CHAPTER 6 - HALOALKANES AND HALOARENES

IUPAC NAMING

TYPES OF HALIDES
• Allylic Halides

Halogen is attached to an allylic carbon. Allylic carbon is one which is

directly bonded to C=C. Allylic carbon is sp3 hybridised.

Example: CH2=CH-CH2Cl

• Benzylic Halides
 Halogen is attached to a benzylic carbon. It is the carbon directly bonded to
a benzene ring. Bezylic carbon is sp3 hybridised.

• Vinylic Halides

Halogen is attached to a vinylic carbon. Double bonded carbons are called

vinylic carbons (sp2).

4) Alkyl halides
The halogen atom is bonded to an alkyl group (R). Eg: CH3Cl
5) Aryl halides
The halogen atom is bonded to an aryl group (Ar). Eg: C 6H5Cl
Nature of Carbon-Halogen Bond
• Since halogen atoms are more electronegative than carbon, the carbon
halogen bond of alkyl halide is polarized.

• Carbon-halogen bond length increases from C—F to C—I due to increase in

size from F2 to I2.

Methods of Preparation
[Link] Alcohols
 • Preparation using SOCl2 is preferred as the reaction gives pure alkyl halides
because SO2 and HCl are gases.

• The order of reactivity of alcohols with a given haloacid is 3° > 2° > 1°.
Qn. Why is sulphuric acid not used during the reaction of alcohols with KI?
Sulphuric acid is a strong oxidising agent. It converts KI to HI and then
oxidises
HI to I2.
2. From Hydrocarbons
• By free radical halogenation

• By electrophilic substitution

• Reactions with iodine are reversible in nature and require the presence of an
oxidising agent (HNO3, HIO4) to oxidise the HI formed during iodination.

• Fluoro compounds are not prepared by this method due to high reactivity of
fluorine.

(c) Sandmeyer’s reaction

 • From alkenes

(i) Addition of hydrogen halides:

As per Markovnikov’s rule.

(ii) Addition of halogens:

Halogen Exchange
• Alkyl iodides are often prepared by Finkelstein reaction.

• Alkyl fluorides are often prepared by Swarts reaction

Instead of AgF, Hg2F2, CoF2 or SbF3 can also be used.

Q:- Write the products of the following reactions:

•
Physical Properties
Melting and boiling points
• Methyl chloride, methyl bromide, ethyl chloride and some chlorofluoro
methanes are gases at room temperature.
• Higher members are liquids or solids.
• Due to greater polarity as well as higher molecular mass as compared to the
parent hydrocarbon, the intermolecular forces of attraction (dipole-dipole
and van der Waals) are stronger. That is why the boiling points of chlorides,
bromides and iodides are considerably higher than those of the hydrocarbons
of comparable molecular mass.
• For the same alkyl group, the boiling points of alkyl halides decrease in the
order:
RI>RBr>RCl> RF.
This is because with the increase in size and mass of halogen atom, the
magnitude of van der Waal forces increases.
• The boiling points of isomeric haloalkanes decrease with increase in
branching due to decrease in surface area and weakening of London forces
• The para-isomers are high melting as compared to their ortho and meta-
isomers. It is due to symmetry of para-isomers that fits in crystal lattice
better as compared to ortho- and meta-isomers.
Density
• 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.
• 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.
• Haloalkanes tend to dissolve in organic solvents.
Chemical Reactions
The reactions of haloalkanes may be divided into the following categories:
(i) Nucleophilic substitution (ii) Elimination reactions (iii) Reaction with
metals.

(i) Nucleophilic substitution reactions

• Groups like cyanides and nitrites possess two nucleophilic centres and are
called ambident nucleophiles.
• They can act as a nucleophile in two different ways [- :C≡N:↔ :C=N-], i.e.,
linking through carbon atom resulting in alkyl cyanides and through nitrogen
atom leading to isocyanides.
Q;-Haloalkanes react with KCN to form alkyl cyanides as main product while
AgCN
forms isocyanides as the chief product. Explain.
KCN is predominantly ionic and provides CN- ions in solution.
Although both carbon and nitrogen atoms are in a position to donate electron
pairs, the attack takes place mainly through carbon atom and not through
nitrogen atom since C—C bond is more stable than C—N bond. However,
AgCN is mainly covalent in nature and nitrogen is free
to donate electron pair forming isocyanide as the main product.
Mechanism:
• Substitution nucleophilic bimolecular (S N2)

Five – membered Transition state

• Since this reaction requires (SN2) the approach of the nucleophile, Tertiary
halides are the least reactive because bulky groups hinder the approaching
nucleophiles.
• Thus the order of reactivity for SN2is:
 Primary halide > Secondary halide > Tertiary halide.

• Substitution nucleophilic unimolecular (SN1)

• Tertiary alkyl halides undergo SN1 reaction very fast because of the high
stability of 30carbocations.
• Step I is the slowest and reversible.
• Thus the order of reactivity for SN1 is:

Tertiary halide > Secondary halide > Primary halide.

• For a given alkyl group, the reactivity of the halide, follows the same order
in both the mechanisms R–I> R–Br>R–Cl>>R–F.

• Allylic and Benzylic halides show high reactivity towards the SN1reaction.
The carbocation thus formed gets stabilised through resonance.
Optical isomers

• They are mirror images and rotate plane polarized light in opposite direction.

