Haloalkanes

and
Haloarenes
Haloalkanes
Halogen derivatives of aliphatic hydrocarbon
Alkyl halide

Haloarenes
Halogen derivatives of aromatic hydrocarbon
Aryl halide
Classification of Organic Halo compounds

1. Based on number of halogen atoms

2. Based on hybridisation
Based on number of halogen atoms:
a) Monohaloalkanes
b) Dihaloalkanes
c) Polyhaloalkanes
Based on Hybridisation:
a) Compounds with sp3 hybridised carbon atom
b) Compounds with sp2 hybridised carbon atom
Based on number of halogen atoms:
1. Monohaloalkanes

Obtained by replacing ONE hydrogen atom of alkane with halogen atom

General formula

Cn H2n+1 X

X= F, Cl, Br, I

Depending on the nature of the carbon atom which is attached to halogen

i. Primary alkyl halide
ii.Secondary alkyl halide
iii.Tertiary alkyl halide
Primary alkyl halide
The Carbon atom containing halogen is attached to ONE alkyl group

Secondary alkyl halide

The Carbon atom containing halogen is attached to TWO alkyl group

Tertiary alkyl halide

The Carbon atom containing halogen is attached to THREE alkyl group
Based on number of hydrogen atoms: (CONTD)
2. Dihaloalkanes
Obtained by replacing TWO hydrogen atom of alkane with halogen atom
2 types

i. Geminal dihalides/ Gem dihalides

Halogen atoms are attached to the Same Carbon atom

ii. Vicinal dihalide/ Vic dihalide

Halogen atoms are attached to the Neighbouring Carbon atoms
Based on number of hydrogen atoms: (CONTD)

3. Polyhaloalkanes

Obtained by replacing more than TWO hydrogen atom of alkane with halogen atom
Based on Hybridisation:
Compounds with sp3 hybridised carbon atom

3 types
i. Alkyl halides
ii.Allylic halides
iii.Benzylic halides

1. Alkyl halides
Compounds with sp3 hybridised carbon atom (contd)

2. Allylic halide
The halogen atom is attached to the saturated Carbon atom which contains a double
bond

3. Benzylic halide
The halogen atom is attached to the saturated Carbon atom present adjacent to the
benzene ring
Compounds with sp2 hybridised carbon atom
2 types
i. Vinylic halide
ii. Aryl halide
Vinylic halide
The halogen is attached to unsaturated Carbon atom

Aryl halide
The halogen is attached to unsaturated Carbon atom of the Benzene ring
Nomenclature of Organic Halo Compounds

1-Bromoethane 1-Chloropropane

2-Bromobutane
2-Chloropropane

1,1-Dichloroethane

2-Chloro, 2-methyl propane 2,2-Dichloropropane

Nomenclature of Organic Halo Compounds

1,2-Dichloropropane 1,2-Dichloroethane

1,2,2,3-Tetrachlorobutane

3-Chloro prop-1-ene
1-Chlorobenzene
Nomenclature of Organic Halo Compounds

2-Chloro eth-1-ene 1-Chloro prop-1-ene

1-Chloro cyclohex-1-ene
4-Chloro pent-2-ene

Chloromethyl benzene 1-Bromo 1-phenyl ethane

Nature of the C-X bond
Halogen is more electronegative than Carbon

C= +ve X= -ve

Atomic size Bond length

I ˃ Br ˃ Cl ˃ F

Reactivity C-I ˃ C-Br ˃ C-Cl ˃ C-F

Methods of preparation Haloalkanes
I. From Alcohols
II. From alkanes
III. From alkenes
IV. By Halogen exchange

From alcohols
Using Phosphorous halides
Using Hydrogen halides
Using Thionyl chloride

By Halogen exchange
Swart’s Reaction
Finkelstein Reaction
Methods of preparation
From Alcohols
a) Using Phosphorous halides
When alcohol is heated with Phosphorous halide, Haloalkanes are formed

