CHAPTER 10

Haloalkanes and
Haloarenes

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1
Classification of
haloalkanes

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Mono, Di, Tri or Polyhalo Compounds
 Haloalkanes may be classified as mono, di,
or polyhalogen (tri-,tetra-, etc.) compounds
depending on whether they contain one,
two or more halogen atoms in their
structures.

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4
Classification of haloalkanes
 Monohaloalkanes may be further classified
according to the hybridisation of the carbon
atom to which the halogen is attached.
 Compounds containing Csp3 −X bond

Compounds containing C sp2 −X bond

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Compounds containing Csp3 −Cl bond
 In this class of Haloalkanes, the –Cl group is
attached to an sp3 hybridised carbon atom of
an alkyl group. They are further classified as
follows:
 Primary, secondary and tertiary alkyl
halides: In these three types of Haloalkanes,
the –Cl group is attached to primary,
secondary and tertiary carbon atom,
respectively as depicted below:
6
Classification of Haloalkanes
Primary (1º) Secondary (2º ) Tertiary (3º)

H CH3 CH3
CH3-C-Cl CH3-C-Cl CH3-C-Cl
H H CH3

1 CH3 2 CH3 3 CH3

attached attached attached
to C-Cl to C-Cl to C-Cl

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Compounds containing Csp3 −Cl bond
 Allylic haloalkane: In these haloalkanes, the
—Cl group is attached to a sp3 hybridised
carbon next to the carbon-carbon double
bond, that is to an allylic carbon.
 CH2 = CH – CH2 Cl

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Compounds containing Csp3 −Cl bond
 Benzylic haloalkane: In these alcohols, the
—Cl group is attached to a sp3—hybridised
carbon atom next to an aromatic ring. For
example

 Allylic and benzylic haloalkanes may be

primary, secondary or tertiary
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Compounds containing Csp2 −Cl bond

 These haloalkanes contain —Cl group

bonded to a carbon-carbon double bond i.e.,
to a vinylic carbon or to an aryl carbon.
These are also known as vinylic
haloalkanes.

 Vinyl chloride: CH2 = CH – Cl

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 Nomenclature
 Haloalkane
 CH3CH2CH(Cl)CH3 2-Chlorobutane
 (CH3)3CCH2Br 1-Bromo-2,2-dimethylpropane
 (CH3)3CBr 2-Bromo-2-methylpropane
 CH2 = CHCl Chloroethene
 CH2 = CHCH2Br 3-Bromopropene

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 Nature of C-X Bond
 Since halogen atoms are more electronegative
than carbon, the carbonhalogen bond of alkyl
halide is polarised; the carbon atom bears a
partial positive charge whereas the halogen
atom bears a partial negative charge.

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 Methods of Preparation
 From Alcohols
 R.OH+H.X –ZnCl2→ R.X+H2O
 R.OH+NaBr+H2SO4→ R.Br+NaHSO4+H2O
 3R.OH+PX3 → 3 R.X+H3PO3
 R.OH+PCl5 → R.Cl+POCl3 + HCl

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 From Hydrocarbons
 By free radical halogenation
 Free radical chlorination or bromination of
alkanes gives a complex mixture of isomeric
mono- and polyhaloalkanes.
 CH3.CH2.CH2.CH3 ----Cl2 /UV--- →
CH3.CH2.CH2.CH2Cl+ CH3.CH2.CHCl.CH3

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 By electrophilic substitution
 Aryl chlorides and bromides can be easily
prepared by electrophilic substitution of
arenes with chlorine and bromine
respectively in the presence of Lewis acid
catalysts like iron or iron(III) chloride.

