UNIT-10: HALOALKANES AND HALOARENES

[Number of Teaching Hours–07 & Total weightage–06 Marks]

“The Halogen derivatives of alkanes and aromatic hydrocarbons are called Haloalkanes and Haloarenes
respectively.”
These are obtained by replacing the hydrogen atoms of Hydrocarbon by halogen atoms (X-F, Cl, Br and I).
Classifications:
Halogen containing Hydrocarbons are classified as mono, di, or polyhalogen (tri-, tetra-,...etc.) compounds
depending on whether they contain one, two or more halogen atoms in their structures.
a.Monohalogen compounds: They contain only one Halogen atom per molecule.
Example: CH3 Cl
Chloromethane
b.Dihalogen compounds: They contain two Halogen atoms per molecule.
X
General Examples: CH2 X X
CH2 X
Dihaloalkane Dihaloarene
The dihalo-compounds having same type of halogen atoms are further classified as,
i.Geminal dihalides or Gem-dihalides: Halogen atoms are present on the same carbon atom.
ii.Vicinal dihalides or Vic-dihalides: Halogen atoms are present on the adjacent carbon atoms.
CH 2 Cl
Examples:
CH3 CHCl 2 CH 2 Cl
Common name: Ethylidene dichloride Ethylene dichloride
[gem-dihalide] [vic-dihalide]
IUPAC name: 1,1-Dichloroethane 1,2-Dichloroethane
c.Polyhalogen compounds: They contain more than two Halogen atoms per molecule.
Examples: CHCl3 CCl4
Trichloromethane [Chloroform] Tetrachloromethane [Carbon tetrachloride]
Classification of Monohalogen compounds: Monohalogen compounds may further be classified based on
hybridization of the Carbon atom to which the halogen is attached, they are discussed below.
1.Compounds Containing sp3 C─X Bond(X is F, Cl, Br & I): In these compounds halogen atom is
attached to the sp3 hybridised carbon atom. They are further classified into three,
a.Alkyl halides or haloalkanes (R─X):
The monohalogen derivatives of Alkanes are called Alkyl halides or haloalkanes. The general fomula of
alkyl halides is CnH2n+1X. Alkyl halides or Haloalkanes are further classified as Primary, Secondary and
Tertiary according to the nature of carbon to which halogen is bonded.
i)Primary Alkyl Halides or 10-Alkyl Halides: The alkyl halides in which halogen atom is bonded to primary
carbon atom(carbon atom bonded to only one alkyl group) are called Primary alkyl halides.
H CH3 Cl CH3 CH 2 Br
General formula: R C X Examples: Methyl Chloride Ethyl Bromide
Chloro methane Bromo ethane
H
ii)Secondary Alkyl Halides or 20-Alkyl Halides: The alkyl halides in which halogen atom is bonded to
secondary carbon atom(carbon atom bonded to two alkyl groups) are called Secondary alkyl halides.
Cl
H
CH3 CH CH 2 CH3
General formula: R C X Example:
sec-Butyl Chloride
R 2-Chloro Butane
0
iii)Tertiary Alkyl Halides or 3 -Alkyl Halides: The alkyl halides in which halogen atom is bonded to
tertiary carbon atom(carbon atom bonded to three alkyl groups) are called Tertiary alkyl halides.
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 R CH3
General formula: R C X Example: CH3 C Br
R CH3
tert-Butyl bromide
2-Bromo-2-methyl propane
b.Allylic halides:
The monohalogen derivatives of alkenes or cycloalkenes, in which the halogen atom is bonded to sp3-
hybridised carbon atom next to carbon-carbon double bond (C=C).
X
General Examples:
CH2 CH CH2 X
3-haloprop-1-ene 3-halocyclohexene
c.Benzylic halides: The monohalogen derivatives of Aromatic hydrocarbons, in which the halogen atom is
bonded to sp3- hybridized carbon atom next to an aromatic ring.
R R
CH2 X CH X C X
General Examples:
R
P rimary Secondary Tertiary [Where R-CH3,C 2H5 etc....]

2.Compounds Containing sp2 C─X Bond:

a.Vinylic halides: The monohalogen derivatives of alkenes or cycloalkenes, in which the halogen atom is
bonded to sp2- hybridized carbon atom of a carbon-carbon double bond (C=C).
2
sp -Hybridised Carbon atom X Br

General Examples: CH CH X Examples: CH2 CH Cl

2
Haloethene Halocyclohexene Chloroethene Bromocyclohexene.

b.Aryl halides or Haloarenes: The monohalogen derivatives of aromatic hydrocarbons, in which the
halogen atom is bonded to the sp2-hybridised carbon atom of an aromatic ring.
X X Cl Br

General Examples: Examples:

Halobenzene Chlorobenzene
CH3 CH3
p-Halotoluene p-Bromotoluene

Nomenclature:
In Common or Trivial system, names are derived by naming the alkyl group followed by the halide.
Prefixes such as n- , iso- , neo- , sec- , tert- can be used based on structure.
In IUPAC system, Alkyl halides are named as “ Haloalkanes”.Aryl halides are named as “Halobenzenes”.
For dihalobenzene, the locants (numerals) 1,2 ; 1,3 and 1,4 are used.
Structure Common name IUPAC name
CH3 CH2 CH2 F n-Propyl floride 1-Floropropane
Cl
sec-Butyl Chloride 2-Chlorobutane
CH3 CH 2 CH CH3
CH3
CH3 C Br tert-Butyl bromide 2-Bromo-2-Methyl propane
CH3

