Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Chapter-4

Alkyl and Aryl Halides

Part-II: Aryl Halides

University syllabus: Alkyl Halides: Alkyl Halides (up to 5 Carbons): Introduction and IUPAC
nomenclature, Types of Nucleophilic Substitution (SN1 , SN2 and SNi) reactions. Preparation: from
alkenes and alcohols. Reactions: hydrolysis, nitrite and nitro formation, nitrile and isonitrile
formation. Williamson’s ether synthesis: Elimination vs. substitution. (Ref.-1: 165-211 and 943-967)

4.1. Definition: The parent family of organic compounds is alkanes. When one or more
hydrogen atom/s in alkane are replaced by halogen atom/then compound formed is called as
alkyl halide. Another parent structure in organic compound is benzene ring. When one or
more hydrogen atom/s on benzene ring are replaced by halogen atom/then compound formed
is called as aryl halide.
Br
CH3Cl

CCl4 CH4 CH2Cl2 Cl

Br
Aryl Halides
CHCl3
Br
Cl
I

Alkyl halides
4.2. IUPAC Names of Alkyl Halides:
The most versatile system is the IUPAC. The rules are:
a. Select as the parent structure. It should contain longest continuous carbon chain that contains the
halide group.
b. The parent structure is named after number of carbon atoms.
c. Depending upon the number of carbon atoms in parent structure name of the alkane is derived.
Name of alkyl halide is then derived from name of parent alkane by writing name of halide before
the name of alkane. e.g. CH3-CH2-Br Bromoethane
d. Position of halide group in alkane chain is indicated by a number of C atom to which halide group
is attached. Numbering of C atom in parent alkane is done so that C bearing halide have lowest
possible number. e.g. CH3-CHBr-CH3 2-Bromopropane
f. Indicate the positions of sub groups in parent chain by name of group and number of C atom.

H H 1. Longest chain of carbon atom is numbered from left side

H2
so that C bearing have lowest possible number.
H3C C C C2 CH3
5 4 3 1 2. Parent chain have 5 carbons; hence name of alkane is
CH3 Br pentane.
3. At C-2, Br is attached hence, 2-bromopentane.
4. At C-4, methyl group is bonded, hence
4-methyl-2-bromopentane is the iupac name of alkane.

2 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Table: Common and IUPAC names of some of the alkyl Halides

4.3. Classification of Aryl and Alkyl halides: Halogen derivatives of hydrocarbons

are classified a) On the basis of parent hydrocarbon structure or b) Number of halogen atoms

Classification on the basis of parent hydrocarbon Classification on the number of

(monohalogenation derivative) halogen atoms
a. Alkyl halides or haloalkanes: Parent hydrocarbon is Alkane. a) Monohalogen derivatives:
e.g. CH3Br - methyl bromide Molecule alkyl or aryl halide consists
of only halogen in the structure.
b. Allylic halides: Parent hydrocarbon is Alkene but halide is
not bonded to double bonded C atom. e.g. CH3Br, Ar-Cl, CH3CH2Cl,
e.g. CH2=CH-CH2Cl – 3 chloropropene b. Dihalogen derivatives:
c. Benzylic halide: Parent hydrocarbon is benzyl group i.e. Molecule alkyl or aryl halide consists
Ar-CH2. e.g. Ar-CH2Cl – Benzoyl Chloride of two halogen in the structure.
d. Vinylic halides: parent Parent hydrocarbon is Alkene and e.g. CH2Cl2, Cl-Ar-Cl,
halide is bondeded to double bonded C atom. ClCH2CH2Cl, etc.
e.g. CH3-CH = CH2-Cl Vinyl chloride c) Trihalogen derivatives: Molecule
e. Haloalkyne: When a halogen atom is bonded to triply bonded alkyl or aryl halide consists of three
C atom in alkyne the alkyl halide is haloalkyne. halogen in the structure.
e.g. HC ≡ C-Cl - Chloroacetylene e.g. CHCl3, 1,2,4 tribromobenzene
f. Aryl halides: When a halogen atom is bonded to benzene ring
directly. e.g. Ar-Cl, Chlorobenzene.