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16
Sandmeyer’s reaction

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 From alkenes
 Addition of hydrogen halides: An alkene is
converted to corresponding alkyl halide by
reaction with hydrogen chloride, hydrogen
bromide or hydrogen iodide.
 CH2 = CH2 + HCl → CH3- CH2Cl

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 Halogen Exchange
 Alkyl iodides are often prepared by the
reaction of alkyl chlorides/bromides with
NaI in dry acetone. This reaction is known
as Finkelstein reaction.
 R.X+NaI → RI+NaX

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 Physical Properties
 They are colourless when pure. However,
bromides and iodides develop colour when
exposed to light. Many volatile halogen
compounds have sweet smell.
 Lower members are gases at room
temperature. Higher members are liquids or
solids.
 The haloalkanes are only very slightly
soluble in water.
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 Chemical Reactions
The reactions of haloalkanes may be divided
into the following categories:
 Nucleophilic substitution
 Elimination reactions
 Reaction with metals.

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Nucleophilic substitution reactions
 ᵟ+ ᵟ-
 Nu- + C-X → C-Nu + X-

 E.g. OH-, CN-, R-

 This reaction can take place in two different
mechanisms
 SN2 Mechanism
 SN1 Mechanism
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SN2 Mechanism

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 SN2 Mechanism
 In SN2 Mechanism, the rate depends upon the
concentration of both the reactants. The
incoming nucleophile interacts with alkyl
halide causing the carbonhalide bond to break
while forming a new carbon-OH bond. These
two processes take place simultaneously in a
single step and no intermediate is formed. As
the reaction progresses and the bond between
the nucleophile and the carbon atom starts
forming, the bond between carbon atom and
leaving group weakens.

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 As this happens, the configuration of carbon
atom under attack inverts in much the same
way as an umbrella is turned inside out
when caught in a strong wind. This process
is called as inversion of configuration.

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 Since this reaction requires the approach of
the nucleophile to the carbon bearing the
leaving group, the presence of bulky
substituents on or near the carbon atom
have a dramatic inhibiting effect. Tertiary
halides are the least reactive because bulky
groups hinder the approaching
nucleophiles. Thus the order of reactivity
followed is:
 Primary halide > Secondary halide >
Tertiary halide.
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27
Substitution nucleophilic
unimolecular (SN1)
 SN1 reactions are generally carried out in polar
protic solvents (like water, alcohol, acetic acid,
etc.). The reaction between tert-butyl bromide
and hydroxide ion yields tert-butyl alcohol and
follows the first order kinetics.
 (CH3)3C-Br+ OH- → (CH3)3C-OH+ Br-

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 Mechanism
 It occurs in two steps. In step I, the polarised
C—Br bond undergoes slow cleavage to
produce a carbocation and a bromide ion. The
carbocation thus formed is then attacked by
nucleophile in step II to complete the
substitution reaction.
 (CH3)3C-Br → (CH3)3C+ + Br-
 (CH3)3C+ +OH- → (CH3)3C-OH

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 Step I is the slowest and reversible. Since the rate
of reaction depends upon the slowest step, the rate
of reaction depends only on the concentration of
alkyl halide and not on the concentration of
hydroxide ion.
 Further, greater the stability of carbocation,
greater will be its ease of formation from alkyl
halide and faster will be the rate of reaction. In
case of alkyl halides, 30 alkyl halides undergo SN1
reaction very fast because of the high stability of 30
carbocations.
 Primary halide < Secondary halide < Tertiary
halide.
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Stereochemical aspects of
nucleophilic substitution reactions
 If the light is rotated towards left
(anticlockwise direction), the compound is
said to be laevorotatory or the l-form and a
negative (–) sign is placed before the degree
of rotation. If rotation is to right, it is called
Dextrorotatory (+).Such (+) and (–)
isomers of a compound are called optical
isomers and the phenomenon is termed as
optical isomerism.

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 Asymmetric carbon or stereocentre is
responsible for optical activity. Asymmetric
carbon is one with 4 different substituents
attached to the same carbon atom. The
mirror image and such a molecule are always
nonsuperimposable.

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 racemic mixture
 A mixture containing two enantiomers in
equal proportions will have zero optical
rotation, as the rotation due to one isomer
will be cancelled by the rotation due to the
other isomer. Such a mixture is known as
racemic mixture or racemic
modification. The process of conversion of
enantiomer into a racemic mixture is known
as racemisation.

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 Retention
 Retention of configuration is the
preservation of integrity of the spatial
arrangement of bonds to an asymmetric
centre during a chemical reaction or
transformation. Here the optical rotation of
the reactant and product are the same.