Preparation of Alkyl chlorides

When Ethyl alcohol is heated with Phosphorous pentachloride, Ethyl chloride is formed

Cl PCl3 Cl
Methods of preparation (Contd) From Alcohols (Contd)

b) Using Hydrogen halides

When alcohol is heated with Hydrogen halide, in the presence of Anhydrous Zinc Chloride ,
Haloalkanes are formed

Preparation of Alkyl Chlorides (Groove’s process)

When Ethyl alcohol is heated with HCl in the presence of Anhydrous ZnCl2, Ethyl chloride is
formed

Conc HCl + Anhydrous ZnCl2

Lucas Reagent
Reactivity order for alcohol
Tertiary ˃ Secondary ˃ Primary
Methods of preparation (Contd)

b) Using Hydrogen halides (Contd)

Preparation of Alkyl Bromides

When alcohol is heated with constant boiling Hydrobromic acid (48%) in the presence of
H2SO4, Alkyl Bromide is formed

Preparation of Alkyl Iodides

When alcohol is refluxed with constant boiling Hydroiodic acid (57%), Alkyl Iodide is formed
Methods of preparation (Contd)

c) Using Thionyl Chloride (Darzen’s Process)

When alcohol is heated with Thionyl chloride in the presence Pyridine ; Alkyl Chloride is formed

Preparation of Alkyl Chlorides

When Ethyl alcohol is heated with Thionyl chloride in the presence of pyridine , Ethyl Chloride is
formed

What is the role of Pyridine in the Darzen’s process?

Methods of preparation (Contd)

From Alkanes
When alkanes react with halogen in diffused sunlight, alkyl halides are formed

Free-Radical mechanism

Cl• Cl•
Methods of preparation (Contd)

From Alkanes (Contd)

When propane reacts with chlorine, the major product formed is 2-Chloropropane

1° Carbocation 2° Carbocation

Secondary ˃ Primary
Methods of preparation (Contd)

From Alkenes
Preparation of Monohaloalkanes
When Alkenes react with Halogen acids in the presence of acetic acid or methylene chloride
medium, alkyl halides are formed

Minor Product Major Product

Markovnikov’s Rule

The negative part of the addenum attacks the Carbon across the double bond with less
number of Hydrogen atoms
Methods of preparation (Contd)

From Alkenes (Contd)

Preparation of Dihaloalkanes

When alkenes reacts with halogens in carbon tetrachloride, dihaloalkanes are formed

When Ethene reacts with Bromine in carbon tetrachloride, 1,2-Dibromoethane is formed

Brown colour Bromine is discharged

Test for unsaturation

Methods of preparation (Contd)

By Halogen Exchange reaction

Finkelstein reaction
When alkyl chlorides/ bromides are treated with Sodium iodide in the presence of dry
acetone; halogen exchange takes place to form Alkyl Iodides

Swart’s reaction
When alkyl chlorides/ bromides are treated with Metallic fluorides; halogen exchange takes
place to form Alkyl Fluorides

Metallic fluorides like CoF3 (Cobalt fluoride), SbF3 (Antimony fluoride) also can be used
Properties of Haloalkanes
I. Physical properties
a) Boiling point
1) RI ˃ RBr ˃ RCl
Atomic size Vander waal’s force of attraction
2) Haloalkanes ˃alkanes (Same molecular masses)
dipole-dipole interaction of C-X bond
3) Decreases as branching increases
4) Increases as number of carbon atom increases in the alkyl
group
b)Density
RI ˃ RBr ˃ RCl

c) Solubility
Insoluble in water Hydrogen bond
Properties of Haloalkanes
II. Chemical properties
i. Action of KOH or NaOH
a) Nucleophilic substitution reaction ii. Action of Sodium alkoxide
iii. Action of Ammonia
iv. Action of Potassium cyanide
b) Elimination reaction v. Action of Silver cyanide
vi. Action of Potassium nitrite
vii. Action of Silver nitrite
c) Reaction with Metals viii.Action of Silver salt of Carboxylic acid
ix. Action of Lithium Aluminium Hydride
x. Action of Alkyl Lithium
II. Chemical properties (Contd)

a) Nucleophilic substitution reaction

Halogen is more electronegative than Carbon

C= +ve X= -ve

Electrophile Attracts Nucleophile

Nucleophilic Substitution Reaction

a) Nucleophilic substitution reaction (Contd)

i. Action of KOH or NaOH

When an alkyl halide is heated with aqueous potassium hydroxide solution an alcohol is formed.