3 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

4.4 Methods of preparation of alkyl halides:

4.4.1: From alcohol: The most widely used method of preparation of alkyl halide is
replacement of hydroxyl group of an alcohol by halogen atom. Alcohols are available in a
wide variety. The hydroxyl group may be replaced by halogen atom using (a) halogen acid,
(b) phosphorous halide or (c) thionyl chloride.
a) Reaction between alcohol and halogen acid: The conditions for reaction of
alcohol with halogen acid (HX) depend on the structure of the alcohol and particular halogen
acid used. The order of reactivity of alcohols with a given haloacid is 3˚>2˚>1˚.
Reaction
R-OH + HX RX + H2O
Cond.

.
Alkyl chlorides can be prepared from action of Hydrogen chloride and zinc chloride
(Grooves' process) with primary and secondary alcohols But, tertiary alcohols readily react
with concentrated hydrochloric acid in absence of zinc chloride.
Anhydrous
R-OH + HCl RCl + H2O
ZnCl2
Anhydrous
C2H5-OH + HCl C2H5Cl + H2O
ethanol ZnCl2 ethyl chloride

CH3 CH3

H3C C OH + Conc. HCl H3C C Cl + H2O

CH3 CH3
t-butyl chloride
t-butyl akcohol .

.
For preparing alkyl bromides, constant boiling hydrobromic acid (48%) is used.
Primary alkyl bromides can also be prepared by reaction with NaBr and H 2SO4. HBr is to be
generated in situ.

4 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

NaBr, H2SO4
R-OH + HBr RBr + H2O
Heat

NaBr, H2SO4
C2H5-OH + HBr C2H5Br + H2O
ethanol Heat ethyl Bromide
.
Good yield of alkyl iodides may be obtained by heating alcohols with sodium or
potassium iodide in 95 % phosphoric acid. HI is to be generated in situ.
NaI, H3PO4
R-OH + HI RI + H2O
Heat

NaI, H3PO4
CH3CH2CH2-OH + HI CH3CH2CH2-I + H2O
Heat 1-iodopropane
n -propyl alcohol
.
b) By using Phosphorous Halide: An alkyl halide may be prepared by action of
phosphorous halide on alcohol (PX3, PX5). Phosphorous tribromide and triiodide are usually
generated in situ (produced in the reaction mixture) by the action of red phosphorous on
bromine and iodine respectively. PCl3 and PCl5 are available in ready. Phosphorous
pentachloride reacts with alcohol to give alkyl chloride.
3R-OH + PX3 3 RX + P(OH)3 or H3PO3

3C2H5-OH + PCl3 3 C2H5Cl + H3PO3

ethanol ethyl chloride
.
H H
3 C CH3 PBr3 3 C CH3 + P(OH)3 +HCl
OH Br .
R-OH + PCl5 RCl + POCl3 +HCl

C2H5-OH + PCl5 C2H5Cl + POCl3 +HCl

ethanol ethyl chloride .
c) By using thionyl chloride: Thionyl chloride reacts with straight chain primary
alcohols to give alkyl chloride. The by-products obtained are gases. There, we get pure alkyl
halide behind. . Thus, this method is preferred for preparation of alkyl chloride.
heat
R-OH + SOCl2 RCl + SO2 + HCl

C2H5-OH + SOCl2 C2H5Cl + SO2 + HCl

ethanol ethyl chloride
.

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

4.4.2: From Alkenes: Alkyl halides can be obtained from saturated as well as
unsaturated hydrocarbons by various reactions. Alkyl halides are formed on addition of
hydrogen halide to alkenes. Addition of HX to alkene across C=C lead to the formation of
alkyl halides.
X

C C +H X C C

Alkene H
Alkyl Halide

H3C CH3 Br CH3

C C +H Br H3C C C H
H3C H
CH3 H
2-methyl 2-butene
2-methyl 2-bromobutane

H CH3 Br CH3

C C +H Br H C C H
H3C H
CH3 H
2-butene
2-bromobutane
.
In addition of HX to alkene, Markownikov rule is followed.
CH3
H3C Br
H
H
+H Br H

1-methyl-1-cyclohexene 1-methyl-1-bromocyclohexane

CH2 H3C Br

+ H Br

methylenecyclohexane 1-bromo-1-methylcyclohexane
.
Alkyl fluorides can also be prepared from alcohols.

.
Addition of X2 to alkene across double bond lead to the formation of vicinal dihalide.
H CH3 Br CH3

C C + Br Br H C C H
H3C H
CH3 Br
2-butene 1,2-bromobutane
.