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 Br
iso-Propyl bromide 2-Bromopropane
CH3 CH CH3
CH3
CH3 C CH 2 I neo-Pentyl Iodide 1-Iodo-2,2-dimethyl propane
CH3
CH2 CH Cl Vinyl Chloride Chloroethene
CH2 CH CH2 Br Allyl bromide 3-Bromo-propene
CH2Cl 2 Methylene Chloride Dichloromethane
CHCl 3 Chloroform Trichloromethane
CHBr3 Bromoform Tribromomethane
CCl 4 Carbon tetrachloride Tetrachloromethane
Br

Bromobenzene Bromobenzene

Cl
CH3 1-Chloro-2-Methylbenzene or
o-Chloro toluene
2-Chlorotoluene

Br
o-dibromobenzene 1,2-dibromobenzene
Br
CH 2 Cl
Benzyl Chloride Chlorophenyl methane


Nature of CX Bond:
 Since halogen atoms are more electronegative than carbon, the C−X bond of alkyl halide is polarised. The
carbon atom bears a partial positive charge where as the halogen atom bears a partial negative charge. Hence
CX bond is polar.
R
 From C−F to C−I, the size of the halogen increases and Carbon-Halogen
 
bond length also increases Hence, Reactivity increases.
C X
Hence in Alkyl Halides, R'

☞ The Bond length and Reactivity follows Order: R''

R−I R−Br R−Cl R−F. Where R, R' and R'' Hydrogens or
any Alkyl groups

Methods of preparation:
I.Preparation of Haloalkanes:
1.From Alcohols using Halogen acids: Alcohols on heating with conc.Haloacids in presence of Anhydrous
ZnCl2, Alkyl halides are formed. The process is called as Grove’s Process.
Anh.ZnCl2
R OH + HX R X + H2O
(Conc.) 
Alcohol Alkyl halide

1.The mixture of conc.HCl and Anh.ZnCl is known as Lucas reagent.

Note:2.Anh.ZnCl2 acts as dehydrating agent[Removes
2
water].

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 Anh.ZnCl2
Example: C2H5 OH + HCl C 2 H5 Cl + H2 O
(Conc.) 
Ethyl alcohol Ethyl chloride
2.From alcohols using Thionyl Chloride:
Alcohols on heating with thionyl chloride in presence of pyridine, Alkyl chlorides are formed. The process is
called as Darzen’s process.
Pyridine
R OH + SOCl 2 R Cl + SO 2 + HCl
Alcohol  Alkyl Chloride
Example: Pyridine
C2H5 OH + SOCl 2 C2H5 Cl + SO 2 + HCl

Ethyl alcohol Ethyl chloride

Note: Pyridine[Basic] is used to neutralize hydrogen choride gas[Acidic] formed during reaction. 
3.From alcohols using PX3(Phosphorus trihalides):
(a)Alcohols on treating with Phosphorous trichloride give Alkyl Chlorides.
3 R OH + PCl3 3 R Cl + H3PO3
Alcohol Alkyl Chloride

Since, Phosphorus tribromide and Phosphorus triiodide are unstable compounds. They are
 Note: usually prepared in situ (produced in the reaction mixture) by the reaction of red
phosphorus with bromine and iodine respectively. 
(b)Alkyl bromides and Alkyl iodides are obtained by treating the Alcohols with bromine or iodine in
presence of red Phosphorous.
Red P / X2
R OH R X Here; X is Br and I.
Alcohol Alkyl halide
Red P / Br2
Examples: C2 H5 OH C2 H5 Br
Ethyl alcohol Ethyl bromide

Red P / I2
C2 H5 OH C 2 H5 I
Ethyl alcohol Ethyl iodide
4.From alcohols using PCl5:
Alcohols react with Phosphorus pentachloride to form Chloroalkanes.
R OH + PCl5 R Cl + HCl + POCl3
Alcohol Alkyl Chloride
Example:
C2H5 OH + PCl5 C2H5 Cl + HCl + POCl3
Ethyl alcohol Ethyl chloride

5.Halogen exchange method:

(a) Finkelstein reaction: When Alkyl chlorides or Alkyl bromides are heated with NaI in presence of dry
acetone, Alkyl iodides are formed. The reaction is known as Finkelstein reaction.
dry Acetone
R X + NaI R I + NaX Where X is Cl or Br

Alkyl iodide
Examples:
dry Acetone dry Acetone
C2H5 Cl + NaI C2H5 I + NaCl & C2H5 Br + NaI C 2 H5 I + NaBr
 
Ethyl chloride Ethyl iodide Ethyl bromide Ethyl iodide

Note: NaCl or NaBr thus formed is precipitated in dry acetone. It facilitates the forward reaction
according to Le Chatelier’s Principle. 
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(b) Swart’s reaction: When Alkyl chlorides or Alkyl bromides are heated with metallic fluorides such as
AgF or Hg2F2 or CoF3, Alkyl florides are formed. The reaction is known as Swart’s reaction.
R X + AgF R F + AgX & 2 R X + Hg2F2 2 R F + Hg2X2
Alkyl floride Alkyl floride Where X is Cl or Br.
Examples:
C2H5 Cl + AgF C2H5 F + AgCl & 2 C2H5 Cl + Hg2F2 2 C2H5 F + Hg2Cl 2
Ethyl chloride Ethyl floride Ethyl chloride Ethyl floride
6.From alkanes by free radical halogenation:
When alkanes are treated with Cl2 or Br2 in presence of UV-light(or heat), a complex mixture of mono and
Polyhaloalkanes is formed.
For Example: n-Butane is treated with chlorine in presence of UV-light(or heat) gives 1-Chlorobutane and
2-Chlorobutane.
Cl
UV-light
2 CH3 CH2 CH2 CH3 + 2 Cl2 CH3 CH2 CH2 CH2 Cl + CH3 CH CH2 CH3 + 2 HCl
or 
n-Butane 1-Chlorobutane 2-Chlorobutane

