Unit: 10 Haloalkanes and Haloarenes

The compounds in which one or more hydrogen of alkane is replaced by halogen are
called haloalkanes. They contain halogen atom (s) attached to the sp 3 hybridized
carbon atom of an alkyl group.
Haloarenes contain halogen atom (s) attached to sp 2 hybridized carbon atom (s) of
an aryl group.
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).

Many halogen containing organic compounds occur in nature and some of

these are clinically useful:-
 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.

10.1.1 Classification of Halogen Derivatives:- Haloalkanes and haloarenes may

be classified as follows:
1. On the Basis of Number of Halogen Atoms
These may be classified as mono, di, or polyhalogen (tri-, tetra-)
compounds depending on one, two or more halogen atoms in their
structures. For example,

10.1.2 Compounds Containing sp3 C—X Bond (X = F, Cl, Br, I)

(a) Alkyl halides or haloalkanes (R—X) :
 In alkyl halides, the halogen atom is bonded to an alkyl group (R).
 form a homologous series represented by CnH2n+1X.

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  are further 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) i.e. to
an allylic carbon.
E.g. 3-Haloprop-1-ene; 3-Halobut-1-ene
(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. E.g
Benzyl halide

10.1.3 Compounds Containing sp2 C—X Bond- This class includes:

(a) Vinylic halides
These are the compounds in which the
halogen atom is bonded to an sp2-
hybridised carbon atom of a carbon-carbon
double bond (C = C).
E.g. Haloethene and 1-Halocyclohex-1-ene
(b) Aryl halides
These are the compounds in which the halogen atom is
bonded to the sp2-hybridised carbon atom of an
aromatic ring. E.g. Halobenzene.
CH3
10.2 Nomenclature:
 The common names of alkyl halides are derived by naming the alkyl group
followed by the halide. Alkyl halides are named as halo substituted
hydrocarbons in the IUPAC system of nomenclature. Haloarenes are the
common as well as IUPAC names of aryl halides.
 For dihalogen derivatives, the prefixes o-, m-, p-are used in common
system but in IUPAC system, the numerals 1,2; 1,3 and 1,4 are used.
 The dihaloalkanes having the same type of halogen atoms are named as
alkylidene or alkylene dihalides.
 The dihalo-compounds having same type of halogen atoms are further
classified as
i. Germinal halides (halogen atoms are present on the same carbon atom)
ii. 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.

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  In IUPAC system, they are named as dihaloalkanes.

Common Name: Bromobenzene m- Dibromobenzene sym- Tribromobenzene

IUPAC Name: Bromobenzene 1,3- Dibromobenzene 1,3,5- Tribromobenzene

IUPAC Name: 2-bromopropane

H2C – CHCl2 H2C – CH2

I I
Cl Cl
Common Name: Ethylidene chloride Ethylene dichloride
(gem-dihalide) (vic-dihalide)
IUPAC Name: 1,1-Dichloroethane 1,2- Dichloroethane

Table 10.1: Common and IUPAC names of some Halides

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Haloalkanes- General formula is R-X where X= Cl, Br, I and F
Common Name is Alkyl Halide
IUPAC Name is Haloalkane

10.3 Nature of C–X Bond:-

Halogen atoms are more electronegative than carbon, the carbon-halogen bond of
alkyl halide is polarized where the carbon atom bears a partial positive charge
whereas the halogen atom bears a partial negative charge.
The size of halogen atom increases as we go down the group in the periodic table,
fluorine atom is the smallest and iodine atom is the largest. Therefore the carbon-
halogen bond length increases from C—F > C—Cl > C—Br > C—I.