6 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Nature of intermolecular forces in alkyl halides: Halogens (X = F, Cl, Br and I)

are more electronegative than carbon. Carbon atom that carries halogen develops a partial
positive charge while the halogen carries a partial negative charge. Thus carbon-halogen
bond in alkyl halide is a polar covalent bond. Therefore, alkyl halides are moderately polar
compounds.

+ -
C X

Size of the halogen atom increases from fluorine to iodine. Hence the C-X bond
length increases. The C-X bond strength decreases with an increase in size of halogen. This is
because as the size of p-orbital of halogen increases the p-orbital becomes more diffused.
Table-Bond properties of C-X bond in CH3X

4.5 Reactions of alkyl Halides:

4.5.1 Nucleophilic substitution reactions
Types of Reagent:
a. Nucleophile: A reagent which is electron rich and can donate electron to substrate
at electron deficient centre. It is either negatively charged species or consists of lone
pair of electron on one of the atom in it. Nucleophile is a Lewis Base.
Example- :NH3, CN ̶ Cl ̶ , Br ̶ etc.
b. Electrophile: It is the electron deficient species which can accept electron to form
the product. It either positively charged or have incomplete octate. Electrophile is a
Lewis acid.
Example – H+, Br+, H3C+ etc.

a) Substitution Reactions (Hydrolysis of alkyl halides): In these reactions one of the atom
or group from substrate molecule is replaced by another group from reagent.

In above reaction –Br group of bromomethane is replaced / substituted by –OH group as

reagent.
7 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44
Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Substitution Reactions

Nucleophilic Substitution Electrophilic Substitution

reaction reaction

Aliphatic Nucleophilic Substitution Reaction: Reagent is nucleophile and substrate

molecule has electron deficient Carbon.

b) Aliphatic Electrophilic Substitution Reaction: Reagent is electrophile and substrate

molecule has electron rich carbon in its structure.
CH4 +Cl2 → CH3Cl + HCl
In present syllabus we have study Aliphatic Nucleophilic Substitution reaction mechanism in
detail.

Aliphatic Nucleophilic Substitution reactions are two types:

Nucleophelic Substitution Reactions

Nucleophilic Substitution Nucleophilic Substitution

Unimolecular (SN1) bimolecular (SN2)

a. Nucleophilic Substitution Unimolecular (SN1):

Aliphatic Nucleophilic Substitution reactions may take place via ionization
mechanism, where heterolytic dissociation of C-X bond in the substrate take place to form
carbocation. This dissociation is followed by rapid combination of the electrophilic
carbocation with a Lewis base (nucleophile) present in the medium.
Example:
(CH3)3CBr OH CH3)3COH
t-butylbromide t-butyl alcohol
In this reaction first step is slow hence rate of reaction depends on this step i.e. formation of
carbonium ion.
Rate α [(CH3)3CBr]
Rate = k1 [(CH3)3CBr]
k1 is first order rate constant for the reaction.
As rate of reaction depends only concentration of only one molecule i.e. substrate in
the reaction is unimolecular reaction.
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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Mechanism of reaction:
Step -1: Formation of Carbonium ion.
H3C CH3

C Br C + Br-
H3C + - CH3
H3C
H3C
t-butylbromide t-butylcarbonium ion
.
This step is slow hence rate of reaction depends on this step only.
Formation of carbonium ion is facilitated by –
i. Polarity of C – Br bond.
ii) Methyl groups bonded to electrophilic carbon which stabilizes carbonium ion by electron
donating inductive effect (+I).
The carbonium ion formed is planar in nature due to sp2 hybridization of central C
atom. It is the reaction intermediate of this reaction. Formation of carbonium ion is
endothermic reaction and hence take place with change in internal energy.
Step -2: Attack of nucleophile on electrophilic carbon to form the product:
CH3 H3C

1) C OH C OH
H3C 50% Retention
CH3
H3C H3C of confiuration
t-butylcarbonium ion t-butyl alcohol
CH3 CH3

HO C 50% Inveersion
2) OH C CH3 of confiuration
CH3 CH3
H3C
t-butyl alcohol
t-butylcarbonium ion .
In carbonium ion central carbon is positively charged. Hence, as soon as it is formed
Nucleophile OH ̶ attack on it to form the product i.e. t-butyl alcohol. The carbonium ion is
planar in nature. Hence attack of nucleophile can take place on either face of ion. i) Front
face attack gives rise to product where configuration is same as that of reactant i.e. retention
of configuration (product-1). ii) Back face attack gives rise to product where configuration is
opposite as that of reactant i.e. inversion of configuration take place (product-1). Both
products are formed in equal amount hence we get racemic mixture of products.

