Haloalkanes and Haloarenes

-H
CH4 CH3X
+X

Haloalkanes/haloarenes are
compounds in which at least
one halogen atom replaces
hydrogen atom of an -H
alkane/aromatic compound.
+X
Haloalkanes and Haloarenes in Daily Life

Bromochlorodifluoromethane is
used in fire extinguishers.

Dichlorodiphenyltrichloroethane
(DDT) is used as pesticides.
 Medicinal Uses of Haloalkanes and Haloarenes

Goitre is caused due to the

Malaria is treated using
deficiency of hormone. Thyroxine
Chloroquine which contains
which contains iodine is used to
chlorine.
treat it.

Halothane is used as Chloramphenicol – Chlorine

an anaesthetic during surgery. It containing antibiotic is used for
contains fluorine, chlorine, the treatment of typhoid fever.
and bromine.
 Classification of Haloalkanes and Haloarenes
Classification

Number of halogens present Hybridisation of 'C' in C—X bond

Depending on the number

of halogens present

Monohaloalkane/ Dihaloalkane/ Polyhaloalkane/

monohaloarene dihaloarene polyhaloarene
 Mono-haloalkanes and Mono-haloarenes

Mono-haloalkanes Mono-haloarenes

Number of halogens (X) = 1

Number of halogens (X) = 1

Di-haloalkanes and Di-haloarenes

Example

Number of halogens (X) = 2

 Classification of Dihaloalkane

Dihaloalkane

Vicinal dihalide Geminal dihalide

H2C CH2

X X
 Polyhaloalkane/ Polyhaloarene

Number of halogens (X)

present in the compound > 2

Polyhalogen compounds
can be named as tri, tetra, etc.

Trihaloalkane Trihaloarene
 Polyhaloalkanes and Polyhaloarene

Polyhaloarene
Polyhaloalkanes

Number of halogens (X) = 3 Number of halogens (X) = 4

 Halo-compounds

Compound containing sp3 C-X bond

Alkyl Allylic Benzylic

halides halides halides

1° 2° 3°
 Types of Alkyl Halides

Alkyl halides

Primary (1°) Secondary (2°) Tertiary (3°)

 Primary Alkyl Halide

Number of carbons attached to

the C-atom of sp3 C-X bond = 1

Primary (1°)
 Secondary Alkyl Halide

Number of carbons attached to

the C-atom of sp3 C-X bond = 2

Secondary (2°)
 Tertiary Alkyl Halide

Number of carbons attached to

the C-atom of sp3 C-X bond = 3

Tertiary (3°)
 Allylic Halides

Halogen atom bonded to an sp³-C

atom which is directly attached to a
carbon-carbon double bond (C＝C)
Allylic Carbon

The allylic carbon is

highlighted in a circle.
Benzylic Halides

Halogen atom bonded

to a sp³-C atom which is
directly attached to
a benzene ring.
 Halo-compounds
Compounds containing
sp2 C-X bond

Vinylic halides Aryl halides

Halogen atom is attached Halogen atom is bonded

to a sp²-C atom of C＝C. to a sp²-C atom of an aromatic ring.
 Nature of C-X Bond

δ+ δ- More
C X electronegative

Less
electronegative

Generally,

Electronegativity Polarisation
difference of C-X bond
 Bond Length

Down the group C-X bond length

C-F < C-Cl < C-Br < C-I

Increasing bond length

 Bond Enthalpy

Generally, Bond length Bond enthalpy

C-F > C-Cl > C-Br > C-I

Increasing bond enthalpy

 Nature of C-X Bond

Dipole moment of
a bond depends on

|Δ E.N.| Bond length

CH3 - Cl > CH3 - F > CH3 - Br > CH3 - I

 Types of Halo Compounds

Alkyl halides Aryl halides

 Physical
Properties

Chemical
Preparation
Properties

Halo
Compounds

Let’s see preparation of

halo compounds
Preparation from Alcohols

R-OH R-X

Hydrohalic acid,
Reagents
phosphorus halides
used
and thionyl chloride
 Preparation from Alcohols and HX

General reaction

CH3 CH3

CH3CH2 C OH + HCl CH3CH2 C Cl + H2O

CH3 CH3

Reactivity of HX Reactivity of ROH

HI > HBr > HCl 3° > 2° > 1°

 Preparation from Alcohols and HCl

Rate of the reaction can

be increased by using
ZnCl2 as a catalyst.