10.4 Methods of Preparation of Haloalkanes

1. From Alcohols: Alkyl halides are best prepared from alcohols where the
hydroxyl group of an alcohol is replaced by halogen on reaction with
concentrated halogen acids, phosphorus halides or thionyl chloride.
ZnCl2
R – OH + HX R – X + H2O
R – OH + NaBr + H2SO4 R – Br + NaHSO4 + H2O
Phosphorus tribromide and triiodide are usually generated in situ (produced in
thereaction mixture) by the reaction of red phosphorus with bromine and iodine
respectively.
3R – OH + PX3 3R – X + H3PO3 (X = Cl, Br)
∆
3CH3CH2 – OH + PCl3 3CH3CH2 – Cl + H3PO3
Ethyl alcohol Ethyl Chloride
R – OH + PCl5 R – Cl + POCl3 + HCl
The preparation of alkyl chloride is carried out either by passing dry hydrogen
chloride gas through a solution of alcohol or by heating a solution of alcohol in
concentrated aqueous acid.
red P/X2
R – OH X2= Br2,I2 R–X

R – OH + SOCl2 R – Cl + SO2↑ + HCl↑

CH3CH2 – OH + SOCl2 CH3CH2 –Cl + SO2↑ + HCl↑
Ethyl alcohol Ethyl Chloride
Thionyl chloride is preferred because the other two products are escapable gases. Hence
the reaction gives pure alkyl halides.

With tertiary alcohols, the reaction is conducted by simply shaking with concentrated HCl at
room temperature. Constant boiling with HBr (48%) is used for preparing alkyl bromide.
Good yields of R—I may be obtained by heating alcohols with sodium or potassium iodide in
95% orthophosphoric acid.

The reactivity order of halogen acids (haloacid) is HI > HBr > HCl or 3° > 2° > 1°.

The above methods are not applicable for the preparation of aryl halides because the
carbon-oxygen bond in phenols has a partial double bond character and is difficult to break
being stronger than a single bond.

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2. From Hydrocarbons
(a) By free radical halogenations
Free radical chlorination or bromination of alkanes gives a complex mixture of
isomeric mono- and poly haloalkanes, which is difficult to separate as pure
compounds. Cl2/UV light
CH3CH2CH2CH3 CH3CH2CH2CH2Cl + CH3CH2CHClCH3
Butane Or heat 1-chlorobutane (28%) 2-chlorobutane (72%)

(b) By electrophilic substitution

Aryl chlorides and bromides can be easily prepared by electrophilic substitution of
arenes with Cl and Br respectively in the presence of Lewis acid catalysts like
iron or iron(III) chloride.

Toluene o-Halotoluene p-Halotoluene

The ortho and para isomers can be easily separated due to large difference in their
melting points.
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
When a primary aromatic amine,
dissolved or suspended in cold
aqueous mineral acid, is treated with
sodium nitrite, a diazonium salt is
formed.
Mixing the solution of freshly prepared
diazonium salt with cuprous chloride
or cuprous bromide results in the
replacement of the diazonium group
by –Cl or –Br.
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.
(d) From Alkenes
(i) Addition of hydrogen halides: An alkene is converted to corresponding alkyl
halide by reaction with hydrogen chloride, hydrogen bromide or hydrogen
iodide. \ / \ /
C = C + HX C—C
/ \ / I I\
H X
H3C-HC=CH2 + H-I CH3-CH2-CH2- I + CH3-CHI-CH3
Minor Major

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 H3C-HC=CH-CH3 + HBr CH3-CH2-CH- CH3
2-Butene I
Br
2-Bromobutane
(ii) Addition of halogens: In the laboratory, addition of bromine in CCl 4 to an
alkene results in discharge of reddish brown colour of bromine constitutes an
important method for the detection of double bond in a molecule. The
addition results in the synthesis of vic-dibromides, which are colourless.
CCl4
H2C= CH2 + Br2 BrCH2-CH2Br
Ethene Vicidibromide

3. Halogen Exchange
Alkyl iodides are prepared by the reaction of alkyl chlorides/bromides with NaI in
dry acetone. This reaction is known as Finkelstein reaction. NaCl or NaBr thus
formed is precipitated in dry acetone. It facilitates the forward reaction according
to Le Chatelier’s Principle.
R – X + NaI Acetone R – I + NaX (X= Cl, Br)
Reflux
The synthesis of alkyl fluorides is best accomplished by heating an alkyl
chloride/bromide in the presence of a metallic fluoride such as AgF, Hg 2F2, CoF2
or SbF3. The reaction is termed as Swarts reaction.
H3C – Br + AgF H3C – F + AgBr
Methyl Bromide Methyl Flouride