IllustrationIdentify all the possible monochloro structural isomers expected to be formed on free
radical monochlorination of (CH3)2CHCH2CH3. [NCERT example]
Answer: In the given molecule, there are four different types of hydrogen atoms. Replacement of these
hydrogen atoms will give the following ;
1.(CH3)2CHCH2CH2Cl 2. (CH3)2CHCH(Cl)CH3
3.(CH3)2C(Cl)CH2CH3 4.CH3(CH2Cl)CHCH2CH3

7.From Alkenes:
(i)Addition of Hydrogen halide(HCl, HBr or HI):
When alkenes react with halogen acids corresponding Alkyl halides are formed.
CH2 CH2 + HX CH3 CH2 X Where X-Cl, Br and I.
Ethene Ethyl halide
The order of reactivity of hydrogen halide is: HI > HBr > HCl.
☞In case of Unsymmetrical alkenes addition takes place as per the Markownikoff’s rule. According to
Markownikoff’s rule “Negative part of hydrogen halide(H+X−) is added to the double bonded carbon
containing least number of Hydrogens”.
Example: Propene reacts with HI, gives two products, however only one is major product as per
Markownikoff’s rule.
CH3 CH2 CH2 I
1-Iodo propane [minor; 19%]
CH3 CH CH2 + HI
I
Propene
CH3 CH CH3
2-Iodo propane [major; 81%]

(ii)Addition of Halogens: Alkenes react with Halogens in presence of Carbon tetrachloride to form vicinal
dihalides.
CCl4 CCl4
R CH CH2 + X2 R CH CH 2 & Example: CH2 CH2 + Br 2 Br CH2 CH2 Br
Alkene X X Ethene Ethylene dibromide
Dihaloalkane [1,2-dibromoethane]

 In the laboratory, addition of bromine in presence of CCl4 to an alkene gives reddish brown colour.
This test is important for the detection of Carbon to Carbon double bond[C=C] in a molecule. 
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II.Preparation of Haloarenes:
1.By Electrophilic substitution:
Aryl Chlorides and Aryl Bromides can be prepared by Electrophilic substitution of arenes with chlorine and
bromine in dark at ordinary temperature in presence of Lewis acid catalyst such as Fe or FeCl3 or FeBr3.
X Cl
Fe or FeX3 Fe or FeCl3
+ X2 + HX & Example: + Cl 2 + HCl
dark dark
Benzene Halobenzene Benzene Chlorobenzene
☞Toluene reacts with Chlorine in the presence of ferric chloride a mixture of ortho and para Chlorotoluene
is formed.
CH3 CH3 CH3
FeCl3 Cl
2 + 2 Cl2 + + 2 HCl
dark

o-Chlorotoluene Cl
p-Chlorotoluene
2.From Diazonium salts[Sandmeyer’s reaction]: Aromatic amines react with nitrous acid(prepared in-situ
from NaNO2 and Conc.HCl) at low temperatures (273-278 K) to form diazonium salts, the reaction is called
Diazotization. NaNO2 + HCl HNO2 + NaCl
+ _
NH2 NaNO2 + HCl N2 Cl
+ O N OH + H Cl + 2 H2O
273 - 278 K
Aniline Benzene diazonium Chloride
☞The freshly prepared diazonium salt is treated with Cuprous chloride or Cuprous bromide to give aryl
chloride or aryl bromide. This reaction is called as Sandmeyer’s reaction.
Cl
CuCl / HCl
_ + N2
+
N2 Cl
Chlorobenzene

Br
Benzene diazonium chloride CuBr / HBr
+ N2
Bromobenzene
☞Replacement of the diazonium group by iodine does not require the presence of cuprous halide and is
done simply by shaking the diazonium salt with potassium iodide.
_
+
N2 Cl I
+ KI + KCl + N2

Benzene diazonium chloride Iodobenzene

Physical properties:
Physical state:
☞The lower alkylhalides (CH3─F, CH3─Cl, CH3─Br, C2H5─Cl) are gases at room temperature. The other
alkylhalides containing upto 18 C are liquids and Still higher members are solids.
Solubility:
☞Haloalkanes and haloarenes are polar molecules. But still they can neither form nor break hydrogen bonds
with water molecules they are slightly soluble in water. They are soluble in organic solvents such as
alcohol, acetone and ether…etc.
Density:
☞The density increases with increase in number of carbon atoms, halogen atoms and atomic mass of the
halogen atoms.

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Melting and boiling points:
☞Due to greater polarity and higher molecular masses of organic halides the inter molecular forces(dipole-
dipole interactions and Van-der-waals forces) are stronger in Halogen derivatives. Therefore melting points
and Boiling points of Alkyl/Aryl halides are higher than corresponding parent Hydrocarbons.
☞For the same alkyl group, the order of boiling points is in the order: R–I > R–Br > R–Cl > R–F.
This is b’coz Van-der-waals forces increases with increase in molecular mass.
☞The Boiling points of isomeric Haloalkanes decreases with increase in branching (greater the branching
lesser is the magnitude of Van-der-waals forces).
CH3
CH3 CH2 CH2 CH2 Br CH3 CH2 CH CH3 CH3 C CH3
Br Br
Boiling points :
375 364 346
in Kelvin
Chemical properties of Haloalkanes:
The reactions of Haloalkanes may be divided into the following categories:
I.Nucleophilic substitution reactions
II.Elimination reactions
III.Reaction with metals.

I.Nucleophilic substitution reactions:

Nucleophilic substitution reactions are those in which incoming nucleophile replaces the
existing halide. Halogens act as good leaving groups and can be replaced as follows,
_
O   _
O
Nu + C X C Nu + X

Examples:
1.With aqueous KOH(potash) or aqueous NaOH or with AgOH (moist silver oxide):
When an Alkyl Halides are heated with aqueous KOH(potash) or aqueous NaOH or moist silver oxide,
corresponding alcohols are formed.