ZnCl2
CH3CH2CH2OH + HCl CH3CH2CH2Cl + H2O
Δ
 Preparation from Alcohols and HCl

R-OH + HCl
When When
ROH = 3° ROH = 1°, 2°

Can react
ZnCl2 is used
without ZnCl2
R-Cl + H2O
A mixture of concentrated
hydrochloric acid and
anhydrous zinc chloride is
called the Lucas reagent.
 Preparation from Alcohols and HX

HI and HBr are often generated CH3CHCH3 Conc. HBr CH3CHCH3

in situ from the halide ion and an acid or NaBr, H2SO4
such as phosphoric or sulfuric acid. OH Br

Δ
CH3CH2CH2OH + HI CH3CH2CH2I + H2O

To prepare HI, KI is not made to

react with conc. H2SO4 or HNO3 as
they are oxidising agents and thus HI is generated from KI and H3PO4.
oxidise iodide ions to iodine (I2).
 Preparation from Alcohols and PX5

3ROH + PX3 3RX + H3PO3 3ROH + PCl3 3RCl + H3PO3

X Cl, Br, I

ROH + PCl5 RCl + HCl + POCl3

3R Cl + H3PO3
 Preparation from Alcohols and PX5

ROH + PCl5 RCl + POCl3 + HCl

+ POCl3 + HCl
 Preparation from Alcohols and SOCl2
General reaction

Pyridine, Δ
ROH + SOCl2 RCl + SO2 + HCl

Good method for the

preparation of alkyl halide

By-products are
gaseous in nature
 Preparation from Alcohols and SOCl2

Pyridine, Δ
ROH + SOCl2 RCl + SO2 + HCl

+ SO2 + HCl
Preparation of Alkyl Halides

From Hydrocarbons

From alkanes From alkenes

Free Radical Halogenation

Halogenation of alkanes
by free radical mechanism

Generates a mixture of
mono/poly haloalkanes
 Mono Halogenation
Cl2

UV light

Rate of reaction of halogens Reactivity of H

F2 > Cl2 > Br2 > I2 3° > 2° > 1°

Preparation of Alkyl Halides

Alkyl halides are prepared

from alkenes in two ways

Mono
Dihaloalkanes
haloalkanes

Addition of HX Addition of X2
 Addition of Hydrogen Halides (HX)

Addition of HBr to a symmetrical Addition of HBr to an unsymmetrical

alkene alkene (Markovnikov's rule)

Example

+ HBr Minor product

+

Major product
 Addition of Halogens

Halogens (Cl2, Br2) add

up to alkenes to form Addition of halogens to
vicinal dihalides. alkenes is an example of electrophilic
addition reaction.

Br

+ Br2 CH2 CH2

Involves halonium
ion formation
Br
Anti-addition
 Preparation of Alkyl Halides

Halogen exchange method is

used to obtain alkyl halides by

Finkelstein Swarts
reaction reaction
 Finkelstein Reaction

Acetone
RX + NaI RI + NaX When RCl or RBr is treated with
a solution of NaI in acetone

X : Cl, Br

Equilibrium is shifted by the

Unlike NaI; NaCl or NaBr precipitation of NaCl or NaBr
is not soluble in acetone.
 Swarts Reaction

General reaction

R-Br/R-Cl R-F

Reagents
AgF, CoF2, Hg2F2
used

Example

CH3-Br + AgF CH3-F + AgBr

 Preparation
of Aryl Halide

Halogenation Via diazonium

of arenes salts
 Preparation of Aryl Halides

Chlorine and bromine in presence of Lewis acid (like AlCl3, FeCl3)

react with benzene by electrophilic substitution reaction.

Cl
FeCl3
+ Cl2 + HCl
25 ℃
 Reactivity of Halogens in ESR

Electrophilic Substitution

F2 Cl2, Br2 I2

Fluorination is Iodination is
highly reactive very slow
 Preparation of Diazonium Salt

+ _

Primary aromatic amines NaNO2

react with nitrous acid at low + NaCl + H2O
HCl, 0-5℃
temperature (273-278 K) to
give aromatic diazonium salts.