4. Halogenation of alkanes:
A. Chlorination- In this method, polysubstitution reactions take place in
presence of U.V light/ Diffused sunlight resulting in formation of di, tri and tetra
derivatives. Hence it is not a good method to prepare chloroalkanes.
U.V light
Diffused
sunlight
Methane

U.V light
Diffused
Methyl chloride sunlight

U.V light
Diffused
sunlight

U.V light
Diffused
sunlight

AlBr3
B. Bromination- CH4 + Br2 CH3Br + HBr
Methane Δ Bromomethane

C. Iodination- CH4 + I2 ↔ CH3I + HI

Methane Methyliodide
To stop reversibility of this reaction, oxidizing agents -HIO3 or HgO used.
5CH4 + 2I2 + HIO3 → 5CH3I + 3H2O
Methane Iodic acid Methyliodide
2CH4 + 2I2 + HgO → 2CH3I + HgI + H2O

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5. Markonikoff and Antimarkonikoff’s Rule:
Markownikov rule:-negative part of the addendum (adding molecule) gets attached to
that carbon atom which possesses lesser number of hydrogen atoms. e g

Peroxide effect or Kharasch(Anti Markownikoff’s addition):- In 1933 Kharasch and

Mayo observed that when HBr is added to an unsymmetrical double bond in
thepresence of organic peroxide, the reaction take places opposite to the
Markovnikovrule.

6. Hunsdiecker Reaction: Bromoalkane can be easily prepared by refluxing the

silver salt of a fatty acid with bromine in CCl 4; this reaction is called Hunsdiecker
reaction.
CH3CH2COOAg + Br2 CCl4, reflux CH3CH2Br + CO2 + 2AgBr
Silverpropanoate Bromoethane

Methods of preparation:-
1. Vicinal dihalide
CCl4
CH2 = CH2 + Br2 CH2 Br - CH2Br
Ethene Ethylene dibromide

2. Geminal dihalide
HBr HBr
CH ≡ CH CH2 = CH Br CH3-CH-CH2
Acetylene Vinylbromide Ethyldiene dibromide

10.5 Physical Properties of Haloalkanes:-

1. Boiling point orders
 Boiling point of alkyl halide decreases in order R – I > R – Br > R – CI > R – F
because with increase in size and mass of halogen atom the magnitude of
van der waals forces increase.
 Boiling point of isomeric haloalkanes decrease with increase in branches i.e
tert < sec < pri
 Boiling point of isomeric dihalobenzenes are nearly the same but para-isomer
have higher melting point compared to ortho and meta- isomer due to their
symmetry.
 As size of alkyl group increases the attraction gets stronger and boiling point
increases with increase in size of alkyl group.
 Methyl chloride, methyl bromide, ethyl chloride and some
chloroflouromethane are gases at room temperature.
 Higher members are liquid or solids.

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  Boiling point of Cl, Br & I are higher due to greater polarity and higher
molecular mass, intermolecular forces of attraction such as dipole-dipole
interaction and strong van der waals forces.
 CH3 – (CH2)2 – CH2Br > (CH3)2 CHCH2Br > (CH3)3CBr
 CH3CH2CH2 > CH3CH2X > CH3X
2. Bond strength of haloalkanes decreases as the size of the halogen atom
increases. Thus, the order of bond strength is CH3F > CR3Cl > CR3Br > CH3I
3. Dipole moment decreases as the electronegativity of the halogen decreases.
4. Haloalkanes though polar but are insoluble in water as they do not form
hydrogen bonding with water. But haloalkanes are soluble in organic solvents
because new intermolecular attraction between solvents and haloalkane
molecules have same strength as the ones being broken.
5. Density– increases with increase in number of carbon atom, halogen atom and
atomic mass of halogen atom; order is R-I > R-Br > R-Cl> R-F (For the same
alkyl group) CH3I > C2H5I > C3H7I
6. Alkyl halide are colourless when pure, but bromides and iodides develop colour
when exposed to light.
7. Volatile halogen compound have sweet smell.