RX  KOH 
 ROH  KCl

ii.Action of Sodium alkoxide (Williamson’s Ether Synthesis)

When alkyl halides are heated with sodium alkoxide in alcohol, ethers are formed
RX  NaOR 
 R  O  R  NaX
a) Nucleophilic substitution reaction (Contd)

iii.Action of Ammonia
When alkyl halides are heated with alcoholic ammonia in a sealed tube to 373K,
primary amines are formed.
RX  NH 3 alcohol
 RNH 2  HX

iv.Action of Potassium cyanide: Formation of Nitriles

When an alkyl halide is heated with alcoholic solution of potassium cyanide, alkyl
cyanide (Alkanenitriles) is formed.
RX  KCN alcohol
 R  CN  KX
a) Nucleophilic substitution reaction (Contd)

v. Action of Silver cyanide

When an alkyl halide is heated with alcoholic solution of silver cyanide, alkyl
isocyanide (carbylamines) is formed

RX  AgCN  R  NC  AgX

alcohol

Ionic in nature

Nucleophile
AgCN = Covalent in nature Doesnt ionise

+ - Nucleophile
a) Nucleophilic substitution reaction (Contd)

vi. Action of Potassium Nitrite

When alkyl halides are heated with alcoholic solution of potassium nitrite, alkyl
nitrites are formed

KNO2 is Ionic

Ethyl bromide is heated with alcoholic solution of potassium nitrite, Ethyl nitrite is
formed.
a) Nucleophilic substitution reaction (Contd)

vii.Action of Silver Nitrite

When alkyl halides are heated with alcoholic solution of silver nitrite, nitroalkanes
are formed

AgNO2 is Covalent No Ionisation

Ethyl bromide is heated with alcoholic solution of silver nitrite, Nitroethane is

formed
a) Nucleophilic substitution reaction (Contd)

viii.Action of Silver salt of Carboxylic Acid

When haloalkanes are heated with alcoholic solution of silver salt of carboxylic acids,
esters are formed

Hunsdiecker Reaction

When Bromomethane is heated with alcoholic solution of silver salt of Propanoic

acid, Methyl propanoate ester is formed
a) Nucleophilic substitution reaction (Contd)

ix. Action of Lithium Aluminium Hydride

When alkyl halides are heated with lithium aluminium hydride in dry ether alkanes
are formed.

Ethyl bromide is heated with Lithium aluminium hydride in ether medium, Ethane is formed

x. Action of Alkyl Lithium

Alkyl halides react with alkyl lithium to form higher alkanes

Ethyl bromide is heated with methyl Lithium, Propane is formed

Mechanism of Nucleophilic Substitution
Reaction
Based on the nature of the alkyl halides the nucleophilic
substitution reactions take place by two mechanisms

SN1 Mechanism
Substitution, Nucleophilic, Unimolecular

SN2 Mechanism
Substitution, Nucleophilic, Bimolecular
Mechanism of Nucleophilic Substitution Reaction (Contd)

SN2 Mechanism
Example:

When methyl bromide is heated with aqueous potassium hydroxide

solution methyl alcohol is formed

Nucleophile OH– attacks the carbon atom from the side opposite to the Br-

The mechanism involves only one step

Mechanism of Nucleophilic Substitution Reaction (Contd)

SN2 Mechanism (Contd)