R X + KOH (aq) R OH + KX
Alkyl halide Alkyl alcohol

R X + NaOH (aq) R OH + NaX
Alkyl halide Alkyl alcohol
H2O
2 R X + Ag2 O 2 R OH + 2 AgX [ Ag2 O + H2 O 2 AgOH ]

Alkyl halide Alkyl alcohol Moist
2.With alcoholic KCN ( potassium cynide ): When alkyl halides[ or Haloalkanes] are heated with alcoholic
potassium cyanide, Alkylcyanides (alkane nitrile) are formed.

R X + KCN(alc) R CN + KX
Haloalkane Alkyl cynide or Cynoalkane
3.With alcoholic AgCN : When alkyl halides[ or Haloalkanes] are heated with alcoholic silver cyanide,
Alkylisocyanides(Carbylamines) are formed.

R X + AgCN (alc) R NC + AgX
Haloalkane Alkyl isocynideor Carbyl amine
4.With silver salt of carboxylic acids: When alkyl halides are heated with silver salt of carboxylic acids,
esters are formed.
O O

R C O Ag + X R R C O R + AgX
Silver salt of Alkyl halide Ester
Carboxylic acid

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IllustrationHaloalkanes react with KCN to form alkyl cyanides as main product while AgCN forms
isocyanides as the main product. Explain. [NCERT Example]
Answer: KCN is ionic and provides cyanide 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. This is because, C—C bond is more stable than C—N bond. Hence KCN react to form
cyanides. However, AgCN is covalent in nature and nitrogen is free to donate electron pair forming
isocyanides as the main product.
☞Ambident Nucleophiles: Groups which possess two nucleophilic centres are called ambident
nucleophiles. Groups like cyanides and nitrites possess two nucleophilic centres. Cyanide group is a
resonance hybrid of two contributing structures.
_
O .. O_
C N :C N:
Hence, Cynide group can act as a nucleophile in two different ways i.e., One by linking through carbon
atom resulting in alkyl cyanides and another through nitrogen atom leading to isocyanides.

Mechanisms of Nucleophilic substitution Reactions:

The Nucleophilic substitution reactions of Alkyl halides have been found to proceed in two types of
mechanisms. 1.Substitution nucleophilic first order(SN1).
2.Substitution nucleophilic second order(SN2).
1.Substitution Nucleophilic first order(SN1): or [Substitution nucleophilic Unimolecular reaction]
Tertiary alkyl halides undergo SN1 reaction.
Example: Hydrolysis of tert-butyl bromide with aqueous Sodium hydroxide gives tert-butyl alcohol.
CH3 CH3
CH3 C Br + NaOH CH3 C OH + NaBr
(aq)
CH3 CH3
Tertiary Butylbromide Tertiary Butylalcohol

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Mechanism: The SN1 mechanism involves two steps,
Step 1[Slow step]: Tertiary Butyl bromide undergoes slow ionization to form sp2-Hybridised planar
tertiary butyl carbocation and Bromide ion.
CH3 CH3
Slow _
CH3 C Br C+ + Br
CH3 H3C CH3
Tertiary Butylbromide Tertiary Butyl carbocation
−
Step 2[Fast step]: The nucleophile OH from aqueous NaOH attacks polar carbocation(sp2) from either
side to give tertiary butyl alcohol.
CH3 CH3
_
Fast
C+ + OH CH3 C OH
H3C CH3 CH3
Tertiary Butyl carbocation Tertiary Butylalcohol
The product formed is Racemic mixture.
The rate of reaction depends on the concentration of only one reactant i.e tert-Butyl bromide.
Hence it is unimolecular reaction and follows first order kinetics. Rate [tert-Butyl bromide]1
The Order of reactivity of haloalkanes towards SN1 reaction: 3o > 2o > 1o > Methyl halide.

 For a given alkyl group & halogen atom present R–X, In both SN1 & SN2 follows the order of
reactivity is: R–I > R–Br > R–Cl > R–F. [increase in the bond length increases the reactivity].

2.Substitution nucleophilic second order(SN2): or [Substitution nucleophilic Bimolecular reaction]

Primary alkyl halides undergo SN2 reaction.
Example: When Methyl chloride is heated with aqueous NaOH, methyl alcohol is formed.
CH3 Cl + NaOH (aq) CH3 OH + NaCl
Methyl chlorideor Methyl alcoholor
Chloromethane Methanol
Mechanism: The SN2 mechanism involves single step.
The nucleophile (OH−) attacks the carbon atom of methyl chloride from the back side of leaving
group (Cl−) to form transition state. It is unstable and contains both partial C−OH bond and C−Cl bond.
Finally C−Cl bond is broken. The product methyl alcohol formed has inversion of configuration.
H H * H
_ _
HO + C Cl HO C Cl HO C + Cl
H H H H H H
Methyl chloride Transition state Methyl alcohol
The rate of reaction depends on concentration of both methyl chloride as well as nucleophile (OH−),
Hence it is bimolecular reaction and follows second order kinetics. Rate [CH3−Cl]1 [OH−]1
The Order of reactivity of haloalkanes towards SN2 reaction: Methyl halide > 1o > 2o > 3o.
Differences between SN1 and SN2 reactions:
Sl.No SN1 reaction SN2 reaction
i. It is unimolecular reaction. It is bimolecular reaction.
ii. It follows the first order kinetics. It follows the second order kinetics.
The order of reactivity The order of reactivity
iii. o o o
3 > 2 > 1 > Methyl halide. Methyl halide > 1o > 2o > 3o.
Rate depends only on the concentration of Rate depends only on the concentration of
iv.
alkyl halide. both alkyl halide and nucleophile.
v. It ends with Racemisation. It ends with Inversion of configuration.
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Stereochemical aspects of nucleophilic substitution reactions:
i)Optical active compounds: The compounds which rotate the plane polarised light are called Optical active
compounds.
ii)Optical isomers: Two or more compounds having same molecular formula and structural formula but
differing in the direction of rotation of plane polarised light are called Optical isomers and the phenomenon
is called as Optical isomerism.