10.6 Chemical Reactions of Haloalkanes

1. Nucleophilic Substitution Reactions (SN reactions)
In this type of reaction, a nucleophile reacts with haloalkane (the substrate)
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. Since the substitutionreaction is initiated by a nucleophile, it is
called nucleophilic substitution reaction. It is one of the most useful classes of
organic reactions of alkylhalides in which halogen is bonded to sp3 hybridised
carbon. R-X + Nu- → R-Nu + X-
\ ẟ+ ẟ˗ \
Nu + –C-X → ̶ C-Nu + X-
-

/ /

Nucleophilic substitution reactions are of two types:-

(a) SN1 type (Substitution nucleophilic unimolecular)- reactions proceed in two
steps: These reactions are generally carried out in polar protic solvents (like water,
alcohol, acetic acid, etc.). The reaction between tert-butyl bromide and hydroxide ion
yields tert-butyl alcohol and follows the first order kinetics, i.e., the rate of reaction
depends upon the concentration of only one reactant, which is tert- butyl bromide.
(CH3)3CBr + -
OH → (CH3)3COH + Br -
2-Bromo-2-methylpropane 2-Methylpropan-2-ol
It occurs in two steps:-
In step I, the polarised C—Br bond undergoes slow cleavage to produce a
carbocation and a bromide ion. It is the slowest and reversible; it involves the C–Br
bond breaking for which the energy is obtained through solvation of halide ion with
the proton of protic solvent.
Since the 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.

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Further, greater the stability of carbocation, greater will be its ease of formation from
alkyl halide and faster will be the rate of reaction. In case of alkyl halides, 30 alkyl
halides undergo SN1 reaction very fast because of the high stability of 30
carbocations.
In step II, thecarbocation thus formed is then attacked by nucleophile to complete
the substitution reaction. CH3
(CH3)3CBr I + Br-
+
2-Bromo-2-methylpropane C
/ \
CH3 CH3 tert-butyl carbocation

+ OH- (CH3)3COH tert-butylalcohol

(b) SN2 type (Substitution nucleophilic bimolecular)- The reaction between CH3Cl
and hydroxide ion to yield methanol and chloride ion follows a second order kinetics,
i.e., the rate depends upon the concentration of both the reactants.
It depicts a bimolecular nucleophilic displacement (S N2) reaction; the incoming
nucleophile interacts with alkyl halide causing the carbon halide 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. As the reaction progresses and the bond between the nucleophile and the
carbon atom starts forming, the bond betweencarbon atom and leaving group
weakens. As this happens, the configuration of carbon atom under attack inverts in
the same way as an umbrella is turned inside out when caught in a strong wind,
while the leaving group is pushed away. This process is called as inversion of
configuration. (100% inversion)

Tertiary halides are the least reactive because bulky groups hinder the approaching
nucleophiles. Thus the order of reactivity followed is:
Primary halide > Secondary halide > Tertiary halide

During SN2 reaction, inversion of configuration occurs (Walden inversion) i.e.,

starting with
 dextrorotatory halide a laevo product is obtained and vice-versa,
 Rate of reaction in SN2 mechanism depends on the strength of the attacking
nucleophile.
 Strength of some common nucleophiles is
:CN- > : I- > : OR- > : OH- > CH3COO: > H2O > F-
 Non-polar solvents, strong nucleophiles and high concentration of nucleophiles
favour SN2 mechanism.
 Relative reactivity of alkyl halides for same alkyl group is RI > RBr > RCI > RF