Aniline Benzene diazonium

chloride
 Sandmeyer Reaction

+ _ CuCl
+ N2

Treatment of diazonium
salts with cuprous chloride
or bromide leads to aryl
chlorides or bromides,
respectively. It follows free CuBr
radical mechanism. + N2
 Formation of Iodobenzene

Replacement of diazonium group

with iodine doesn’t require cuprous
iodide. It can be done with KI. It also
follows free radical mechanism.

+ _
I

+ KI + N2 + KCI
 Formation of Fluorobenzene

The diazonium group can be replaced

by fluorine by treating the diazonium
salt with Fluoroboric acid (HBF4). It
follows SN1 mechanism.

Heat
+ HBF4 + N2 + BF3

ppt
 Physical
Properties

Chemical
Preparation
Properties

Halo
Compounds

We have seen preparation

of halo compounds. Now
let’s discuss physical
properties of these
compounds.
 Colour and odour

Boiling point

Physical
Melting point
Properties

Solubility

Density
 Colour and Odour

Generally, alkyl halides are

colourless in their pure form.
Generally, volatile
halogen
compounds have
a sweet smell.
But bromides & iodides develop
colour when exposed to light.
 Boiling Point

Boiling point is the

temperature at
which organic
liquid overcomes
intermolecular forces
of attraction and
gets converted to
gaseous state.
 Boiling Point of Haloalkanes
depends on

Polarity and
Branching of
molar mass of
parent chain
the compound
 Boiling Points of Haloalkanes

Polarity of C X bond

C < C < C < C

Polarity of Dipole-dipole
C X bond attraction

Order of van der Waals forces

< < <

Boiling Points of Haloalkanes

Order of B.P.

< < <

 400

300

B.P. (K)
200
Here boiling point is
shown on the graph:
For the same halogen, 100
as the length of
hydrocarbon chain
0
increase, b.p. increases.
CH3Cl CH3CH2Cl CH3CH2CH2Cl
 400

300

B.P. (K)
200
Here boiling point is
shown on the graph:
For same hydrocarbon 100
chain, as the size of
halogen increase, b.p.
0
increases. CH3Cl CH3Br CH3I
 400

300

B.P. (K)
200
G G G
a a a
100
s s s

0
CH3X CH3CH2X CH3CH2CH2X

Chlorides
Bromides
Iodides
 Boiling Points of Haloalkanes

1
Boiling point ∝ Branching

> >

B.P. (K): 375 364 346

Boiling point increases

Boiling Points of Haloalkanes vs Hydrocarbon

Haloalkanes have greater

polarity and higher molar mass
compared to parent hydrocarbon.

B.P. of haloalkanes is
greater than their parent
hydrocarbon due to

Strong intermolecular force

of attraction (Dipole–dipole
and van der Waals forces)
 Boiling Points of Haloarenes

Boiling points of isomeric

dihalobenzenes are
nearly the same.
Cl
Cl
Cl
Cl

Cl
Cl

B.P.: 453 K B.P.: 446 K B.P.: 448 K

 Melting Point of Dihalobenzenes

Para-isomers have high M.P. as

compared to their ortho and meta-isomers.

Cl
Molecules with better packing
Cl
have higher melting point. Cl
Cl

Cl
Cl

M.P.: 256 K M.P.: 249 K M.P.: 323 K

 Solubility of Haloalkanes in Water

Energy required to overcome Energy required to break

attractions between + H-bonds between H2O
haloalkane molecules molecules

is greater than

Energy released when new

bonds are setup between
haloalkane and H2O molecules
Solubility of Haloalkanes in Water

Hence, solubility
of haloalkanes
in water is low.
 Solubility of Haloalkanes in Organic Solvents

Energy required to overcome Energy required to

attractions between + overcome interactions
haloalkane molecules between organic solvent

is nearly same as

Energy released when new

bonds are setup between
haloalkanes & organic solvent

Hence, haloalkanes are

soluble in organic solvents.
Density of Halo Compounds

Bromo, iodo, & polychloro

derivatives of hydrocarbons
are heavier than water.

