CHAPTER 10

Haloalkanes and
Haloarenes

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1
Classification of
haloalkanes

2
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.

3
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

5
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
7
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

8
Compounds containing Csp3 −Cl bond
Benzylic haloalkane: In these compounds,
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
9
Compounds containing Csp2 −Cl bond
(a) These haloalkanes contain —X 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
(b) The haloalkane where –X is directly
attached to an aromatic ring- Arylic halide

 Cl

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11
 IUPAC Names :
• Here, the monohalogen derivatives
of alkanes are named as haloalkanes.
The position of the halogen atom
and other substituents (alkyl groups)
are indicated by suitable numbers
i.e., 1,2,3.....etc.
NAMES OF ALKYL GROUPS

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15
Common naming: Alkyl halide
 Haloarenes
Haloarenes or aryl halides are named by adding the
prefix 'halo' (fluoro, chloro, bromo, iodo) before the
name of the aromatic hydrocarbon. In case of di-
substituted compounds, the relative positions of the
substituents 1,2; 1,3 and 1,4 are indicated by the
prefixes ortho (o-), meta (m-) and para (p-)
respectively
 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

20
Methods of Preparation
1. From Alcohols
2. From Hydrocarbons
 (a) From Alkanes
 (b) From Alkenes
 (c) By electrophilic substituion of Aromatic HC
3. Halogen Exchange

21
1. From Alcohols

1. R.OH+H.X –ZnCl2→ R.X+H2O

2. R.OH+NaBr+H2SO4→ R.Br+NaHSO4+H2O
NaBr+H2SO4→ HBr + NaHSO4
R.OH + HBr → R Br + H2O

3.R.OH+NaI+H2SO4→ RI not obtained as HI obtained in step 2 is

oxidizes by H2SO4 to I2 . Therefore a non oxidizing acid like H 3PO4 is
required.
4.R.OH+PX3 → 3 R.X+H3PO3 (X= Cl/Br)
5.R.OH+PCl5 → R.Cl+POCl3 + HCl
6.R.OH+ SOCl2 → R Cl + HCl(g) + SO2(g)-BEST METHOD as the
by products are escapable gases. 22
R.OH+H.X –ZnCl2→ R.X+H2O
I

This method is suitable only for the prepration of alkyl halides. Aryl halides cant be prepared by this
method as Aromatic alcohols/ Phenols do not undergo nucleophilic substitution due to partial double bond
character between O and Benzene ring.

II Order of reactivity of alcohols

 10 Alcohol< 20 Alcohol < 3o Alcohol
III Order of rectivity of HX
HF < HBr< HCl < HI – Reason: I- is a better nucleophile
 HI Bond strength is weakest thus I- is easily generated. 23
2. From Hydrocarbons
(a) By free radical halogenation of
Alkanes
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

24
(b) From alkenes
(i) ALKENES + HX
(ii) ALKENES + X2

(i)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

25
It is applicable only for the addition of HBr and not HCl
or HI
(ii)Addition of X2

TEST FOR UNSATURATION

28
3. By electrophilic substitution of Benzene
and its derivatives
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.

29
30
Since the above reaction is a reversible reaction, one of the
product needs to be removed from the system. This is done
using an oxidising agent like HNO3 or HIO3. It oxidises HI to
I2.
4.Balz-Schiemann reaction

fluoroboric acid
 3. 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
RI being ionic precipitates out as acetone is
organic solvent. This drives the reaction in the
forward direction.
SWARTS RXN- Metal flourides ( like AgF, Hg2F2
etc) react with alkyl chloride/bromide to form
alkyl flourides.

37
 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. Less energy is released when new
attractions are set up between RX and water as
these aren’t as strong as the H2 bonding in
water.

39
MELTING AND BOILING POINTS
Molecules of organic halogen compounds are generally polar. They have
greater polarity, higher molecular mass and higher intermolecular forces of
attraction (dipole-dipole and van der Waals). Therefore B.Pts of chlorides,
bromides and iodides are considerably higher than those of the hydrocarbons
of comparable molecular mass.
For same alkyl group B.Pts: RI> RBr> RCl> RF, due to increase in size , mass
of halogen atom and magnitude of van der Waal forces.
B.Pts of isomeric haloalkanes decrease with increase in branching.
B.Pts of isomeric dihalobenzenes are very nearly the same. However, the para-
isomers are high melting as compared to their ortho and meta-isomers,due to
symmetry of para-isomers that fits in crystal lattice better as compared to
ortho- and meta-isomers.
ISOMERIC ALKYL HALIDES

For isomeric RX, greater the branching, lesser

is the surface area and lower is the boiling
point . N-Pentane> isopentane> neopentane

41
BRANCHING & SYMMETRY EFFECT ON B.PT
43
44
 Chemical Reactions
The reactions of haloalkanes may be divided
into the following categories:
Nucleophilic substitution
Elimination reactions
Reaction with metals.

