HALOALKANES AND

HALOARENES
INTRODUCTION
▪ The replacement of hydrogen atom(s) in a
hydrocarbon, aliphatic or aromatic, by halogen
atom(s) results in the formation of alkyl halide
(haloalkane) and aryl halide (haloarene),
respectively.
▪ Haloalkanes contain halogen atom(s) attached
to the sp3 hybridised carbon atom of an alkyl
group whereas haloarenes contain halogen
atom(s) attached to sp2 hybridised carbon
atom(s) of an aryl group.
USES
▪ Many halogen containing organic compounds are used as
solvents for relatively non-polar compounds and as starting
materials for the synthesis of wide range of organic
compounds.
▪ Chlorine containing antibiotic, chloramphenicol, produced by
soil microorganisms is very effective for the treatment of
typhoid fever.
▪ Our body produces iodine containing hormone, thyroxine, the
deficiency of which causes a disease called goiter.
▪ Synthetic halogen compounds, viz. chloroquine is used for the
treatment of malaria;
▪ halothane is used as an anaesthetic during surgery.
▪ Certain fully fluorinated compounds are being considered as
potential blood substitutes in surgery.
 CLASSIFICATION
On the Basis of Number of Halogen Atoms

▪ Haloalkanes and haloarenes may be classified as mono,

di, or polyhalogen (tri-,tetra-, etc.)
Monohalocompounds may further be classified
according to the hybridisation of the carbon
atom to which the halogen is bonded.
COMPOUNDS CONTAINING Sp3C-X
BOND
(a) Alkyl halides or haloalkanes (R—X)
▪ In alkyl halides, the halogen atom is bonded to an alkyl group
(R).
▪ They form a homologous series represented by CnH2n+1X.
▪ They arefurther classified as primary, secondary or tertiary
according to the nature of carbon to which halogen is
attached.
(b) Allylic halides
These are the compounds in which the halogen atom
is bonded to an sp3 hybridised carbon atom next
to carbon-carbon double bond (C=C)

(c) Benzylic halides

These are the compounds in which the halogen atom
is bonded to an
sp3-hybridised carbon atom next to an aromatic
ring.
Compounds Containing sp2 C—X
Bond
(a) Vinylic halides
▪ the halogen atom is bonded to an sp2-hybridised carbon atom
of a carbon-carbon double bond (C = C).

(b) Aryl halides

the halogen atom is bonded to
the sp2-hybridised carbon atom of an aromatic ring.
 Nomenclature
▪ Alkyl halides
▪ Common names of are derived by naming the alkyl
group followed by the halide.
▪ In the IUPAC system of nomenclature are named as
halosubstituted hydrocarbons
The dihalo-compounds having same type of
halogen atoms are further classified as
geminal halides (halogen atoms are present on
the same carbon atom) and vicinal halides
(halogen atoms are present on the adjacent
carbon atoms).
In common name system, gem-dihalides are
named as alkylidene halides and vic-dihalides
are named as alkylene dihalides.
In IUPAC system, they are named as
dihaloalkanes.
 Aryl halides
▪ Haloarenes are the common as well as IUPAC names .
▪ For dihalogen derivatives, the prefixes o-, m-, p- are
used in common system. In IUPAC system, the
numerals 1,2; 1,3 and 1,4 are used.
Nature of C-X Bond
▪ Since halogen atoms are more electronegative than
carbon, the carbon halogen bond of alkyl halide is
polarised; the carbon atom bears a partial positive
charge whereas the halogen atom bears a partial
negative charge.
▪ Since the size of halogen atom increases as we go down
the group in the periodic table. Consequently the carbon-
halogen bond length also increases from C—F to C—I.
 Methods of Preparation
▪ From Alcohols
From Hydrocarbons

(a) By free radical halogenation

(b) By electrophilic substitution

(c) Sandmeyer’s reaction
When a primary aromatic amine, dissolved or suspended
in cold aqueous mineral acid, is treated with sodium
nitrite, a diazonium salt is formed.
Mixing diazonium salt with cuprous chloride or cuprous
bromide results in the replacement of the diazonium
group by –Cl or –Br.
(d) From alkenes
(i) Addition of hydrogen halides:

(ii) Addition of halogens:

