important side 7. Elimination also not observed.
reaction.
8. Electronic factors affect the reaction 8. Steric, not electronic effects, affects
greatly. the rate.
9. The order of reactivity follows the 9. The order of reactivity follows the
sequence: 30 > 20 > 10 > methyl halides. sequence: methyl halides > 10 > 20 > 30.
10. Weak nucleophiles such as water, 10. Strong nucleophiles such as
alcohol, etc. favour these reactions. alkoxide ions favour these reactions.
11. Low concentration of nucleophile 11. High concentration of nucleophile
generally favour these reactions. favours these reactions.
12. Polar protic solvents (water, alcohol, 12. Polar aprotic solvents (acetone,
acids) of high dielectric constants favour acetonitrile, DMF, DMSO) of high

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
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these reactions. dielectric constant favour these

reactions.
However, methanol, ethanol are used as
they are inexpensive.

Elimination reactions: A reaction in which two or four atoms attached to the

adjacent carbon atoms in the substrate molecule are removed to form double or
triple bonds called elimination reaction.

For example: Dehydrohalogenation reaction of 2-halo 2, 3-dimethyl butane using

alcoholic solution of KOH

CH3 CH3
H2O H3C CH3
H3C C C CH3 + KOH C C
+ H2O + KX
alc
H X H3C CH3
Alkyl halide Base
Alkene

Types of elimination reactions: There are two type elimination reactions

1) E1 reaction: E1 reaction stands for unimolecular elimination reaction where rate

of a reaction depends on the concentration of substrate (alkyl halide) only and it is
first order rate reaction.

i. e. Rate α [alkyl halide]

For example: When 2-bromo-2-methylpropane reacts with alcoholic solution of

potassium hydroxide dehydrohalogenation reaction takes place to form to form 2-
methylpropene.

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

CH3 CH3
Dehydrohalogenation
H3C C CH3 + KOH H3C C CH2 + H2O + KBr

Br
2 -methyl propene
2 -bromo - 2 -methyl propane

Rate α [2-bromo-2-methylpropane]

Order of a reaction = 1

Mechanism: Mechanism takes following steps.

Step 1.Ionisation of the C-Br bond of tertiary butyl bromide (2-bromo 2methyl
propane) takes place to from a carbocation intermediate. This step is slow and rate
determining step

CH3 CH3
Slow
+ -
H3C C CH3 H3C C CH3 + Br

Br
A carbocation
2 -bromo - 2 -methyl propane

Step 2: Abstract the proton from the carbocation intermediate by OH- (which is
came from KOH) to the alkene (2-methyl propene). This step is very fast

CH3 CH3

- +
Fast
OH + H CH2 C CH3 H2C C CH3 + H2O

A carbocation 2 -methyl propene

1) E2 reaction: E2 reaction stands for bimolecular elimination reaction where rate

of a reaction depends on the concentrations of both substrate (alkyl halide) and
reagent (base), and it is second order rate reaction.

i. e. Rate α [alkyl halide][base]

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

For example: 1-bromopropane on dehydrohalogenation reaction with alcoholic

solution of KOH to form propene.

Dehydrohalogenation
H3C CH2 CH2 Br + KOH H3C CH CH2 + H2O + KBr
Alc
1 -bromopropane 1 -propene

Rate α [CH3CH2CH2Br][KOH]

Order of a reaction =2

Mechanism: In this mechanism, abstract the proton from alkyl halide by the OH-
of the KOH and expel the bromide ion (Br -) by the alkyl halide simultaneously
takes place to form the carbon-carbon double bond. All bonds forming and bonds
breaking are takes place at the same time in single step.

CH3
Slow
K OH + H CH CH2 Br H3C CH CH2 + H2O + KBr

Potassium hydroxide 1 -bromopropane 1 -propene

Saytzeff rule: When alkyl halide is treated with alcoholic solution of KOH then
dehydrohalogenation reaction takes place to form more than one types of alkenes
in which highly substituted alkene the major product. This rule is called Saytzeff’
rule

Example: When 2-bromobutane is heated with alcoholic solution of KOH to form

2-butene is the major product and 1-butene is the minor product.

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

-
Saytzeff's rule
-
HO HO H3C CH CH CH3

H H H H 2 -butene
KOH
80% (Major product)
H C C C C H
Alcohol
H
Br H H -KBr
-H 2O Anti -Saytzeff's rule
H2C CH CH2 CH3

2 -bromobutane
1 -butene
20% (Minor product)

Hofmann’s elimination reaction: When different alkyl substituents attached to

the nitrogen atom of ammonium ion, then on pyrolysis gives more than one types
of alkenes in which least substituted alkene is the major product. This rule is called
Hofmann’s elimination reaction.

CH3

H2C CH2 + H3C N CH2 CH2 CH3

CH3 ethene
H N,N -dimethylpropanamine
..........