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We can sum up the order of reactivity of alkyl halides towards S N1 and SN2
reactions as follows:
For the same reasons, allylic and benzylic halides show high reactivity towards the
SN1 reaction. The carbocation thus formed gets stabilised through resonance.
For a given alkyl group, the reactivity of the halide, R-X, follows the same order in
both the mechanisms R–I > R–Br > R–Cl >> R–F. i.e 3 o > 2 o > 1o
 Rate, r = k [RX]. It is a first order reaction.
 Reactivity order of alkyl halide towards SN1 mechanism
 3° > 2° > 1°
 Polar solvents, low concentration of nucleophiles and weak nucleophiles favour
SN1 mechanism.
 In SN1 reactions, partial racemisation occurs due to the possibility of frontal as
well as backside attack on planar carbocation.

(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: Certain compounds rotate the plane
polarised light when it is passed through their solutions. Such compounds are
called optically active compounds.
The angle by which the plane polarised light is rotated is measured by an
instrument called polarimeter.
If thecompound rotates the plane polarised light to the right, i.e., clockwise
direction, it is called dextrorotatory (Greek for right rotating) or the d-form and is
indicated by placing a positive (+) sign before the degree of rotation.
If the light is rotated towards left (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 compoundare called optical
isomers and the phenomenon is termed as optical isomerism.

(ii) Molecular asymmetry, chirality and enantiomers:

The symmetry and asymmetry are also observed in many day to day
objects: a sphere, a cube, a cone, are all identical to their mirror images and can
be superimposed. While the objects, which are, superimposable on their mirror
images are called achiral.

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 However, many objects are non super imposable on their mirror images. For
example, your left and right hand look similar but if you put your left hand on your
right hand, they do not coincide. The objects which are non superimposable on
their mirror image (likea pair of hands) are said to be chiral and this property is
known as chirality.

The stereoisomers related to each other as nonsuperimposable mirror images are

called enantiomers. Enantiomers possess identical physical properties namely,
melting point, boiling point, refractive index etc. They only differ with respect to the
rotation of plane polarised light. If one of the enantiomer isdextro rotatory, the other
will be laevorotatory.
A mixture containing two enantiomers in equal proportions will have zero optical
rotation, as the rotation due to one isomer will be cancelled by the rotation due to the
other isomer. Such a mixture is known as racemic mixture or racemic
modification. A racemic mixtureis represented by prefixing dl or (±) before the
name, for example(±) butan-2-ol. The process of conversion of enantiomer into a
racemic mixture is known as racemisation.

(iii) Retention: of configuration is the preservation of integrity of the spatial

arrangement of bonds to an asymmetric centre during a chemical reaction or
transformation. In general, 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. Consider as an example, the reaction that takes place when (–)-2-
methylbutan-1-ol is heated with concentrated hydrochloric acid.

(iv) 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 50:50 mixture of the above two is obtained then the process is called
racemisation and the product is optically inactive, as one isomer will rotate light in
the direction opposite to another.

3. Elimination Reactions
When a haloalkane with β -hydrogen atom is heated with alcoholic solution of
potassium hydroxide, there is elimination of hydrogenatom from β -carbon and a
halogen atom from the β -carbon atom where the product formed is alkene. Since β
–hydrogenatom is involved in elimination, it is called β -elimination.

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Russian chemist, Alexander Zaitsev (also pronounced as Saytzeff) who in 1875
formulated a rule which can be summarised as “in dehydrohalogenation
reactions, the preferred product is that alkene which has the greater number of
alkyl groups attached to the doubly bonded carbon atoms.” Thus, 2-
bromopentane gives pent-2-ene as the major product.