Front side attack of nucleophile on Back side attack of nucleophile on

carbonium ion carbonium ion

9 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Reactant undergo Nucleophilic substitution reaction via SN1 mechanism when-

i. Substrate is tertiary
ii. Solvent is polar
Both of these factors help to stabilize carbonium ion hence reaction take place via SN1 path.
Energy profile diagram:
During chemical reactions energy changes takes place in molecule. They are
represented graphically and this graph is called as energy profile diagram. It is as shown
below.

Diagram represents the energy changes during the chemical transformation via SN1
mechanism.
a. The substrate (CH)3C-Br has lowest energy.
b. In first step C-Br bond starts breaking and energy increases. This T.S.-1. The energy
difference between reactant and T.S.-1 is the change in internal energy of reaction i.e. ∆E.
c. The bond between C-Br break completely to for carbonium ion. this take place with slight
decrease in energy and represented by minima between two transition states.
d. The attack of OH ̶ to form partial formation of C-OH bond represents the second T.S.
which slightly higher energy than carbonium ion but less than first T. S.
e. The product formed is t-butyl alcohol which has lower energy than reactant. The energy
difference between reactant and product is the heat of reaction i.e. ∆H.
b. Nucleophilic Substitution bimolecular (SN2):
Aliphatic Nucleophilic Substitution reactions may take place via attack of nucleophile
at electrophilic C in substrate where breaking of bond between leaving group-carbon and
incoming group-carbon take place simultaneously. This led to the formation of product in
single step.
Example:
CH3Br OH CH3OH
methyl bromide
In this reaction rate of reaction depends on conc. of substrate (CH3Br) as well as
conc. of nucleophile (OH-).
Rate α [CH3Br] [OH-]
Rate = k2 [CH3Br] [OH-]
K2 is second order rate constant for the reaction.
As rate of reaction depends only concentration of both molecule i.e. substrate and
nucleophile this reaction is bimolecular reaction.
Mechanism of reaction:

10 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

This reaction is one step reaction. SN2 reactions take place via attack of nucleophile at
electrophelic C in substrate where breaking of bond between leaving group-carbon and
incoming group-carbon take place simultaneously. This led to the formation of product in
single step.
H H
H
+ - Slow Fast
C Br HO C Br HO C BrH-
OH H
H H H
H H
Methyl bromide Transtion state methyl alcohol
.
In substrate central carbon is partially positively charged as it is bonded to electron
withdrawing Br atom. Hence, nucleophile OH ̶ attack on this carbon to form the product from
back side of Br atom. The attack of nucleophile on central C atom lead to the formation of
partial C-OH bond. Likely at the same time C-Br bond starts breaking. This gives rise to the
formation of pentavalent transition state. Formation of transition state is slow step while
breaking of transition state to product is very fast.
Back side attack: Nucleophile, OH ̶ attack on the carbon from back side of Br atom. Since
Br atom is larger in size as well has partial –ve charge. The nucleophile OH- also have –ve
charge, hence it is repelled from Br atom. Thus, due to similar charges on Br and OH- ions
and larger size Br atom, OH attack on C from back side of Br atom (See diagram given
below).

Figure: Space filling model of methyl bromide

Stereochemistry: Due to back side attack of nucleophile complete inversion of configuration
take place in SN2 reaction.
Reactant undergo Nucleophilic substitution reaction via SN2 mechanism when-
i. Substrate is primary
ii. Solvent is non-polar
Both of these factor help to reaction to take place via SN2 path.
Energy profile diagram:
During chemical reactions energy changes takes place in molecule. They are
represented graphically and this graph is called as energy profile diagram. It is as shown
below.