iii)Dextro and leavo rotatory substances:

The solution of the substance which rotates the plane polarised light to the right (clockwise) is called Dextro
rotatory substance. It is denoted by (+) sign or ‘d’.
The solution of the substance which rotates the plane polarised light to the left (Anticlockwise) is called
Leavo rotatory substance. It is denoted by (-) sign or ‘l’.
Examples: d-(+)-Lactic acid and l-(–)-Lactic acid.
iv)Optical activity:The Property of the substance to rotate the plane polarized light is called Optical activity.
☞Recemic mixture:
Equimolar mixture of dextrorotatory and leavo rotatory isomers is called Racemic mixture.
Note:
Racemic mixtures are optically inactive because the optical rotation due to d-isomer is cancelled by the
optical rotation of l-isomer.
The device used to study/ measure the magnitude of rotation of plane polarised light is Polarimeter.
In order to show optical isomerism, the compound should contain Chiral carbon.

☞Chiral carbon or Assymetric carbon or Stereocentre:

The Carbon which is bonded to four different atoms or groups is called a Chiral carbon or asymmetric
carbon. It is generally indicated by asterisk C*. The chiral carbon is also called as Stereogenic centre or
Stereo centre.

☞Chirality: The molecules which are non-super imposable on their mirror images are called Chiral
molecules. The property is known as Chirality. The Chiral molecule should contain Chiral carbon.

Similarly, the molecules which are super imposable on their mirror images are called Achiral molecules. The
property is known as Achirality.


Memory tip:
Super imposable Achiral molecules Symmetric carbon.
Non-super imposable Chiral molecules Asymmetric carbon.

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 All Optically active substances are chiral in nature. The chirality and achirality in molecules can be
explained by taking Propan-2-ol and Butan-2-ol and their mirror images. As follows.

Example 1: Propan-2-ol ;

It is clear that A and C are Super imposable mirror

images. Hence, Propan-2-ol contains symmetric
carbon, Hence Propan-2-ol Achiral molecule.

Example 2: Butan-2-ol ;

Here, D and F are the Non-super imposable mirror

images. Butan-2-ol contains asymmetric carbon,
Hence Butan-2-ol is Chiral molecule.

☞Enantiomers: Optically active isomers which are Non-superimposable mirror images are called
enantiomers. This phenomenon is called Enantiomerism.
The Enantiomers only differ with respect to the rotation of plane polarised light. If one of the Enantiomers is
dextrorotatory the other will be Leavo rotatory. The Enantiomers possess identical physical properties like
Melting point, Boiling point, Solubility, Refractive index etc.

☞Racemization: The process of conversion of enantiomers into a Racemic mixture is known as

Racemisation.

 Illustration to show Inversion, retention and racemisation:
There are three outcomes for a reaction at an asymmetric carbon atom. Consider the replacement of a group
X by Y in the following reaction;

☞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+B) i.e equal amount mixture of the above two is obtained then the process is called racemisation
and the resulting product is optically inactive.

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Stereochemical aspects of SN2 reaction:
SN2 reactions of Optically active Alkyl halides[Haloalkanes] are accompanied by inversion of
configuration.
☞Reason: During SN2 mechanism the nucleophile attacks the stereo centre from the side opposite to the
halogen atom. Hence the inversion of configuration takes place.
Example: When ()-2-BromoOctane is heated with aqueous sodium hydroxide, (+)-Octan-2-ol is formed.
Here the –OH group occupies the position opposite to that of Bromine. Hence inversion of configuration
takes place.
H3C H3C
_ _
H C Br + OH H C OH + Br

H13C6 H13C6

Stereochemical aspects of SN1 reaction:

SN1 reactions of Optically active Alkyl halides[Haloalkanes] are accompanied by recemisation.
☞Reason: During SN1 mechanism the first step involves formation of carbocation. It is sp2 hybridised and
has planar structure. Therefore the nucleophile can attack this planar carbocation from both sides giving
mixture of d and l isomers forming racemic mixture.
Example: 2-bromobutane on heating with aqueous solution of sodium hydroxide gives a racemic mixture
containing 50% d-(+)-Butan-2-ol and 50% l-()-Butan-2-ol. Hence the mixture is called as (dl)-Butan-2-ol.
H3C CH3
_
H C Br C+ + Br
H CH2 CH3
H3C CH2

CH3 _ CH3 _ H3C

HO OH
HO C H C+ H C OH
H CH2 CH3
CH2 CH3 H3C CH2
(+)-Butan-2-ol ()-Butan-2-ol
II.Elimination reactions:
Dehydrohalogenation or β-elimination:
Haloalkanes undergo Elimination reaction when heated with alcoholic potassium hydroxide.
H
 
B: + C C C C + B H + X
X Alkene
Haloalkane Where B is Base & X is halogen[Leaving group].

☞There is elimination of a halogen atom from the α-carbon atom and hydrogen atom from β-carbon to
form an alkene. Since β-hydrogen atom is involved in elimination, it is called β-elimination.
 