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

▪ The synthesis of alkyl fluorides is best accomplished by

heating an alkyl chloride/bromide in the presence of a
metallic fluoride such as AgF, Hg2F2, CoF2 or SbF3. The
reaction is termed as Swarts reaction
 Physical Properties
▪ Alkyl halides are colourless when pure. However, bromides and iodides
develop colour when exposed to light.
Melting and boiling points
▪ Methyl chloride, methyl bromide, ethyl chloride and some
chlorofluoromethanes are gases at room temperature. Higher members
are liquids or solids.
▪ The boiling points of chlorides, bromides and iodides are considerably
higher than those of the hydrocarbons.
▪ The attractions get stronger as the molecules get bigger in size and have
more electrons.
▪ Order of boiling points: RI> RBr> RCl> RF.
▪ The boiling points of isomeric haloalkanes decrease with increase in
branching .
▪ Boiling points of isomeric dihalobenzenes are very nearly the same.
▪ The para-isomers are high melting as compared to their ortho and meta-
isomers.
Density
▪ Bromo, iodo and polychloro derivatives of hydrocarbons are heavier
than water. The density increases with increase in number of carbon
atoms, halogen atoms and atomic mass of the halogen atoms

Solubility
▪ The haloalkanes are only very slightly soluble in water. In order for a
haloalkane to dissolve in water, energy is required to overcome the
attractions between the haloalkane molecules and break the
hydrogen bonds between water molecules. Less energy is released
when new attractions are set up between the haloalkane and the
water molecules as these are not as strong as the original hydrogen
bonds in water. As a result, the solubility of haloalkanes in water is
low. However, haloalkanes tend to dissolve in organic solvents
because the new intermolecular attractions between haloalkanes
and solvent molecules have much the same strength as the ones
being broken in the separate haloalkane and solvent molecules.
Chemical Reactions
Reactions of Haloalkanes
(i) Nucleophilic substitution reactions
▪ A nucleophile reacts with haloalkane having a partial positive
charge on the carbon atom bonded to halogen. A substitution
reaction takes place and halogen atom, called leaving group
departs as halide ion.

▪ Groups like cyanides and nitrites possess two nucleophilic centres

and are called ambident nucleophiles. Cyanide group is a hybrid of
two contributing structures and therefore can act as a nucleophile
in two different ways , linking through carbon atom resulting in
alkyl cyanides and through nitrogen atom leading to isocyanides.
▪ Similarly nitrite ion also represents an ambident nucleophile . The
linkage through oxygen results in alkyl nitrites while through
nitrogen atom, it leads to nitroalkanes.
Mechanism:
▪ (a) Substitution nucleophilic bimolecular (SN2)
▪ Follows a second order kinetics, 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.
▪ Inversion of configuration happens during the reaction
▪ order of reactivity followed is:
Primary halide > Secondary halide > Tertiary halide.
(b) Substitution nucleophilic
unimolecular (SN1)
▪ SN1 reactions are generally carried out in polar protic solvents.
▪ Follows the first order kinetics, the rate of reaction depends upon
the concentration of only one reactant.
▪ Step I:the polarised C—Br bond undergoes slow cleavage to produce
a carbocation and a bromide ion.
▪ step II: The carbocation thus formed is then attacked by nucleophile .
▪ 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.
▪ Order of reactivity: R–I> R–Br>R–Cl>>R–F.
(c) Stereochemical aspects of
nucleophilic substitution reactions
▪ A SN2 reaction proceeds with complete stereochemical inversion
while a SN1 reaction proceeds with racemisation .

(i) Plane polarised light and optical activity: optically active

compounds rotate the plane polarised light (produced by passing
ordinary light through Nicol prism) when it is passed through their
solutions.
▪ If the compound rotates the plane polarised light to the clockwise
direction, it is called dextrorotatory or the d-form and is indicated
by placing a positive (+) sign before the degree of rotation.
▪ If the light is rotated towards anticlockwise direction) the
compound is said to be laevorotatory or the l-form and a negative
(–) sign is placed before the degree of rotation.
▪ Such (+) and (–) isomers of a compound are called optical isomers
and the phenomenon is termed as optical isomerism.
(ii) Molecular asymmetry, chirality and
enantiomers:
▪ crystals of certain compounds exist in the form of mirror images.
Aqueous solutions of both types of crystals showed optical rotation,
equal in magnitude (for solution of equal concentration) but
opposite in direction.
▪ Arrangement of four groups around a central carbon is tetrahedral
and if all the substituents attached to that carbon are different, such
a carbon is called asymmetric carbon or stereocentre.
▪ The asymmetry of the molecule is responsible for the optical
activity.
▪ The stereoisomers related to each other as nonsuperimposable
mirror images are called enantiomers
(iii) 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.
▪ If during a reaction, no bond to the stereocentre is
broken, the product will have the same general
configuration of groups around the stereocentre as that
of reactant. Such a reaction is said to proceed with
retention of the configuration.
(iv) Inversion, retention and
racemisation:
for a reaction at an asymmetric carbon atom.
▪ If (A) is the only compound obtained, the process is called retention
of configuration.
▪ If (B) is the only compound obtained, the process is called inversion
of configuration.
▪ If a 50:50 mixture of the above two is obtained then the process is
▪ called racemisation and the product is optically inactive.
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.
▪ it is often called β-elimination.
▪ If there is possibility of formation of more than one alkene due to
▪ the availability of more than one β-hydrogen atoms, usually one
alkene is formed as the major product.
▪ The formation of products is governed by 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”
Reaction with metals
▪ An important class of organo-metallic compounds discovered by
Victor Grignard in 1900 is alkyl magnesium halide, RMgX, referred
as Grignard Reagents. These reagents are obtained by the reaction
of haloalkanes with magnesium metal in dry ether.
▪ One of the methods for converting halides to hydrocarbons.