Number of carbon/halogen atoms &

atomic mass of the halogen atoms

Density
 2.0

1.5
Density
1.0
For same hydrocarbon (g/mL)
chain, as the size of
halogen increase, density 0.5
increases.
0.0 n-C3H7Br n-C3H7I
n-C3H7Cl
 2.0

1.5

Density increases with

Density
number of halogens. (g/mL) 1.0
0.5

0.0
CH2Cl2 CHCl3 CCl4
 Physical
Properties

Chemical
Preparation
Properties

Halo
Compounds

We have seen preparation

and physical properties of
halo compounds. Now
let’s discuss chemical
properties of these
compounds.
 Major Reactions of
Halo Compounds

Reaction with
Substitution Elimination
metals

Functional group Dehydro- Synthesis

transformation halogenation of alkyne
Functional Group Transformation

–
OH

–
RO

–
SH

–
CN
R = Me, 1 o,
or 2o
X = Cl, Br, or I
-
 Dehydrohalogenation

General reaction

EtONa
EtOH

Example

EtONa
+
EtOH
81% 19%
 Synthesis of Alkynes

Alkynes can be synthesised from alkenes

via vicinal dihalides

2NaNH2
+ 2NH3 + 2NaBr
 Mechanism

Step 1
+ + +

Step 2

+ + +
 Reactions with Metals

Grignard
Wurtz reaction
reagent
 Preparation of Grignard Reagent

Grignard reagents are prepared

by the reaction of an organic
halide with magnesium metal
Compounds that contain in an anhydrous ether solvent.
carbon–metal bonds

Grignard reagent RMgX

 Preparation and Properties

A Grignard reagent forms a

complex with its ether solvent.
Et2O
RX + Mg RMgX

Et2O
ArX + Mg ArMgX
 Structure and Reaction of Grignard Reagent

Grignard reagents are

very strong bases.
The C-Mg bond in
Grignard reagents is
covalent and not ionic.

They react with any compound

that has a hydrogen atom attached
to an electronegative atom such
δ- δ+ as oxygen, nitrogen, or sulphur.
R ‒ MgX
 Reaction of Grignard Reagent

The reactions of Grignard

reagents with water and alcohols
are acid–base reactions.

Reaction of Grignard Reagent with H2O

δ- δ+ δ+ δ-
–

:
: :

R — MgX + H — O — H R—H+ HO + Mg2+ + X‒

:

:
 Reaction of Grignard Reagent with Alcohol

δ- δ+ δ+ δ-
–

:
:
R — MgX + H — O — R’ R — H + R’ O + Mg2+ + X‒
:

:
 Wurtz Reaction

In this method two moles

of alkyl halides are treated
with 'Na' metal in dry ether
for preparation of higher alkanes
from 1° or 2° alkyl halides.

Na
R—X + 2Na + X—R R—R + 2NaX
Ether (dry)
 Wurtz Reaction

1° or 2° alkyl halides can give

Wurtz reaction, but in case of 3o alkyl
halides, coupling reaction and
SN2 reaction are not possible.

So, disproportion and elimination

reactions take place.

Na
+
Ether (dry)
 Reactions of Haloarenes

Nucleophilic Electrophilic Reaction with

substitution substitution metal
Nucleophilic Aromatic Substance (SNAr)

General reaction

+ Nu– + X–

X = Halogen
Nucleophilic Aromatic Substance (SNAr)

> > >

Rate of SNAr increases

Electrophilic Substitution in Haloarenes

> > >

Rate of electrophilic substitution

in haloarenes (nitration)
 Recall

General reaction

+ + HA

X = F, Cl, Br, I

Halo groups are

ortho-para directors and
are deactivating groups.
 Fittig Reaction

Aryl halides also give

analogous compounds when
treated with sodium in dry
ether, in which two aryl
groups are joined together.