Examples: CH3 CH2 Cl + KOH (alc) CH2 CH2 + KBr + H2O
Chloroethane Ehene

CH3 CH CH3 + KOH (alc) CH3 CH CH2 + KCl + H2O

Cl
Propene
2-Chloropropane

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☞If more than one type of β-carbon atoms are present, more than one alkene are formed. Among them one
of the alkenes is a major product according to Saytzeff’s rule [also pronounced as Zaitsev rule]. This rule
states that,
“During dehydrohalogenation reaction, if more than one type of β-carbon atoms are present, hydrogen
atom is mostly eliminated from β-carbon atom containing least number of hydrogens”.
CH3 CH2 CH CH CH3 + KBr + H2O
Br Pent-2-ene (major product, 81%)
Example : CH3 CH2 CH2 CH CH3 + KOH (alc)
    '
2-Bromopentane
CH3 CH2 CH2 CH CH2 + KBr + H2O
Pent-1-ene (minor product, 19%)

III.Reaction with metals:

a)With Magnesium:
Preparation of Grignard reagent: When alkyl halide heated with magnesium in dry ether medium, Alkyl
magnesium halide is formed, Alkyl magnesium halide is also called as Grignard reagent.
dry Ether
R X + Mg R Mg X

Alkyl halide Alkyl magnesium halideor
Grignard reagent
Example:
dry Ether
C2H5 Br + Mg C2H5 M g Br

Ethyl bromide Ethyl magnesium bromide

b)With Sodium(Wurtz reaction):

Alkyl halides react with Sodium in presence of dry ether medium to form Higher Alkanes, The reaction is
known as Wurtz reaction.
dry ether
R X + 2 Na + X R R R + 2 NaX
Alkyl halide Alkyl halide Alkane
Examlpes : dry ether
CH3 Cl + 2 Na + Cl CH3 CH3 CH3 + 2 NaCl
Methyl Chloride Methyl Chloride Ethane

dry ether
CH3 CH2 Br + 2 Na + Br CH2 CH3 CH3 CH2 CH2 CH3 + 2 NaBr
Ethyl bromide Ethyl bromide Butane

Chemical properties of Haloarenes:

I.Nucleophilic Substitution reactions:
Haloarenes or Arylhalides are less reactive towards nucleophilic substitution reactions than Haloalkanes due
to following conditions.
1.Due to resonance in Haloarenes but not in Haloalkanes: In aryl halides C−X bond acquires partial
double bond character due to resonance and hence C−X bond becomes stronger.
.. ..
: Cl : Cl Cl Cl : Cl :

I II III IV V

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2.Difference in the Hybridisation of the carbon atom of C−X bond: In Haloalkanes, the carbon atom of
C−X bond is sp3 hybridised while in Haloarenes carbon is sp2 hybridised. The sp2 hybridised carbon atom
has more s-character(33.33%) and is more electronegative.
If more the s-character more is electronegativity, then stronger is C−X bond.
Electronegativity order in different hybridisation is: sp > sp2 > sp3.

Hence in Haloarenes the halogen is strongly held by Carbon atom due to double bond character. Thus the
cleavage of C−X bond in haloarenes is difficult.
3.Instability of Phenyl cation: Phenyl cation formed by dissociation of Aryl halide is highly unstable as it is
not resonance stabilised. Therefore haloarenes cannot undergo substitution by SN1 mechanism.
X
C+
_
+ X

Halobenzene Unstable Phenyl cation

4.Benzene is ring is electron rich so nucleophile cannot attack it easily due to electron- electron cloud
repulsion.

Nucleophilic substitution reactions of Chlorobenzene:

☞Replacement by Hydroxyl group:
When Chlorobenzene is heated with aqueous sodium hydroxide at 623K under 300 atmosphere pressure,
sodium phenate is formed, which on acidification gives phenol. This reaction is called as Dow’s process and
is used for the commercial production of Phenol from chlorobenzene.
Cl ONa ONa OH
623 K H+
+ NaOH + HCl & + H2O + NaOH
300 atm

Chlorobenzene Sodium phenate Sodium phenate Phenol

However, the presence of electron withdrawing groups such as –NO2, –CN, –CHO, –COOH…etc. at ortho
and para positions increases the reactivity of haloarenes.
Examples : Cl OH Cl OH
(i) NaOH, 443 K NO2 NO2
(i) NaOH, 368 K
(ii) H+ (ii) H+

NO2 NO2 NO2 NO2

4-Nitro phenol 2,4-dinitro phenol

Cl OH
O2N NO2 O2N NO2
warm
H2O

NO2 NO2
2,4,6-trinitrochlorobenzene 2,4,6-trinitro phenol (Picric acid)
The effect of more reactivity is only pronounced when Nitro(–NO2) group is introduced at ortho- and para-
positions. But no effect of reactivity of haloarenes is observed if present at meta- position.

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II.Electrophilic substitution reactions:
The resonance structures of Halobenzene, show electron density on ortho and para- positions. Therefore
incoming electrophile preferably attacks these positions. Hence, the halogen atom attached to Benzene is
ortho and para-directing. Electrophilic substitution reactions of Halobenzene produce ortho and para-
products. .. ..
:X : X X X :X :

I II III IV V

 Among ortho and para- substituted products, para-substituted product is a major product. This is
due to the steric hindrance at ortho position.
a.Halogenation: Chlorobenzene reacts with chlorine in presence of anhydrous ferric chloride/ iron
filings/red phosphorus catalyst to give ortho and para isomers.
Cl Cl Cl
Anh. FeCl3 Cl
2 + 2 Cl2 + + 2 HCl