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.
Reactions of Haloarenes
Nucleophilic substitution
▪ Aryl halides are extremely less reactive towards nucleophilic substitution
reactions due to the following reasons:
(i) Resonance effect : In haloarenes, the electron pairs on halogen atom are in
conjugation with π-electrons of the ring. C—Cl bond acquires a partial
double bond character due to resonance. As a result, the bond cleavage in
haloarene is difficult and therefore, they are less reactive towards
nucleophilic substitution reaction.

(ii) Difference in hybridisation of carbon atom in C—X bond: in case of

haloarene, the carbon atom attached to halogen is sp2-hybridised.
▪ 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
therefore, haloarenes are less reactive than haloalkanes towards
nucleophilic substitution reaction.

(iii) 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.
(iv) Because of the possible repulsion, it is less likely for the electron rich
nucleophile to approach electron rich arenes.
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.
▪ The presence of an electron withdrawing group (-NO2) at ortho- and
para-positions increases the reactivity of haloarenes.
•Nitration
Electrophilic substitution reactions
▪ Halogen atom besides being slightly deactivating is o, p directing;
therefore, further substitution occurs at ortho- and parapositions.

▪ Halogenation

▪ Nitration
Sulphonation

Friedel-Crafts reaction
Reaction with metals

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.

Fittig reaction
Aryl halides also give analogous compounds when treated with
sodium in dry ether, in which two aryl groups are joined together. It
is called Fittig reaction.
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.
▪ Exposure to lower levels of methylene chloride in air can lead
to slightly impaired hearing and vision.
▪ Higher levels of methylene chloride in air cause dizziness,
nausea, tingling and numbness in the fingers and toes. In
humans, direct skin contact with methylene chloride causes
intense burning and mild redness of the skin. Direct contact
with the eyes can burn the cornea.
Trichloromethane (Chloroform)
▪ Chemically, 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.
▪ Inhaling chloroform vapours depresses the central nervous system.
▪ Breathing about 900 parts of chloroform per million parts of air for a
short time can cause dizziness, fatigue, and headache. Chronic
chloroform exposure may cause damage to the liver (where
chloroform is metabolised to phosgene) and to the kidneys, and
some people develop sores when the skin is immersed in
chloroform. 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.
Triiodomethane (Iodoform)
▪ It was used earlier as an antiseptic but the antiseptic properties are
due to the liberation of free iodine and not due to iodoform itself.
Due to its objectionable smell, it has been replaced by other
formulations containing iodine.
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.
▪ Most freon, even that used in refrigeration, eventually makes its way
into the atmosphere where it diffuses unchanged into the
stratosphere. In stratosphere, freon is able to initiate radical chain
reactions that can upset the natural ozone balance.
4 Tetrachloromethane (Carbon
tetrachloride)
▪ It is for use in the manufacture of refrigerants and propellants
for aerosol cans.
▪ It is used as feedstock in the synthesis of chlorofluorocarbons
and other chemicals, pharmaceutical manufacturing, and
general solvent use.
▪ Exposure to carbon tetrachloride can cause liver cancer in
humans. The most common effects are dizziness, light
headedness, nausea and vomiting, which can cause
permanent damage to nerve cells. In severe cases, these
effects can lead rapidly to stupor, coma, unconsciousness or
death. Exposure to CCl4 can make the heart beat irregularly or
stop. The chemical may irritate the eyes on contact.
▪ It depletes the ozone layer. Depletion of the ozone layer
increase human exposure to ultraviolet rays, leading to
increased skin cancer, eye diseases and disorders, and possible
disruption of the immune system.
Dichlorodiphenyltrichloroethane (DDT)

▪ DDT was the first chlorinated organic insecticides.

▪ The use of DDT increased enormously on a worldwide basis after
World War II, primarily because of its effectiveness against the
mosquito that spreads malaria and lice that carry typhus.
▪ Problems related to extensive use of DDT began to appear in the
late 1940s. Many species of insects developed resistance to DDT,
and it was also discovered to have a high toxicity towards fish.
The chemical stability of DDT and its fat solubility compounded
the problem. 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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