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 Inversion
 Inversion of configuration is the inversion of
the spatial arrangement of bonds to an
asymmetric centre during a chemical
reaction or transformation. Here the optical
rotation of the reactant and product are
different.

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Optical Activities of SN and SN 1 2
 SN2 mechanism has the inverted configuration
as compared to the reactant. This is because the
nucleophile attaches itself on the side opposite
to the one where the halogen atom is present.
 SN1 reactions are accompanied by racemisation.
The attack of the nucleophile may be
accomplished from either side resulting in a
mixture of products, one having the opposite
configuration of the other.
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Elimination reactions

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 Elimination reactions
 When a haloalkane with β-hydrogen atom is
heated with alcoholic solution of potassium
hydroxide, there is elimination of hydrogen
atom from β-carbon and a halogen atom
from the α-carbon atom. As a result, an
alkene is formed as a product. Since β-
hydrogen atom is involved in elimination, it
is often called β-elimination.

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REACTION WITH 2 β-HYDROGENS
 CH3.CH2.CH2.CH.Br.CH3

 CH3.CH2.CH2.CH = CH2
 1-pentene (19%)
 CH3.CH2.CH = CH.CH3
 2-pentene (81%)

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 Zaitsev rule
 In dehydrohalogenation reactions, the
preferred product is that alkene which has
the greater number of alkyl groups attached
to the doubly bonded carbon atoms.

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 Reaction with metals
CH3.CH2.Br + Mg - dry ether → CH3.CH2.MgBr
 Similar compounds are referred as Grignard
Reagents. Such compounds are included in
the family organo-metallic compounds.

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Reactions of Grignard Reagents
 ᵟ- ᵟ+
 R-MgX
 R-MgX+ H2O → R.H + MgX.OH
 alkane

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 Wurtz reaction
 Alkyl halides react with sodium in dry ether to
give hydrocarbons containing double the
number of carbon atoms present in the halide.
This reaction is known as Wurtz reaction.
 2RX+ 2 Na → R.R+ 2NaX

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 Reactions of Haloarenes
 Nucleophilic substitution
 Aryl halides are extremely less reactive
towards nucleophilic substitution reactions
due to:
 Resonance effect
 Difference in hybridisation of carbon atom
in C—X bond
 Instability of phenyl cation
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 Resonance in chlorobenzene

C—Cl bond acquires a partial double bond character

due to resonance. As a result, the bond cleavage in
haloarene is difficult than haloalkane and therefore,
they are less reactive towards nucleophilic
substitution reaction.

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 Difference in hybridisation of
carbon atom in C—X bond
In haloalkane, the carbon atom attached to halogen
is sp3 hybridised while in case of haloarene, the
carbon atom attached to halogen is sp2-hybridised.

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 The sp2 hybridised carbon with a greater s-
character is more electronegative and can hold
the electron pair of C—X bond more tightly
than sp3-hybridised carbon in haloalkane with
less s-chararcter. Thus, C—Cl bond length in
haloalkane is 177pm while in haloarene is 169
pm. Since it is difficult to break a shorter bond
than a longer bond, therefore, haloarenes are
less reactive than haloalkanes towards
nucleophilic substitution reaction.

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 Instability of phenyl cation
 In case of haloarenes, the phenyl cation
formed as a result of self-ionisation will not
be stabilised by resonance and therefore, SN1
mechanism is ruled out.
 Another reason
 Because of the possible repulsion, it is less
likely for the electron rich nucleophile to
approach electron rich arenes.
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 Replacement by hydroxyl group
 Chlorobenzene can be converted into
phenol by heating in aqueous sodium
hydroxide solution at a temperature of 623K
and a pressure of 300 atmospheres.

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 OH

NaOH,623K, 300atm

H+

Phenol

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 The presence of an electron withdrawing group
(-NO2) at ortho- and para-positions increases
the reactivity of haloarenes.
OH
NaOH,443K

H+

p-nitrophenol

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Electrophilic substitution reactions
 Halogen atom besides being slightly
deactivating is o, p directing; therefore,
further substitution occurs at ortho- and
para positions with respect to the halogen
atom.