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POLARISED LIGHT: NICOL PRISM
47
 A B
A and B are non superimposable mirror images and hence are
optically active. If A rotates the plane polarised light in right direction,
B will rotate it in the left direction by same angle.ie if A is
dextrorotatory(d) then B will be leavorotatory(l). Hence A and B are
OPTICAL ISOMERS
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50
51
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.
52
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.

53
 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.

54
 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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 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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58
SN2 Mechanism

slow
fast

59
 SN2 Mechanism
1. SN2 stands for nucleophilic substitution-
bimolecular. The rate of reaction depends upon the
concentration of both the reactants( RX and Nu) ie
second order kinetics
2. ONE STEP REACTION-The incoming nucleophile
interacts with alkyl halide causing the carbon halide
bond to break while forming a new carbon-nu 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.

60
3.As the attack of nu is from the opposite
direction, 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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4. 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
an inhibitig 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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63
Substitution nucleophilic unimolecular (SN1)

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Substitution nucleophilic unimolecular (SN1)

SN1 reactions are generally carried out in polar

protic solvents (like water, alcohol, acetic acid,
etc.) since polar solvents stabalize the
carbocation formed.

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 Mechanism
1.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.
slow
(CH3)3C-Br → (CH3)3C+ + Br-
- fast
 (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. Therefore it follows first order
kinetics
2 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. 67
68
Elimination reactions

69
 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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 Saytzeff 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
R X + Mg – dry ether → R Mg X
CH3.CH2.Br + Mg - dry ether → CH3.CH2.MgBr
Similar compounds are referred as Grignard
Reagents( Alkyl magnesium halide) . Such
compounds are included in the family
organo-metallic compounds.

73
Reactions of Grignard Reagents
 ᵟ- ᵟ+
R-MgX
R-MgX+ H2O → R.H + MgX.OH
 alkane
Therefore in presence of traces of moisture, GR
will react with it to for the corresponding
Hydrocarbons. Hence the reactions of GR should
be carried out under anhydrous conditions.
74
 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

75
 REACTIONS OF HALOARENES
NUCLEOPHILIC SUBSTITUTION
1.

2. ELECTROPHILIC SUBSTITUTION

3. REACTION WITH METALS

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1. Nucleophilic substitution
Aryl halides are extremely less reactive towards
nucleophilic substitution reactions due to:
Resonance effect leading to partial double bond
character between C—X .
Difference in hybridisation of carbon atom in C
—X bond. In ary compounds C is sp2 hybridized.
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.

78
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.

79
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.

80
 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.
81
 Under drastic conditions Aryl halides may
undergo nu substitution reaction as given below
1. 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.

82
 OH

NaOH,623K, 300atm

H+

Phenol

83
The presence of an electron withdrawing
group (-NO2) at ortho- and para-positions
increases the reactivity of haloarenes.
OH
NaOH,443K

H+

p-nitrophenol

84
85
86
2. 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.

87
88
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.
89
90
 Nitration

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

91
Halogenation
Cl
Cl2

Anhyd.
AlCl3
Cl

1,2-dichlorobenzene 1,4-dichlorobenzene

92
Sulphonation
SO3H

2-chlorobenzene sulphonic acid SO3H

4-chlorobenzene sulphonic acid

93
Friedel-Crafts reaction
CH3
CH3Cl
CH3Cl

Anhyd.
AlCl3
1-chloro-2-methylbenzene CH3

1-chloro-4-methylbenzene

94
95
 3. 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.

96
 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.

97
 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.
98
99
 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.
100
Triiodomethane (Iodoform)
It was used earlier as an antiseptic but due
to its objectionable smell, it has been
replaced by other formulations containing
iodine.

101
 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.
102
 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.
103
 Freon and ozone
In stratosphere, freon is able to initiate
radical chain reactions that can upset the
natural ozone balance

104
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.

105
 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.

106
DDT structure

107