11 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Diagram represents the energy changes during the chemical transformation via SN2
mechanism.
a. The substrate CH3-Br has lowest energy.
b. The T.S. has highest energy and the difference between reactant and T.S. represents the
change in internal energy of reactant i.e. ∆E.
c. The product formed is methyl alcohol which has lower energy than reactant. The energy
difference between reactant and product is the heat of reaction i.e. ∆H.

c. When substrate is secondary the nucleophilic substitution reaction take place by

both mechanism.
C6H5

C6H5 C OH
H3C
25%
C Br H Retention of Coniguration
H3C
C6H5
H
HO C CH3

H 75%
Inversion of Coniguration
.
In this reaction 25% retention and 75% inversion take place. It means that this reaction
take place via SN1 as well as SN2 mechanism.
a. If reaction take place by SN1 way then we expect 50% retention and 50% inversion
b. If reaction takes place by SN2 way then we expect 100% inversion.
In this reaction 25% retention and 75% inversion take place indicating that this reaction take
place via SN1 as well as SN2 mechanism.

d. Stability of carbonium ion: Stability of carbonium ion is affected by atoms / groups

bonded to +vely charged carbon atom.
i) Electron donating atoms or groups +vely charged carbon atom increases stability of
carbonium ion. Electron donating groups able to neutralize some of the +ve charge on
carbon atom, therefore electron donating atoms or groups increases stability of carbonium
ion.
H H CH3 CH3

C C C C
H H H CH3 H CH3 H3C CH3
-CH3 group is electron donor by inductive effect hence stability increases with increase in
number of -CH3 groups in carbonium ion.
ii) Electron withdrawing atoms or groups on +vely charged carbon atom decreases stability of
carbonium ion. Electron withdrawing groups increases the magnitude of +ve charge on
carbon atom, therefore electron withdrawing atoms or groups decreases stability of
carbonium ion.
H H CH3 H

C C C C
H CCl3 H CHCl2 H CH2Cl H CH3
-Cl atom is electron withdrawing by inductive effect hence stability decreases with increase
in number of Cl atoms in CH3 group.

12 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Difference in SN1 and SN2 reaction

SN1 reaction SN2 reaction
A two-step mechanism A one-step mechanism
A unimolecular rate-determining step A bimolecular rate-determining step

Products have both retained and inverted Product has inverted configuration relative to
configuration relative to the reactant the reactant
Reactivity order: Reactivity order:
3o > 2o > 1o > methyl methyl > 1o > 2o > 3o

Table: Nucleophilic Substitution reactions of alkyl halides

4.5.2 Nitrite and nitro formation:

Alkyl halides on reaction with potassium nitrite yield alkyl nitrite where O of NO2
group is bonded to C of alkyl group.
R-X + K-O-N=O R-O-N=O + KX

CH3-Cl + K-O-N=O CH3-O-N=O + KCl

Methyl chloride Meethyl nitrite
.
Alkyl halides on reaction with silver nitrite yield nitro alkane where N of NO2 group
is bonded to C of alkyl group.
R-X + Ag-O-N=O R-NO2 + AgX
O
CH3-Cl + Ag-O-N=O H3C N + AgCl
O
Methyl chloride
Nitro Methane .
4.5.3, Nitrile and isonitrile formation: Alkyl halides on reaction with potassium
cyanide and yield alkyl cyanide where C of CN group is bonded to C of alkyl group.
13 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44
Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

alcohol
R-X + K-CN R-CN + KX
Heat
CH3-Cl + K-CN CH3-CN + KCl
Methyl chloride Methyl cynide
i.e. acetonitril
.
Alkyl halides on reaction with Silver cyanide and yield alkyl isocyanide where N of CN
group is bonded to C of alkyl group.
R-X + Ag-CN R-NC + AgX
alkyl isocynide
CH3-Cl + Ag-CN H3C NC + AgCl
Methyl chloride
. methyl isocynide .

4.5.4 Williamson’s ether synthesis: Alkyl halide react with sodium ethoxide to form
the ethers. Simple as well as mixed ethers can be prepared in laboratory by Williamson
Synthesis.
Alcohol
C2H5 ONa + Br C2H5 C2H5 O C2H5
sodium Ethoxide Heat Diethy ether .
ONa O CH3
OH
CH3Br
+ alcoholic NaOH

Phenol Sodium Phenoxide Methyl phenyl ether .

This reaction follows SN2 mechanism. Ether is formed as a result of backside attack by
alkoxide/ phenoxide ion (a nucleophile) on alkyl halide.
H3C H
H
Alcohol H C O C
C Br 3
H3 C O H
H CH3
Methy ethyl ether
Ethyl Bromide
The alkyl halide used in this reaction must be primary. For example: t-butyl methyl
ether can be synthesised by reaction of methyl bromide with sodium t-butoxide.

H3C H H3C
Alcohol
C O C Br C O CH3
H3C H
H3C
H3C H H3C
t-butoxide Mehyl Bromide Methy t-butyl ether
.
If secondary or tertiary alkyl halides are used, the reaction leads mainly to alkene
formation (elimination reaction).