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53
 Due to resonance, the electron density
increases more at ortho- and para-positions
than at meta-positions. Further, the halogen
atom because of its –I effect has some
tendency to withdraw electrons from the
benzene ring. As a result, the ring gets
somewhat deactivated as compared to
benzene and hence the electrophilic
substitution reactions in haloarenes occur
slowly and require more drastic conditions
as compared to those in benzene.
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 Nitration

1-chloro-2-nitrobenzene 1-chloro-4-nitrobenzene

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Halogenation
Cl
Cl2

Anhyd.
AlCl3
Cl

1,2-dichlorobenzene 1,4-dichlorobenzene

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Sulphonation
SO3H

2-chlorobenzene sulphonic acid SO3H

4-chlorobenzene sulphonic acid

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Friedel-Crafts reaction
CH3
CH3Cl
CH3Cl

Anhyd.
AlCl3
1-chloro-2-methylbenzene CH3

1-chloro-4-methylbenzene

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 Reaction with metals
 Fittig reaction
 Aryl halides when treated with sodium in
dry ether, two aryl groups are joined
together. It is called Fittig reaction.

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 Wurtz-Fittig reaction
 A mixture of an alkyl halide and aryl halide
gives an alkylarene when treated with
sodium in dry ether and is called Wurtz-
Fittig reaction.

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 Polyhalogen Compounds
 Dichloromethane (Methylene chloride)
 Dichloromethane is widely used as a solvent
as a paint remover, as a propellant in
aerosols, and as a process solvent in the
manufacture of drugs. It is also used as a
metal cleaning and finishing solvent.
 Methylene chloride harms the human
central nervous system.
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 Trichloromethane (Chloroform)
 chloroform is employed as a solvent for fats,
alkaloids, iodine and other substances. The
major use of chloroform today is in the
production of the freon refrigerant R-22. It was
once used as a general anaesthetic in surgery.
 Chloroform is slowly oxidised by air in the
presence of light to an extremely poisonous
gas, carbonyl chloride, also known as
phosgene. It is therefore stored in closed dark
coloured bottles completely filled so that air is
kept out.
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Triiodomethane (Iodoform)
 It was used earlier as an antiseptic but due to
its objectionable smell, it has been replaced
by other formulations containing iodine.

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 Tetrachloromethane
(Carbon tetrachloride)
 It is used in the manufacture of refrigerants and
propellants for aerosol cans. It is also used as
feedstock in the synthesis of chlorofluorocarbons
and other chemicals, pharmaceutical
manufacturing, and general solvent use.
 Exposure to carbon tetrachloride causes liver
cancer in humans. Exposure to CCl4 can make the
heart beat irregularly or stop. The chemical may
irritate the eyes on contact.
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 Freons
 The chlorofluorocarbon compounds of methane
and ethane are collectively known as freons.
They are extremely stable, unreactive, non-toxic,
non-corrosive and easily liquefiable gases. Freon
12 (CCl2F2) is one of the most common freons
in industrial use. It is manufactured from
tetrachloromethane by Swarts reaction. These
are usually produced for aerosol propellants,
refrigeration and air conditioning purposes.

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 Freon and ozone
 In stratosphere, freon is able to initiate
radical chain reactions that can upset the
natural ozone balance

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p,p’-Dichlorodiphenyltrichloroethane(DDT)
 DDT, the first chlorinated organic
insecticides, was originally prepared in 1873,
but it was not until 1939 that Paul Muller of
Geigy Pharmaceuticals in Switzerland
discovered the effectiveness of DDT as an
insecticide. Paul Muller was awarded the
Nobel Prize in Medicine and Physiology in
1948 for this discovery.

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 DDT ,the danger
 DDT is not metabolised very rapidly by
animals; instead, it is deposited and stored
in the fatty tissues. If ingestion continues at
a steady rate, DDT builds up within the
animal over time. The use of DDT was
banned in the United States in 1973,
although it is still in use in some other parts
of the world.

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DDT structure

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