HALOALKANES AND HALOARENES

In aliphatic or aromatic compounds, the replacement of hydrogen atom(s) by halogen atom(s)

results in the formation of alkyl halide (haloalkane) and aryl halide (haloarene), respectively.

In case of haloalkanes, halogen atom is attached to the sp3 hybridised carbon atom of an
alkyl group whereas in haloarenes, halogen atom is attached to sp2 hybridised carbon atom of
an aryl group.

Classification of Haloalkanes:

The halogen derivatives of hydrocarbons may be classified as fluoro, chloro, bromo or iodo
compounds according to the type of halogen present.

Depending upon the number of halogens present, the halogen derivatives can be classified as
mono, di, tri or polyhalo compounds.

On the basis of the nature of the carbon to which halogen atom is attached, halogen
derivatives are classified as 1o, 2o, 3o, allylic, benzylic, vinylic and aryl derivatives.

For example:

1o, 2o and 3o halides: halogen atom is bonded to primary, secondary or tertiary carbon atom
of an an alkyl group.

Allylic halides: Halogen atom is bonded to an sp3-hybridised carbon atom next to carbon-
carbon double bond (C=C) i.e. to an allylic carbon.

Benzylic halides: Halogen atom is attached to an sp3 - hybridised carbon atom next to an
aromatic ring.

Vinylic halides: Halogen atom is bonded to an sp2-hybridised carbon atom of a carbon-

carbon double bond (C = C).
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Aryl halides: Halogen atom is bonded to the sp2-hybridised carbon atom of an aromatic ring.

Note: Here X represents a halogen atom, i.e., X=  F, Cl, Br, I.

Nature of C-X bond in haloalkanes

X is more electronegative than carbon. So, the C-X bond is polarized with C having a partial
positive charge and X having a partial negative charge.

Preparation of Haloalkanes

Haloalkanes can be prepared by a number of methods:

1. By free radical halogenation of alkanes:

Chlorination or bromination of alkane usually gives a complete mixture of isomeric mono

and poly halo alkanes.

2. By electrophilic addition of HX to alkene:

An alkene is converted to corresponding alkyl halide by reaction with hydrogen chloride,

hydrogen bromide or hydrogen iodide.

3. From alcohol:

The hydroxyl group of an alcohol is replaced by halogen on reaction with concentrated

halogen acids, phosphorus halides or thionyl chloride to give the corresponding alkyl halide.
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4. By halogen exchange:

(a) Finkelstein reaction:

Alkyl iodides can be prepared by the reaction of alkyl chlorides/ bromides with NaI in dry
acetone.

(b) Swarts reaction:

Alkyl fluorides can be prepared by heating an alkyl chloride/bromide in the presence of a

metallic fluoride such as AgF, Hg2F2, CoF2 or SbF3.

Preparation of haloarenes

Haloarenes can be synthesised by any of the following reactions:

1. By electrophilic substitution reaction:

This involves the direct halogenation of benzene ring in the presence of Lewis acid catalysts
like iron or iron (III) chloride.

2. By Sandmeyer’s reaction:
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Aniline is treated with sodium nitrite to give a diazonium salt which is then treated with
cuprous chloride or cuprous bromide to produce the corresponding aryl halide:

3. By Balz – Schiemann reaction:

This involves the conversion of aryl amines to aryl fluorides via diazotisation and subsequent
thermal decomposition of the derived aromatic fluoborate to produce the corresponding aryl
fluoride.

4. From diazonium group:

Treatment of diazonium salt with potassium iodide gives aryl iodide.

Physical properties of Haloderivatives

Physical properties of haloderivatives are different than those of the simple hydrocarbons.
These are described below:

•    Alkyl halides are colourless when pure but bromides and particularly iodides develop
colour when exposed to light.

•    The alkyl halides have higher molecular mass as compared to alkanes.
 HALOALKANES AND HALOARENES

•    Halogen compounds have higher boiling points than the corresponding hydrocarbon. This
is because the greater polarity as well as higher molecular mass as compared to the parent
hydrocarbon causes the intermolecular forces of attraction (dipole-dipole and van der Waals)
to be stronger in the halogen derivatives.