14 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

H3C H3C
H H H
Alcohol
C O H2C C CH3 C OH +HC
H3C H3C 2 C CH3
H3C Br H3C
t-butoxide Propene
. 2-Brompropane t-butyl alcohol
Aryl halide do not form ether with alkoxide. Since aryl halide undergo
electrophilic substitution reaction at benzene ring other than halide
position.

4.5.5 Elimination: When alkyl halide having at least one β-hydrogen is boiled with
alcoholic solution of potassium hydroxide, it undergoes elimination of hydrogen atom from
β-carbon and halogen atom from α - carbon resulting in the formation f an alkene.
H
OH
Alcoholic
C C
+ H2O + Br-
  C C
NaOH
Br .
This reaction is called β-elimination (or 1,2 - elimination) reaction as it involves
elimination of halogen and a β – hydrogen atom. This reaction leads to more unsaturated
product than substrate. Such as alkene from alkane. When atoms or groups are loosed from
adjutant carbon atom then elimination reaction is called as beta elimination.

Elimination Reactions

E1 - mechanism E2 - mechanism

a) E1- Mechanism: E1 reaction take place via. formation of carbonium ion and it is two
step reaction. In first step heterolysis of C–X bond take place to form carbonium ion while in
second step base attack on beta H atom to form the product. The rate of this reaction is
observed to be depends only on concentration of substrate.

Rate α [2-bromo 2-mehyl propane]

Rate = k1 [2-bromo 2-mehyl propane]
Thus, reaction is named as E1 i.e. elimination unimolecular reaction.

OH H CH3
H CH3 H CH3
fast
  Step-1 C C
H C C CH3 Slow H C C CH3
H CH3
H Br H 2 methyl propene
Carbonium ion

2-bromo 2 methyl propane

15 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

In 2-bromo 2-methyl propane α-carbon is tertiary in nature. It consists of –Br group

which is electronegative in nature. Thus, this C–Br bond is polar in nature and can undergo
heterolytic fission to form carbonium ion and Br-. It is easily stabilised as it is tertiary in
nature.

In second step base such as OH- attack on β-H which is abstracted as H+ and electrons
in this C–H bond are added between α and β Carbon atoms to form C=C. this step is very
fast.

Elimination takes place via. E1 path when substrate can form stable carbonium ion i.e.
carbonium ion is tertiary.

b) E2- Mechanism: E2 reaction take one step where abstract of proton and dissociation of
group take place simultaneously. Attack of base OH- on beta H atom, dissociation of C–Cl
bond and formation of C=C take place simultaniously. The rate of this reaction is observed to
be depends on concentration of substrate as well as reagent.

Rate α [OH-] [2-bromo 2-mehyl propane]

Rate = k2 [OH ̶ ] [2-bromo 2-mehyl propane]
Thus, reaction is named as E1 i.e. elimination unimolecular reaction.

H H H H
OH 

H C C H C C HCl

H Cl H H
1-chloroethane ethene

In 1-chloro ethane, α-carbon is primary in nature. It consists of –Cl group which is

electronegative in nature. Thus, this C–Cl bond is polar in nature and can undergo heterolytic
fission to form carbonium ion and Cl .̶ But carbonium is less stable hence it is not formed.
Elimination takes place via. E2 path when substrate cannot form stable carbonium ion i.e.
carbonium ion is primary.

c. Saytzeff Elimination: Rule: When alkene formed is asymmetric in nature then more
substituted alkene is formed as a major product.

H CH3
1-2 elimination
C C
H CH3 H
   H C CH3
H2
H C C C CH3 2 methyl butene minor
1 2 3 4
products
H Br H
H CH3
2-bromo 2 methyl butane
2-3 elimination
C C
H3C H
2 butene, Major product

16 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

In above reaction, two products are possible, since there are β -H atoms C-1 and C-3.
Thus, 1,2 and 2,3 eliminations are possible. 1,2 elimination form less substituted product (2-
methyl butene) while 2,3 elimination form more substituted product (2-butene). More
substituted product i.e. alkene is more hence it is formed in larger amount i.e. it is major
product (2-butene). Less substituted alkene is less stable hence it is formed in less amount i.e.
minor product (2-methyl butene).