Example:
Hydrolysis of Methyl bromide (1-Bromomethane)
Slow

Exists a transition state in which both OH– and Br – are attached to C

Inversion of configuration
C–OH bond becomes stronger C–Br bond weakens
Rate depends upon the concentration of both the reactants
Follows a second order kinetics
Order of reactivity CH3+ ˃Primary ˃Secondary ˃ Tertiary
Mechanism of Nucleophilic Substitution Reaction (Contd)

SN1 Mechanism
Example: When t-butyl bromide is heated with aqueous potassium hydroxide, tertiary butyl
alcohol is formed

Three bulky groups are attached to carbon containing halogen atom

Steric hindrance

Nucleophile OH- cannot attack the carbon atom from the side opposite to halogen atom

Hence SN1 mechanism involves two steps

Mechanism of Nucleophilic Substitution Reaction (Contd)

SN1 Mechanism
Example:
Hydrolysis of t-butyl bromide (2-Methyl, 2-bromopropane)
Step 1 : Formation of carbocation
Protic solvent
Slow Step

Step 2 : Attack of nucleophile on carbocation

Retention of Configuration
Mechanism of Nucleophilic Substitution Reaction (Contd)

SN1 Mechanism

SN1 reactions are generally carried out in polar protic solvents like
water, alcohol, acetic acid etc.
Steric hindrance

Rate of the reaction depends upon the concentration of only one

reactant Slow step Formation of Carbocation

Follows first order kinetics

Reactivity order Tertiary ˃ Secondary ˃ Primary ˃ CH 3+

II. Chemical properties (Contd)

b) Elimination Reaction

γ β α
Hydrogen is removed from β carbon atom

β -Elimination
Saytzeff’s (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 .”
Example:
Dehydrohalogenation of 2-bromobutane using alcoholic potash

2-Butene
Major product

C with MORE no of Hydrogen

1-Butene
Minor product
C with LESS no of Hydrogen
II. Chemical properties (Contd)

c) Reaction with Metals

i. Action of Magnesium formation of Grignard Reagent
When an alkyl halide reacts with magnesium powder in dry ether medium, alkyl magnesium
halide is formed.

Grignard reagents are highly reactive should be prepared in

moisture-proof conditions
ii. Wurtz reaction
When two molecules of alkyl halides react with sodium in dry ether medium higher alkanes
are formed.
Methods of preparation Haloarenes
1) From Aromatic hydrocarbons (Electrophilic substitution reaction)
Example 1 : Benzene reacts with Chlorine in the presence of Ferric chloride to form
Chlorobenzene

Example 2 : Toluene reacts with Chlorine in the presence of Ferric chloride to form a mixture of
Ortho and Para Chlorobenzne
Methods of preparation Haloarenes (Contd)

2) Sandmeyer’s Reaction

When Benzene diazonium chloride is treated with Cuprous chloride in HCl, Chlorobenzene is
formed
Properties of Haloarenes

Aryl halides are less reactive towards Nucleophilic Substitution

reaction. Why?

1. Resonance Effect
2.Hybridisation of Carbon atom
3.Instability of Phenyl Cation
4.High electron density on Benzene ring
Properties of Haloarenes (Contd)

i) Resonance effect

Due to resonance the carbon halogen bond acquires a partial double bond nature

Higher energy is required to break this bond

Cannot undergo Nucleophilic Substitution reaction
Properties of Haloarenes (Contd)

ii) Hybridisation of Carbon Atom

sp2 hybridised

More electronegative sp ˃ sp2 ˃ sp3

Shared pair of electrons between carbon and halogen cannot be

effectively drawn towards the halogen atom.
Bond becomes less polar
Increases the strength of the bond
Difficult to break

Cannot undergo Nucleophilic Substitution reaction

Properties of Haloarenes (Contd)

iii) Instability of Phenyl cation

Phenyl cation
Highly unstable
Not resonance stabilised

Cannot undergo Nucleophilic Substitution reaction

Properties of Haloarenes (Contd)

iv) High electron density on Benzene

Delocalisation of π electrons

Carbon atom in benzene is an electron rich centre

Nucleophiles cannot easily approach

Repulsion

Cannot undergo Nucleophilic Substitution reaction

I. Nucleophilic substitution reaction of Haloarenes

Action of NaOH
When chlorobenzene is heated with aqueous sodium hydroxide at 623K and 300 atm
pressure, sodium phenate is formed which on acidification with HCl gives phenol