•    For monohalogen compounds, the boiling point increases with increasing molecular mass
of the halogen group with a fixed hydrocarbon group,

•    All halogen derivatives of hydrocarbon are insoluble in water as they are incapable of
forming hydrogen bonds with water but alkyl halides are soluble in non-polar solvents, R‒F <
R‒Cl < R‒Br < R‒I

•    The density increases with increasing number and the atomic mass of the halogen.

•    Halogen compounds are less inflammable than the hydrocarbons. The inflammability
decreases with increasing halogen content.

Reactions of Haloalkanes

The reactions of haloalkanes may be divided into the three main categories:

(i) Nucleophilic substitution

(ii) Elimination reactions

(iii) Reaction with metals

Nucleophilic substitution: A nucleophile attacks the haloalkane which is having a partial

positive charge on the carbon atom bonded to halogen. Halide ion separates following a
substitution reaction.

Reactivity of Haloalkanes towards nucleophilic substitution:

For the same alkyl group, as we move from F to I, strength of C−X bond decreases, therefore,
the reactivity order is:     R− I > R−Br > R−Cl > R−F

Mechanism of nucleophilic substitution reaction:

The nucleophilic substitution reaction can proceed via SN1 mechanism or SN2mechanism.

•     Unimolecular nucleophilic substitution, SN1: This type of nucleophilic substitution

takes place in two steps, first step being the rate determining step involves the formation of
carbonium ion.

The reactivity order of haloalkanes towards SN1reaction is:

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        1° R−X < 2° R−X < 3° R−X

•     Bimolecular nucleophilic substitution, SN2: This type of nucleophilic substitution takes

place in one step. The incoming nucleophile interacts with alkyl halide causing the C−X bond
bond to break while forming a new C−OH bond.

The reactivity of alkyl halide towards SN2 reaction is:

       3° R−X < 2° R−X < 1° R−X

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 resulting in the formation of an alkene. The reaction follows the Saytzeff rule
which states that “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:

Reaction with Magnesium: Alkyl halides react with magnesium in the presence of dry ether
to form corresponding alkyl magnesium halide which is also known as Grignard’s reagent.

Recation with sodium: Alkyl halides react with sodium to form an alkane with double
number of carbon atom than that present in alkyl halide. This reaction is also known as
Wurtz reaction.

2R‒X + 2 Na → R ‒ R + 2NaX

Stereoisomerism

Stereoisomerism is due to the different orientation of atoms or groups in space. There are two
types of stereoisomerism:

(i) Geometrical isomerism: It arises due to the presence of like groups on the same side of
the plane (cis) or on the opposite side of the plane (trans).

(ii) Optical isomerism: It arises due to the presence of non-superimposable mirror images.
Conditions for optical isomerism to take place are:
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•     Presence of chiral carbon or asymmetric carbon, i.e., The C attached to four different
groups. Chiral carbon is denoted as C*.

•     Presence of non-superimposable mirror images

Enantiomers

The two non-superimposable mirror images are called enantiomers. Enantiomers have similar
physical & chemical properties but differ in their

•    effect on the plane polarised light

•    reactivity towards chiral reagent.

Enantiomers are of two types:

•    Dextrorotatory (+): These rotate the plane polarised light in a clockwise direction

•    Laevorotatory (–): These rotate the plane polarised light in an anticlockwise direction

Racemic mixture

A mixture containing two enantiomers in equal proportions is called racemic mixture. A

recemic mixture is optically inactive as the effect of one isomer gets cancelled by another
isomer.

Racemisation

The process of conversion of enantiomers into a racemic mixture is known as racemisation.

Reactions of Haloarenes

Nucleophilic substitution:
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Aryl halides are almost unreactive towards nucleophilic substitution reaction. This is because
of double character of C – X bond due to resonance. Therefore, it is difficult to remove X
from C – X bond.

Effect of NO2 group on the reactivity of aryl halide towards nucleophilic substitution
reactions:

Presence of an electron withdrawing group like NO2 group increases the reactivity of aryl
halides towards nucleophilic substitution reaction.