Chlorobenzene 1,2-Dichlorobenzene
(minor)
Cl
1,4-Dichlorobenzene
(major)
b.Nitration:
Chlorobenzene heated with Nitrating mixture[Conc.HNO3 + Conc.H2SO4] to form ortho and para-isomers.
Cl Cl Cl
Conc. H2SO4 NO2
2 + 2 HNO3 + + 2 H 2O
(Conc.)
Chlorobenzene
o-Nitro Chlorobenzene NO2
(minor) p-Nitro Chlorobenzene
(major)
c.Sulphonation: Sulphonation occurs when Chlorobenzene is heated with concentrated H2SO4 to form ortho
and para-isomers.
Cl Cl Cl
 SO 3H
2 + 2 H 2 SO 4 + + 2 H 2O
(Conc.)
Chlorobenzene o-Chlorobenzene SO 3H
sulphonic acid
p-Chlorobenzene
(minor) sulphonic acid
(major)
d.Friedal-Crafts reactions:
i.Friedal-Crafts alkylation: Chlorobenzene reacts with alkyl chloride in presence of anhydrous aluminium
chloride, to form Ortho and para products.
Cl Cl Cl
Anh. AlCl3 CH3
2 + 2 CH 3 Cl + + 2 HCl

Chlorobenzene o-Methyl Chlorobenzene

CH3
(minor) p-Methyl Chlorobenzene
(major)

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ii.Friedal-Crafts acylation: Chlorobenzene reacts with acetylchloride in presence of anhydrous aluminium
chloride, to form Ortho and para products.
Cl Cl Cl
O COCH3
Anh. AlCl3
2 + 2 CH3 C Cl + + 2 HCl

Chlorobenzene o-Acetyl Chlorobenzene

COCH3
(minor) p-Acetyl Chlorobenzene
(major)
III.Reaction with metals:
(a)Wurtz−Fittig reaction:
An Aryl halide and an Alkyl halide react with sodium metal in dry ether to give Alkylarene. This reaction is
called as Wurtz-Fittig reaction.
X R
dry Ether
+ 2 Na + X R + 2 NaX
Alkylhalide
Arylhalide Alkylarene
(b)Fittig reaction:
The two molecules of aryl halides react with sodium metal in dry ether to give Diphenyl or Biphenyl. This
reaction is called as Fittig reaction.
X X
dry Ether
+ 2 Na + + 2 NaX

Arylhalide Arylhalide Diphenyl or Biphenyl

❖Polyhalogen compounds:
☞ Carbon compounds containing more than one halogen atoms are called Polyhalogen compounds.
Some important polyhalogen compounds are described as follows:

a)Dichloromethane (Methylene chlorideCH2Cl2):

☞It is colourless, sweet smelling volatile liquid having low boiling point of 313 K. It is prepared by direct
chlorination of Methane.
h
CH4 + 2 Cl2 CH2Cl2 + 2 HCl
Dichloromethane
☞Uses: It is used
i.As a solvent in manufacture of drugs.
ii.For metal cleaning.
iii.As a paint remover.
iv.As a propellant in aerosols.
v.As refrigerant and dewaxing agent.

 Harmful effects (Physiological effects):

i.It has a harmful effect on human central nervous system.
ii.It can affect vision and hearing.
iii.It can causes dizziness and nausea.
iv.It can cause burning and redness of skin.

KONNUR SCIENCE P.U. COLLEGE, YALLATTI P.U.CII  CHEMISTRY. Page 16 of 20

b)Trichloromethane (Chloroform or methyledine trichloride, CHCl3):
☞Uses: It is used i.As a solvent for fats, waxes, rubber, resins iodine etc.
ii.For manufacture of drug, medicines and insecticide.
iii.It was earlier used as an anesthetic but due to side effects, it is not used now days.
iv.As preservative of anatomical species and important reagent in laboratory.
v.In the production of Freon refrigerant R-22.
☞Storage: Chloroform is slowly oxidised by air in the presence of light to an extremely poisonous gas,
carbonyl chloride, also known as phosgene.
Sunlight
2 CHCl3 + O 2 2 COCl2 + 2 HCl
Chloroform P hosgene
It is therefore stored in closed dark coloured bottles completely filled so that air is kept out.
 Harmful effects (Physiological effects):
i.It can depress the human central nervous system.
ii.It can affect liver, kidney and can develop sore on skin.
iii.It can cause dizziness, headache and fatigue.
iv.It can undergo oxidation with air in presence of light to form poisonous gas phosgene (COCl2), hence
chloroform kept in dark bottle, filled to neck so that air is completely excluded.

c)Triiodomethane (Iodoform, CHI3 ):

☞Uses: It is used
i.As a anesthetic.
ii.For dressing wounds.
iii.Washing surgical instruments.

d)Tetrachloromethane (Carbon tetra chloride,CCl4):

☞Uses: It is used
i.Manufacture of refrigerants and Propellants for aerosol.
ii.Synthesis of chlorofluoro carbons(CFC’s) and other chemicals.
iii.Pharmaceutical manufacturing, and general solvent.
iv.As an important reagent in laboratory and fire extinguisher.
Because of its harmful effects it is banned now and used in some limited industrial applications.
 Harmful effects (Physiological effects):
i.It can cause liver cancer in humans.
ii.It can cause dizziness, nausea and vomiting.
iii.It can make the heart beat irregularly or stop and It can irritate eyes on contact.
v.It can deplete the ozone layer.

☞e)Freons: The Chlorofluoro compounds of methane and ethane are called freons.
They are extremely stable, unreactive, non-toxic, non-corrosive and easily liquefiable gases. Freon-12
(dichlorodifluro methane,CCl2F2) is one of the most common freons in Industrial use.
☞Uses: It is used
i.For aerosol propellants.
ii.as Refrigerants in refrigerators and air conditioning.
iii.as foams to spray out deodorants, shaving creams, hair sprays.