4.5.6 Elimination vs. substitution:

Alkyl halides undergo substitution as well as elimination reaction. Both reactions are brought
about by basic reagent, hence there is always a competition between these two reactions. The
reaction which actually predominates depends upon following factors.
a. Nature of alkyl halides: Tertiary alkyl halides prefer to undergo elimination reaction
whereas primary alkyl halides prefer to undergo substitution reaction.
b. Strength and size of nucleophile: Bulkier electron rich species prefers to act as base by
abstracting proton, thus favours elimination. Substitution is favoured in the case of
comparatively weaker bases, which prefer to act as nucleophile
c. Reaction conditions: Less polar solvent, high temperature favours elimination where as
low temperature, polar solvent favours substitution reaction.

17 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Part-II: Aryl Halides

Aryl Halides: Introduction and IUPAC nomenclature, Preparation: (Chloro, bromo and iodo-benzene
case): from phenol, Sandmeyer and Gattermann reactions. Reactions (Chlorobenzene): Aromatic
nucleophilic substitution (replacement by –OH group) and effect of nitro substituent. Benzyne
Mechanism: KNH2/NH3 (or NaNH2/NH3). Reactivity and Relative strength of C-Halogen bond in alkyl,
allyl, benzyl, vinyl and aryl halides. (Ref.-1: 165-211 and 943-967)

4.6 IUPAC Nomenclature:

F Cl Br I

Fluorobenzene Chlorobenzene Bromobenzene Iooobenzene

Br Cl Cl Br

Cl Br Br

OH CH3 OH

P-bromophenol P-Chlorotoluene 1,3 dichlorobenzene 2,4,6 trobromo

or 4-bromo phenol or 4-Chlorotoluene m-dichlorobenzene phenol
.
4.7 Methods of Preparation:
4.7.1 From Phenol: Phenolic aryl halides can be obtained from reaction of phenol with X2
under specified condition. When Phenol is treated with Br2 in CS2 mixture of O-bromo
phenol (minor product) and P-bromo phenol (major product) is obtained as product.
OH
OH OH

Br
CS2 + 2HBr
+ Br2 +

O-bromo phenol P-bromo phenol

Phenol Br
.
ii) When Phenol is treated with Br2 in water then 2, 4, 6-tribromo phenol is obtained as
product.
OH OH

Br Br

Water +
+ Br2 3HBr

2,4,6 tri-bromo phenol

Phenol
Br .

18 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

4.7.2 From Benzene: Benzene undergoes halogenation reaction in presence of Lewis

acid such as FeCl3, ALCl3 to form benzene halide.
Cl

FeCl3
+ Cl2 + FeCl4-

Benzene Chlorobenzene
Br

FeCl3
+ Br2 + FeCl3Br-

Benzene Bromobenzene .
4.7.2 From Diazonium salt: One can start from benzene and end up with aryl halide
through number steps as follows.
Step-1-Nitration of benzene: Benzene reacts with nitric acid in presence of H2SO4 to form
Nitro benzene.

Step-2-Reduction of Nitro group: Reduction of nitro benzene with Fe/HCl form aniline.

Step-3-Diazotization: Aniline on reaction with nitrous acid (HCl + NaNO2) form diazonium salt
of benzene.

Step-4-Diazo salt on treatment with specific reagent form aryl halide. Sandmeyer’s Reaction-
Conversion of diazobenze to chloro- and bromo- benzene by action of CuCl or CuBr.

Step-1 NO2 NH2 Step-3 N N Cl

Step-2

HNO3 Fe metal NaNO2 +HCl

H2SO4 HCl Cold

Benzene Nitrobenzene Aniline Benzenediazonium

chloride
F

BF4- Fluorobenzene
Step-4
Cl
N N Cl
CuCl
Chlorobenzene
Br
Benzenediazonium
chloride CuBr Bromobenzene
I

KI i.e. I
Iodobenzene
.

19 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

4.7.2 Gattermann reactions: Sometimes the synthesis is carried out by a modification

known as the Gattermann reaction, in which copper powder and hydrogen halide are used in
place of the cuprous halide.
N N Cl Cl Br

Cu Metal powder
or
HCl or HBr

Benzenediazonium Chlorobenzene Bromobenzene

chloride .
4.8 Reactions of chlorobenzene:
4.8.1 Aromatic Nucleophilic Substitution: In nucleophilic substitution reaction -Cl is
replaced by another nucleophile such as -OH group. Aryl halides show low reactivity towards
nucleophilic substitution reactions. The low reactivity of aryl halides is due to:
i. Resonance effect and ii. sp2 hybrid state of C.
i. One of the lone pairs of electrons on halogen atom is in conjugation with π -electrons of the
ring. For example, the following different resonance structures can be written for
chlorobenzene.