NO2 group increases the reactivity more when present at o- and p- position due to the
increased delocalization of negative charge involving NO2 group.
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Polyhalogen Compounds

Carbon compounds containing more than one halogen atom are known as polyhalogen
compounds. For example: CFCl3, CH2Cl2 etc.

Some important polyhalogen compounds are described below:

1. Dichloromethane, CH2Cl2

Preparation:

Dichloromethane is prepared by the direct chlorination of CH4.

Properties:

•    It is a colourless, sweet-smelling, volatile liquid

•    It has a low boiling point and low inflammability.

•    It is insoluble in water

Uses:

•    It is widely used as a paint remover

•    It is used as a solvent and cleaning agent in chemical manufacture, textiles, electronics,
metals and plastic industries
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•    It is also used as a process solvent in the manufacture of drugs

2. Trichloromethane, CHCl3 (Chloroform)

Preparation:

CHCl3 is manufactured by chlorination of methane followed by separation by fractional

distillation.

Properties:

•    Chloroform is a sweet - smelling liquid

•    Chloroform is slowly oxidised by air in the presence of light to form  poisonous phosgene
gas

To avoid this oxidation chiorofrom is always stored in dark coloured bottles filled to the brim
to exclude any air. Further bottles are also filled with small amount of ethyl alcohol so as to
destroy traces of phosgene if formed, to harmless diethyl carbonate.

Some important chemical reactions of chloroform are:

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Uses:

•    Chloroform is employed as a solvent for fats, alkaloids, iodine and other substances.

•    It mainly used in the production of the freon refrigerant R-22.

3. Triiodomethane, CHI3 (Iodoform)

Preparation:

Any compound containing CH3CO− or CH3CH(OH)− group, when heated with iodine and
aquous NaOH gives yellow precipitate of iodoform.The reaction is known as iodoforin
reaction.

Iodoform can also be prepared conveniently by using bleaching powder, CaOCl2.

Iodoform was used earlier as an antiseptic due to the liberation of free iodine but due to its
objectionable smell, it has been replaced by other formulations containing iodine.
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4. Tetrachloromethane, CCl4 (Carbon tetrachloride)

Preparation:

CCl4 is prepared by reacting carbon disulphide (CS2) with Cl2 in the presence of AlCl3.

Properties:

•    Iodoform is a colourless, non-inflammable, poisonous liquid.

•    When heated with steam at 773 K, it undergoes oxidation to form phosgene, COCl2 gas.

Uses:

•     Carbon tetrachloride is used as a solvent for oils, fats, resins

•     It is used as a refrigerant and a dry cleaning agent

•     It is used as a fire extinguisher under the name pyrene

Note: When carbon tetrachloride is released into the air, it causes the atmospheric
temperature to rise and depletion of ozone layer. Depletion of the ozone layer is believed to
increase human exposure to ultraviolet rays, leading to increased skin cancer, eye diseases
and disorders, and possible disruption of the immune system.

5. Freons

Freons are the chlorofluoro compounds of methane and ethane.

Preparation:

Dichloro difluoro methane or Freon 12 (CCl2F2) is one of the most common freons in and is
manufactured from tetrachloromethane by Swarts reaction

Properties:

•    Freons are extremely stable, unreactive, non-toxic, non-corrosive and easily liquefiable
gases
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•    They lead to the depletion of ozone layer surrounding our planet

Uses:

•    Freons are used in aerosol propellants, refrigeration and air conditioning purposes

6. Benzene hexachloride (BHC)

It is also famous by its trade name, gammaxene or lindane

Preparation:

It is prepared by reacting benzene with chlorine in the presence of sunlight.

Uses:

BHC is mainly sused as a pesticide in agriculture.

7. Dichloro diphenyl trichloroethane (DDT)

Preparation:

It is manufactured by the condensation of chloral with chlorobenzene in the presence of

H2SO4.

Properties:

•    DDT is a white powder insoluble in water.

•    It is a highly stable fat-soluble compound.

Uses:
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•    It is mainly used as an insecticide.