-
Pyrolysis 80% (Major product)
+
H3C N CH2 CH CH3 HO
-H 2O
..........
H2C CH2 CH3

H H2C CH CH3 + H3C N CH2 CH3

1 -propene
N -ethyl N,N -dimethylpropanammonium hydroxide N,N -dimethyethanamine
20% (Minor product)

2) ARYL HALIDES: Those organic compounds in which one or more halogen

groups are directly attached to the benzene ring are called aryl halides.

For example:

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

Cl
Cl Br Cl
Cl Cl
Cl

Cl
Cl
Chlorobenzene Bromobenzene 1,2 -dichlorobenzene Cl
Hexachlorobenzene

Preparation of aryl halides by direct halogenations method:

Cl

FeCl 3
+ Cl 2 + HCl

Benzene
Chlorobenzene

Br

FeBr 3
+ Br2 + HBr

Benzene
Bromobenzene

+ I2
+ HgO + HI + Hg(OH)I
Murcuric oxide
Benzene
Iodobenzene

Relative reactivity of alkyl, allyl, vinyl, aryl and arylalkyl halides taking ethyl
chloride, allyl chloride, vinyl chloride, chlorobenzene and benzyl chloride as
examples towards nucleophilic substitution reaction:

In case of ethyl chloride which is an example of alkyl halides, the chlorine

group is directly attached to the ethyl group (CH3CH2-) and p-orbital of chlorine
atom is overlaps with sp3 hybrid orbital of ethyl carbon atom and also chorine atom

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

is more electronegative than carbon as a result the partial positive charge on carbon
atom and partial negative charge on chorine atom are developed. The positive
charge developed on carbon atom can be stabilized by donation of sigma electron
by methyl group. Therefore the chlorine group is very easy to replaced by a
nucleophile. Hence ethyl chloride is very easy (more reactive) to undergo
nucleophilic substitution reaction.

Charge will be stabilized by sigma bond

In case of allyl chloride, which is an example of allyl halides, the chlorine atom
is directly attached to the 2-propene (allyl group), CH2=CH-CH2- group and p-
orbitals of chlorine atom is overlaps with SP3 hybrid orbital of allyl carbon as a
result a small partial positive charge on carbon and a negative charge on chlorine
atom are developed. The positive charge developed on carbon atom can be
stabilized by donation of pi electron by ethylene group. Therefore, chlorine atom
is easy to replace by a nucleophile. Hence allyl chloride (allyl halide) is easy to
undergo nucleophilic substitution reaction.

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

Charge will be stabilized in moderate distance

In case of vinyl chloride, which is an example of vinyl halides, the chlorine

group is directly attached to the ethene (CH2=CH-) group and the p-orbital of
chlorine atom overlaps with SP2 hybrid orbital (ΠMO) of CH2=CH- carbon atom
as a result the electron delocalized between chlorine and CH 2=CH- groups.
Therefore the C-C bond becomes short and strong and it is very difficult to develop
the partial positive and negative charges and very difficult to replacement of
chlorine atom by a nucleophile. Hence vinyl chloride (vinyl halide) is almost inert
(not reactive) towards nuclephilic substitution reaction.

Charge will be stabilized in shortest distance OR positive charge will not

developed

In case of chlorobenzene which is an example of aryl halides, the chlorine atom

is directly attached to the benzene ring and p-orbital of chlorine atom is overlaps
with SP2 hybrid orbitals (ΠMO) of benzene carbon atom as a result the electron
density disturbs between chlorine atom and benzene ring and develops a double
bonded characters and also bond becomes short and strong. Therefore the partial
positive and negative charges are not developed and replacement of chlorine atom
by a nuclophile is difficult. Hence chlorobenzene is more difficult to undergo
nucleophilic substitution reaction.

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

Positive charge cannot be developed due to double bond character

In case of benzyl chloride, which is an example of aryl alkyl halides, the

chlorine atom is directly attached to the side chain (methylene carbon atom) of the
benzene and p-orbital of chlorine atom overlaps with SP3 hybrid orbital of
methylene group as a result a great partial positive and negative charges developed
between (C6H5CH2+-) benzyl group and chlorine atom. The positive charge on
benzyl group is stabilizes by pi electrons of benzene. Therefore the replacement of
chlorine atom by the nucleophile is most easy. Hence benzyl chloride (aryl alkyl
halides) is most easy to undergo nucleophilic substitution reaction.

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 II Sem. B.Sc. Organic halogen compounds notes prepared by Dr. Dhondiba Vishwanath
Suryawanshi (DVS) Government First Grade College K R Puram Bengaluru-560036.

Charge will be stabilized in longest distance

Therefore, the reactivity of above halides towards nucleophilic substitution

reaction decreases in the order of- Benzyl chloride (aryl alkyl halide) > ethyl
chloride (alkyl halide) > allyl chloride(allyl halide) > vinyl chloride(vinyl
halide) > chlorobenzene (aryl halide)

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