If electron withdrawing groups are present on the ortho

or para positions; milder conditions are required for
Nucleophilic substitution reaction
II. Electrophilic substitution reaction of Haloarenes

Chlorobenzene has delocalised π electron cloud

Undergoes electrophilic substitution reactions to give ortho and para products

Electrophilic Substitution reactions of Chlorobenzene (Contd)

1) Halogenation
When chlorobenzene is heated with chlorine in the presence of
anhydrous aluminium chloride a mixture of ortho and para
dichlorobenzene is formed
Electrophilic Substitution reactions of Chlorobenzene (Contd)

2) Nitration
When chlorobenzene is heated with a mixture of concentrated nitric
acid and concentrated sulphuric acid, a mixture of ortho and para
nitrochlorobenzene is formed
Electrophilic Substitution reactions of Chlorobenzene (Contd)

3) Sulphonation
When chlorobenzene is heated with concentrated sulphuric acid;
mixture of ortho and para chlorobenzene sulphonic acid is formed
Electrophilic Substitution reactions of Chlorobenzene (Contd)

4) Friedel Craft’s ALKYLATION

When chlorobenzene is heated with methyl chloride in the presence
of anhydrous aluminium chloride catalyst; a mixture of ortho and
para chlorotoluene is formed
Electrophilic Substitution reactions of Chlorobenzene (Contd)

5) Friedel Craft’s ACYLATION

When chlorobenzene is heated with acetyl chloride in the presence
of anhydrous aluminium chloride, a mixture of ortho and para
chloroacetophenone is formed
III.Reaction with Metals
Wurtz Fittig Reaction
When a mixture of alkyl halide and aryl halide is heated with sodium in dry ether
medium, alkyl benzene is formed

Fittig Reaction
When aryl halides are heated with sodium in dry ether, two aryl groups join
together forming biphenyl
Home work

1. Although chlorine is an electron withdrawing group, yet it is -ortho, -

para directing in electrophilic aromatic substitution reactions. Why?

2. p-Dichlorobenzene has higher m.p. than those of o- and m-isomers-

Justify

3. The dipole moment of chlorobenzene is lower than that of cyclohexyl

chloride. Why?

4. A hydrocarbon C5H10 does not react with chlorine in dark but gives a
singlemonochloro compound C5H9Cl in bright sunlight. Identify the
hydrocarbon
Some Stereochemical concepts

Optical Isomerism

The compounds which can rotate the plane of polarized light are said
to be optically active
Optically active compounds show optical isomerism

Compounds having same molecular and structural formula but differ

in their action on plane polarised light show optical isomerism
Optical activity
Certain compounds rotate the plane of polarised light when it is passed through
their solutions

The property of the compounds rotating the plane of polarised light is Optical activity

Polariser
• Oscillates in all • Oscillates in one
direction direction
• Nicol Prism
• perpendicular to
plane of
propagation
Plane polarised
Ordinary light
light
The compounds which rotate the plane of polarized light to the right
(clockwise)
Dextro rotatory compounds or ‘d’ compounds
In Latin dexter means right or (+) compounds

The compounds which rotate the plane of polarized light to the left
(anti clockwise)
Laevo rotatory or ‘l’ compounds
In Latin laevous means left or (–) compounds.