• If the compound rotates the plane polarised light to the right, i.e., clockwise
direction, it is called dextrorotatory (+) and if to the left, (anticlockwise
direction), the compound is said to be laevorotatory (–).
• Enantiomers are optically active isomers which are related to each other
as non-superimposable mirror images.
• If all the substituents attached to a carbon is different, such a carbon is called
asymmetric carbon or chiral carbon.
Eg:-Butan-2-ol has four different groups attached to the tetrahedral carbon and
is chiral.
• The objects which are nonsuperimposable on their mirror image (like a pair
of hands) are said to be chiral and this property is known as chirality.
• While the objects, which are, superimposable on their mirror images are
called achiral.
• A mixture containing two enantiomers in equal proportions (1:1 ratio) is
known as racemic mixture.
• It does not rotate plane polarized light as the rotation due to one isomer will
be cancelled by the other isomer.
• A racemic mixture is represented by prefixing dl or (±)
• The process of conversion of enantiomer into a racemic mixture is known as
racemisation.
Inversion, retention and racemisation

• 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 (A + B) is obtained, then the process is called
racemisation.

• SN2 reactions of optically active halides are accompanied by inversion of

configuration.

• SN1 reactions are accompanied by racemisation.

2. Elimination reactions
• When a haloalkane (R-X) with β-hydrogen atom is heated with alcoholic
solution of KOH, hydrogen atom is eliminated from β-carbon and a halogen
atom from the α-carbon atom.
• As a result, an alkene is formed. Since β-hydrogen atom is involved in
elimination, it is often called β-elimination.

Zaitsev Rule
• “In dehydrohalogenation, the preferred product is that alkene which has the
greater number of alkyl groups attached to the double bonded carbon
atoms.”
3. Reaction with metals

• Grignard Reagents are obtained by the reaction of haloalkanes with

magnesium metal in dry ether.

• In Grignard reagent, the carbon-magnesium bond is covalent but highly

polar.
• Grignard reagents are highly reactive and react with any source of hydrogen
to give hydrocarbons.

• It is therefore necessary to avoid even traces of moisture from a Grignard

reagent.
Wurtz reaction
• Alkyl halides react with sodium in dry ether to give hydrocarbons containing
double the number of carbon atoms present in the halide.

Reactions of Haloarenes
1. Nucleophilic substitution

• Aryl halides are extremely less reactive towards nucleophilic substitution

due to:
(i) Resonance effect
• C—Cl bond acquires a partial double bond character due to resonance.

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

• The sp2hybridised carbon with a greater s-character is more electronegative

and can hold the electron pair of C—X bond more tightly. It is difficult to
break a shorter bond than a longer bond.

(iii) Instability of phenyl cation

• In haloarenes, the phenyl cation (C6H5+) formed as a result of self-ionisation

will not be stabilized by resonance.
(iv) Nucleophile-arene repulsion

• Because of the possible repulsion, it is less likely for the electron rich
nucleophile to approach electron rich arenes

Replacement by hydroxyl group

 • The presence of an electron withdrawing group (-NO2) at ortho- and para-
positions increases the reactivity of haloarenes.

• The effect is pronounced when (-NO2) group is introduced at ortho and

para- positions.

• No effect on reactivity of haloarenes is observed by the presence of electron

withdrawing group at meta-position.

2. Electrophilic substitution reactions

• Halogen atom besides being slightly deactivating is o, p directing; therefore,

further substitution occurs at ortho- and para positions.

• Due to resonance, the electron density increases more at ortho- and para-
positions than at meta-positions.
(i) Halogenation
(ii) Nitration

(iii) Sulphonation

(iv) Friedel-Crafts alkylation

(iv) Friedel-Crafts acylation

3. Reaction with metals

Wurtz-Fittig reaction
• A mixture of an alkyl halide and aryl halide gives an alkyl-arene when
treated with sodium in dry ether and is called Wurtz-Fittig reaction.

Fittig reaction
• Aryl halides when treated with sodium in dry ether, in which two aryl
groups are joined together. It is called Fittig reaction.

Dichloromethane (Methylene chloride), CH2Cl2

• Dichloromethane is used as a solvent as a paint remover, as a propellant in

aerosols, and in the manufacture of drugs.
• Methylene chloride harms the human central nervous system. 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), CHCl3
• The major use of chloroform is in the production of refrigerant. It was once
used as a general anaesthetic in surgery.
• Inhaling chloroform vapours depresses the central nervous system.
• 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), CHI3

• It was used earlier as an antiseptic and 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.
Tetrachloromethane (Carbon tetrachloride), CCl4
• It is used in the manufacture of refrigerants and propellants.
• Exposure to carbon tetrachloride causes liver cancer in humans. The most
common effects are dizziness, light headedness and vomiting.
• When carbon tetrachloride is released into the air, it rises to the atmosphere
and depletes the ozone layer.
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. These
are usually produced for aerosol propellants, refrigeration and air
conditioning purposes.
• In stratosphere, freon is able to initiate radical chain reactions that can upset
the natural ozone balance.
p,p’-Dichlorodiphenyltrichloroethane(DDT)
• DDT was used as an insecticide.
• It has high toxicity towards fish. DDT is not metabolized very rapidly by
animals; instead, it is deposited and stored in the fatty tissues.
Important equations

• CH3Br + KCN → CH3CN + KBr (Ethanenitrile/Methyl cyanide)

• CH3Br + AgCN → CH3NC + AgBr (Methyl isocyanide)

• CH3Br + KNO2 → CH3ONO + KBr (Methyl nitrite)

• CH3Br + AgNO2 → CH3NO2 + AgBr (Nitromethane)