 Environmental effects: In Stratosphere, freon is able to initiate chain reaction, It can deplete the ozone layer.
KONNUR SCIENCE P.U. COLLEGE, YALLATTI P.U.CII  CHEMISTRY. Page 17 of 20
f)p,p’-Dichloro Diphenyl Trichloroethane(DDT):
DDT, the first chlorinated organic insecticides, was originally prepared in 1873, but it was not until 1939
that Paul Muller discovered the effectiveness of DDT as an insecticide. Paul Muller was awarded the Nobel
Prize in Medicine and Physiology in 1948 for this discovery.
Cl
☞Uses: Cl C Cl
i.DDT is cheap but powerful insecticide. CH
ii.It is very effective against the mosquito that spreads
malaria and lice that carry typhus.
Cl Cl
p,p'-dichlorodiphenyltrichloro ethane(DDT)
 Environmental and Physiological effects:
Problems related to extensive use of DDT began to appear in the late 1940’s. Many species of insects
developed resistance to DDT. It has high toxicity towards fish. The chemical stability of DDT and it is non-
biodegradable. DDT is not metabolized very rapidly by animals deposited and stored in the fatty tissues.
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.



❖Questions appeared in Annual Examination❖

8. CH3−Br + AgF CH3−F + AgBr Name the reaction. [March-2014 ; 1m]

32.(a) (i).Write the equations for the steps in SN1 mechanism of the conversion of tert-Butyl bromide into
tert-Butyl alcohol.
(ii).Haloarenes are less reactive towards nucleophilic substitution reactions than Haloalkanes. Give
reason.
(b)Complete the following equations:
(i) C2H5OH + SOCl2 ……
(ii)
Cl
dry Ether
2 + 2 Na
…… [March-2014 ; 5m]

8.What are Freaons? [July-2014 ; 1m]

32.(a).Mention the major product formed in the following reactions;
dry ether
(i) C6H5-Br + M g
2-Bromopentane alc.KOH / 
(ii)
dry Acetone
(iii) CH3 Cl + NaI


(b) .Write the equations for the steps in SN1 mechanism of the conversion of tert-Butyl bromide into
tert-Butyl alcohol. [July-2014 ; (3+2)m]
KONNUR SCIENCE P.U. COLLEGE, YALLATTI P.U.CII  CHEMISTRY. Page 18 of 20
8.Name the organic product formed when Chlorobenzene is treated with sodium in dry ether.
[March-2015 ; 1m]
32. (a).Write the equations for the steps in SN1 mechanism of the conversion of tert-Butyl bromide into
tert-Butyl alcohol.
(b)Identify the products A,B and C in the following equation. [March-2015 ; 5m]
Red P NaI C6H5I
CH3 OH A B C
Cl2 Dry acetone Na / dry ether

dry Acetone
8. R X + NaI R I + NaX ; What is the name of the reaction? [July-2015; 1m]
32. a.(i).Explain the SN2 reaction.
(ii).What is the reagent used in the conversion of Alkyl halide into Alkene.
b. Complete the reaction

CH3 CH2 Br + AgCN [July-2015 ; 5m]
(alc)

8. What is “Chirality”? [March-2016 ; 1m]

32.a. Explain the mechanism of SN1 reaction taking 2-Bromo-2-methyl propane(tert-Butyl bromide)
b. Explain Wurtz-fittig’s reaction.
c. Write the general formula of Grignard reagent. [March-2016 ; (2+2+1)m]

Cl
8. Write the IUPAC name of, [July-2016 ;1m]
CH3
32.a. (i).Exaplain SN2 mechanism taking an example of Chloromethane.
(ii).Write the general equation for the reaction of Primary alcohol with SOCl2.
b. (i). CH3−Br + AgF CH3−F + AgBr Name the reaction.
(ii). p-dichloro benzene has higher boiling point than those of ortho and meta isomers. Give reason.
[July-2016 ; 5m]

8.What is the name of the following reaction?

X Ether
2 + 2 Na
-2NaX
[March-2017 ; 1m]
32. a.Write SN2 mechanism for the conversion of Methyl chloride to Methyl alcohol.
b.Aryl halides are extremely less reactive towards nucleophilic substitution reactions. Give any two
reasons.
c.What is asymmetric carbon? [March-2017 ; (2+2+1)m]

8.Name the major product obtained when tertiary butyl bromide is heated with Alcoholic KOH solution.
[July-2017 ; 1m]
32. a.Write the steps involved in SN1 mechanism of conversion of tertiary butyl bromide into tertiary butyl
alcohol and mention its order.
b.Aryl halides are less reactive towards nucleophilic substitution reactions than alkyl halides. Give two
reasons. [July-2017 ; (3+2)m]

KONNUR SCIENCE P.U. COLLEGE, YALLATTI P.U.CII  CHEMISTRY. Page 19 of 20

8.Name the following reaction,
CH3−Br + AgF CH3−F + AgBr [March-2018 ; 1m]
32. a.Write the equations for the steps in SN1 mechanism of the conversion of tert-Butyl bromide into
tert-Butyl alcohol.
b.Explain Fittig reaction.
c.Name the reagent used in the dehydrohalogenation of Haloalkanes.
[March-2018 ; (2+2+1)m]

8.In aryl halides what is hybridization of the Carbon atom to which the halogen is attached?
[July-2018 ; 1m]
32. a)Write the equations for the steps in SN1 mechanism of conversions of tertiary Butyl bromide into
tertiary butyl alcohol.
b)Explain wurtz fittig reaction with equation.
c)Name the reaction.
Acetone
CH3 Cl + NaI CH3 I + NaCl [July-2018 ; (2+2+1)m]
8.Write the general equation for Wurtz reaction. [March-2019 ; 1m]
32. a) Write the equations for the steps involved in the SN1 mechanism of hydrolysis of
2-bromo-2-methyl propane.
b) i) Name the product formed for the reaction of isopropyl iodide on alcoholic KOH.
ii) What is the condition to be satisfied for a compound to be Chiral?
c) What is Racemic mixture? [March-2019 ; (2+2+1)m]

✮ ✭ ✮ ✭ ✮ ✭ ✮ ✭ ✮ ✭ ✮

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