X
Dry ether
2 + 2Na + 2NaX

90
Corey-House
Synthesis
 Corey-House Synthesis

General Reaction

+ R2 CuLi + RCu + LiX

Gilman reagent

92
 Structure of Gilman’s Reagent

_
δ
Preferably
covalent bond
_
+ δ+

Preferably _ Preferably
δ
ionic bond covalent bond

93
 Corey House Synthesis

_
δ+ δ_ δ_ δ+ δ_ +
+

+ RCu + LiX
94
 Corey House Synthesis

Example

CH3CH2CH2CH2Br + (CH3)2CuLi

CH3CH2CH2CH2CH3 + CH3Cu + LiBr

Alkane containing odd

number of carbons
95
 Corey House Synthesis

Example

CH3CH2Br + (CH3CH2)2CuLi

CH3CH2CH2CH3 + CH3CH2Cu + LiBr

Alkane containing even

number of carbons
96
 Polyhalogen Compounds

Carbon compounds containing

more than one halogen atom

Useful in industry and agriculture

Polyhalogen Compounds

Dichloromethane

Trichloromethane

Triiodomethane

Tetrachloromethane

Freons

DDT
 Dichloromethane

Dichloromethane
(Methylene chloride)
Structure Uses Harmful effects
 Uses

Paint remover

Propellent in aerosol
Dichloromethane

Metal cleansing

As a solvent
 Harmful Effects of Dichloromethane

Slight hearing
Direct contact can cause
and vision
impairment

Harms the Tingling and Burning and mild

Harmful
human central numbness in the redness of skin
nervous system
Effects fingers and toes

Nausea Burning of cornea

 Click to edit Master title style
• Click to edit Master text styles Trichloromethane
• Second level
Trichloromethane
• Third level
• Fourth level
(Chloroform)• Fifth level

Structure Uses Harmful effects

26-04-2021 102
 Uses
Click to edit Master title style
Solvent for fats,
• Click to edit Master text styles alkaloids and iodine
• Second level
• Third level
• Fourth level Production of freon
Trichloromethane
• Fifth level
refrigerants (R-22)

Anesthetic in surgery

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 Harmful Effects of Trichloromethane
Click to edit Master title style
Dizziness, fatigue,
Chloroform exposure causes and headache
• Click to edit Master text styles
• Second level
• Third level Damage to liver
• Fourth level and kidneys
• Fifth level

light
2CHCl3 + O2 2COCl2 + 2HCl

Highly poisonous gas Phosgene

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Click to edit Master title style Triiodomethane

• Click to edit Master text styles

• Second level
• Third level Structure Uses
Triiodomethane
• Fourth level

(Iodoform)
• Fifth level

Has antiseptic
properties due
to the liberation
of free iodine.

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 Tetrachloromethane
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• Click to edit Master text styles
Tetrachloromethane
• Second level
(Carbon tetrachloride)
• Third level
• Fourth level
Structure Uses Harmful Effects
• Fifth level

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 Uses
Click to edit Master title style
Manufacture of
• Click to edit Master text styles refrigerants and propellants
• Second level for aerosol cans
• Third level
• Fourth level
• Fifth level
Feedstock in the synthesis
Tetrachloromethane
of chlorofluorocarbons

Pharmaceuticals
manufacturing
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 Uses
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Cleaning fluid
• Click to edit Master text styles
• Second level
• Third level
•Tetrachloromethane
Fourth level Degreasing agent
• Fifth level

Fire extinguisher

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 Harmful Effects of Tetrachloromethane
Click to edit Master title style
• Click
CCl to edit Master text styles
4 exposure causes
CCl4 exposure causes
• Second level
• Third level
• Fourth level Dizziness & light
• FifthNerve
level cell damage headedness

Cardiac arrest Nausea and vomiting

Liver cancer

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 Freons
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Chlorofluorocarbon
• Click to edit Master text styles
compounds of methane
• Second level & ethane are collectively
• Third level known as freons.
• Fourth level
• Fifth level

Freons

Uses and
Structure Harmful Effects
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characteristics 110
 Uses
Click to edit Master title style
Usesstyles
• Click to edit Master text of Freon-12
• Second level
• Third level
• Fourth level
Aerosol
• Fifth level Propellants

Refrigerators

Air-conditioners

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 Characteristics of Freons
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Freons are
• Click to edit Master text styles
• Second level
• Third level Stable In stratosphere, freon is able
• Fourth level
• Fifth level
to initiate radical chain
reactions that can upset
Non-reactive the natural ozone balance.

Non-toxic

Liquefiable gases
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 DDT
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DDT
• Click to edit Master text styles
• Second level
• Third level
• Fourth level
• Fifth level
Structure Uses Harmful Effects

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 Structure
Click to edit Master title style
• Click to edit Master text styles
• Second level
• Third level
• Fourth level
• Fifth level

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 Harmful Effect of DDT
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• Click to edit Master text styles
• Second level DDT is not metabolised
• Third level very rapidly by animals
• Fourth level
• Fifth level

Deposited and stored

in the fatty tissues.

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