Cl Cl Cl Cl
Cl

I IV V
II III .
Resonance structures II, III and IV show double bond character to carbon-chlorine bond.
Thus carbon-chlorine bond in chlorobenzene is stronger and shorter than chloroalkane
molecule, C-Cl bond length in chlorobenzene is 169 pm as compared to C-Cl bond length in
alkyl chloride 178 pm. Hence it is difficult to break.
If phenyl cation produced due to self-ionization of haloarene will not be stabilised by
resonance, which rules out possibility of SN1 mechanism (not possible). Back side attack of
nucleophile is blocked by the aromatic ring, which rules out SN2 mechanism (not possible).
Thus, nucleophilic substitution reaction involving cleavage of C-X bond in haloaryl
compound proceeds with difficulty. The reaction can take place high temp. and pressure.
Cl O Na OH

Aq. NaOH HCl

+ 340 C, 300 atm.

Or Pass CO2 gas

Chlorobenzene Sodium phenoxide Phenol

However, the presence of certain groups at certain positions of the ring, markedly
activate the halogen of aryl halides towards substitutions. For example, presence of electron
withdrawing group at ortho and/or para position greatly increases the reactivity of haloarenes
towards substitution of halogen atom. Greater the number of electron withdrawing groups at
ortho or para position, greater is the reactivity. Electron withdrawing group at meta position
has practically no effect on reactivity.

20 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

OH
Cl Cl HO Cl HO Cl
HO

HO- Slow + Cl-

Step N
N N N N O
O O
O O O O O O O
p-nitro Phenol
p-nitro chlorobenzene
Resonance Stabilization of carbanion Product
Substrate .
Dinitro and trinitro chlorobenzene react under milder condition than the nitrobenzene.
This is due to a greater number of electron withdrawing -NO2 groups which stabilize
carbanion to greater extent.

Cl ONa OH
NO2 NO2 NO2
96 oC H+
+ OH-
NaOH

NO2 NO2 NO2

1-chloro-2,4-dinitrobenzene 2,4-dinitro phenol
Cl OH

O2N NO2 O2N NO2

Warm water
+ OH-

NO2 NO2
1-chloro-2,4,6-trinitrobenzene 2,4,6-trinitro phenol
.

4.8.2 Elimination-addition mechanism for nucleophilic aromatic substitution-

Benzyne Mechanism:
In the absence of activation groups (-Nitro), nucleophilic substitution can be forced to
take place, by use of very strong bases, such as KNH2/liquid NH3. The mechanism of this
reaction is entirely different. The reaction takes place by elimination-addition reaction called
as the benzyne mechanism.
Example: Conversion of bromobenzene to aniline.
Br KNH2 K+ + -NH2 NH2
-
NH2 H
H
KNH2 / NH3 NH3
Elimination KBr addition

Benzyne Aniline
Bromobenzene
.
Intermediate
In above reaction first step is elimination of H and Br on adjutant carbon atom to form
alkyne i.e. benzyne. The strong base -NH2 withdraw ortho-H atom on benzene ring, as it is
slightly acidic nature due to electron withdrawing effect shown by -Br. As H+ is withdrawn
C≡C is formed which facilitate to break C-Br bond. Benzyne is highly unstable as it has sp
hybrid C atoms bonded to sp2 hybrid c atoms. The benzyne then immediately undergoes
addition of NH3 i.e. H – NH2 across C≡C to form aniline. Thus, in all it appears to be
21 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44
Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

nucleophilic substitution product. But it is not. It can be confirmed by labelling C atom

bonded to Br (14C). This can be immediately seen from the following representation. We get
two product in which -NH2 group is bonded to *C atom as well adjutant to *C atom.
Br KNH2 K+ + -NH2 NH2 H
-
NH2 * * H
* H * NH2
KNH2 / NH3 NH3
+
Elimination KBr addition

Benzyne Aniline
Bromobenzene Aniline
. Intermediate
When both ortho positions are occupied by other groups, then this reaction does not
take place. This is due to non-availability of H atom for elimination reaction.
Br

H3CO CH3
No Reaction

22 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44