Dextro and Laevo molecules are isomers Enantiomers

Enantiomers possess identical physical properties namely, M.P, B.P ,refractive index but differ
with respect to the rotation of plane polarized light
Criterion for optical isomerism
1) Asymmetric
Asymmetric molecule :
These are the molecules do not contain plane of symmetry
Plane of Symmetry

Asymmetric carbon atom

A carbon atom which is attached to four different groups is called
asymmetric carbon atom
Criterion for optical isomerism

2) Non-Superimposable
Chiral Molecule
Chiral molecule are the molecules which do not contain plane
of symmetry and show optical activity

Enantiomers
The stereoisomers related to each other as non-superimposable
mirror images are called enantiomers
Enantiomers
The stereoisomers related to each other as non –superimposable mirror images
are called enantiomers
Mirror
d-Lactic acid and l-lactic acid

Racemic mixture
A mixture containing two enantiomers in equal proportions will have zero
optical rotation
Rotation of one isomer will cancel the rotation of the other isomer
The process of conversion of enantiomer into a racemic mixture is
known as racemization
POLY HALOGEN COMPOUNDS
a) Dichloromethane (CH2Cl2)

DCM
Methylene chloride

Uses:
a. Useful solvent for many chemical reactions.
b. Paint remover, degreaser, in decaffeinating coffee and tea,
an aerosol spray propellant, as a metal finishing and cleaning solvent
c. As a chemical to function in a heat engine that can extract mechanical energy from small
temperature differences.
d. To prepare extracts of hops and flavorings.
POLY HALOGEN COMPOUNDS
a) Dichloromethane (CH2Cl2) (Contd)

Effects:

 Harms the central nervous system

 Exposure to lower levels leads to slightly impaired hearing
and vision
 Exposure to higher levels cause dizziness,nausea, tingling
and numbness in the fingers and toes
 Direct skin contact causes intense burning and mildredness
of the skin
 Direct contact with the eyes can burn the cornea
POLY HALOGEN COMPOUNDS
b) Trichloromethane (CHCl3)
TCM
Chloroform
2 CHCl3+ O2→ 2 COCl2 + 2 HCl
Phosgene
Poisonous Gas
Uses:
a. In the production of the freon refrigerant R-22
b. As a solvent for producing dyes and pesticides as solvent for
alkaloids- to extract Morphine from poppies
c. As an anesthetic and in medicines - cough syrups
d. As a preservative for anatomical specimens
POLY HALOGEN COMPOUNDS
b) Trichloromethane (CHCl3) (Contd)

Effects:

 Exposure for a short time can cause dizziness, fatigue, and

headache

 Damages the liver & kidneys

 Develop sores upon skin contact

POLY HALOGEN COMPOUNDS

c) Triiodomethane (CHI3)

Iodoform

Uses:
a. As an antiseptic for treating skin infections, sores, boils, burns etc.
(When applied on the skin iodoform decomposes to release iodine)
b. To manufacture pharmaceuticals
Effects:
 Bad smell
POLY HALOGEN COMPOUNDS

d) Tetrachloromethane (CCl4)

Carbon Tetrachloride

Uses:
a. In the manufacture refrigerants and aerosol propellants
b. In the manufacture of chloroform
c. For dry cleaning
d. As a fire extinguisher
POLY HALOGEN COMPOUNDS
d) Tetrachloromethane (CCl4) (Contd)

Effects:

 Causes liver cancer

 Dizziness, light headedness, nausea and vomiting, which
can cause permanent damage to nerve cells
 Long term exposure leads to coma, unconsciousness or death
 Can make the heart beat irregularly or stop
 Irritates the eyes on contact
 Depletes the ozone layer, leading to increased skin cancer,
eye diseases and disorders & disrupts the immune system
POLY HALOGEN COMPOUNDS
Freons
Chloro fluoro carbon
Uses:
a. As refrigerants
b. As propellants in medicinal application
c. As a degreasing solvents
d. As a precursor to tetrafluoroethylene, the monomer that is
converted to Teflon.
POLY HALOGEN COMPOUNDS
DDT
(p, p’- Dichlorodiphenyl trichloro ethane)

DDT is prepared by the reaction of chloral with chlorobenzene in the presence of sulfuric acid
POLY HALOGEN COMPOUNDS
DDT (Contd)

Effects:

 High toxicity towards fish

 Cannot be metabolised very rapidly by animals, hence deposites
& is stored in the fatty tissues

Use of DDT is banned in the United States since 1973