1. Reaction with Metals

a. Grignard Reagents (Alkyl magnesium halide, RMgX) –
Most organic chlorides, bromides and iodides react with certain metals to give
compounds containing carbon-metal bonds, known as organo-metallic
compounds. An important class of organo-metallic compounds discovered by
VictorGrignard in 1900 is alkyl magnesium halide, RMgX, referred as
Grignard Reagents.
Dry ether
CH3CH2Br + Mg CH3CH2MgBr (Grignard Reagent)
In the Grignard reagent, the carbon-magnesium bond is covalent but highly polar,
with carbon pulling electrons from electropositive Mg; the magnesium halogen
bond is essentially ionic. ẟ- ẟ+ ẟ -
R-MgX
Grignard reagents are highly reactive and react with any source of proton to give
hydrocarbons. Even water, alcohols, amines are sufficientlyacidic to convert
them to corresponding hydrocarbons.
Ether
RMgX + H2O RH + Mg(OH)X

b. 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.
Dry ether
R-X + 2 Na + R-X R-R + 2Na+X-
Alkylhalide Alkane
dry ether
CH3Br + 2 Na + CH3Br CH3CH3 + 2NaBr
Methylbromide Ethane

Haloarenes
Haloarenes- are compounds having halogen
atom directly attached to an aromatic ring.
General formula Ar-X where Ar is phenyl or
substituted phenyl or any other aryl ring.
Common as well as IUPAC name is Aryl
halide.

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Dihalogen derivatives have prefixes o-, m- and p- but in IUPAC system
numericals (1,2), (1,3) and (1,4) are used.
Physical Properties of Aryl Halides
1. Aryl halides are colourless liquids or colourless solids with characteristic odour.
2. Boiling point generally increases with increase in the size of aryl group or halogen
atom.
3. Boiling point order Ar – I > Ar – Br > Ar – Cl > Ar – F
4. The melting point of p –isomer is more than o- and m-isomer.
5. This is because of more symmetrical nature of p-isomer.
6. Due to resonance in chlorobenzene, C-CI bond is shorter and hence, its dipole
moment is less than that of cyclohexylchloride.
Chemical Properties of Aryl Halides
1. Nucleophilic Substitution Reaction
Aryl halides are less reactive towards nucleophilic substitution reaction. Their low
reactivity is attributed due to the following reasons:
1. Due to resonance, C-X bond has partial double bond character.
2. Stabilization of the molecule by hybridization of electrons.
3. Instability of phenyl carbocation.
a. Resonance effect- In haloarenes, the electron pairs on halogen atom are in
conjugation with π-electrons of the ring. The C-Cl bond acquires a partial double
bond character due to resonance. Hence bond cleavage is difficult and so
they are less reactive towards nucleophilic substitution reaction.

b. Difference in hybridization of carbon atom in C—X bond: In haloalkane, the

carbon atom attached to halogen is sp3 hybridised while in case of haloarene, the
carbon atom attached to halogen is sp2-hybridised.

The sp2 hybridised carbon with a greater s-character is more electronegative

and can hold the electron pair of C—X bond more tightly than sp3-hybridised
carbon haloalkane with less s-character. Thus, C—Cl bond length in haloalkane
is 177 pm while in haloarene is 169 pm. Since it is difficult to break a shorter
bond than a longer bond, haloarenes are less reactive than haloalkanes towards
nucleophilic substitution reaction.
c. Instability of phenyl cation: In case of haloarenes, the phenyl cation formed as
a result of self-ionisation will not be stabilized by resonance and SN1 mechanism
is ruled out.
d. Because of the possible repulsion, it is less likely for the electron rich nucleophile
to approach electron rich arenes.

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Replacement by hydroxyl group (Dow process for manufacture of Phenol)
Chlorobenzene can be converted into phenol by heating in aqueous sodium
hydroxide solution at a temperature of 623 K and a pressure of 300 atmospheres.

Chlorobenzene Phenol
However, aryl halides having electron withdrawing groups (like – NO2, -SO3H, etc.)
at ortho and para positions undergo nucleophilic substitution reaction easily.
Presence of electron withdrawing group (-NO2) increases the reactivity.

(Picrylchloride) (Picric acid)

2. Electrophilic Substitution Reactions
Halogens are deactivating but o-, p-directing. Thus, chlorination, nitration,
sulphonation and Friedel Craft’s reaction give a mixture of o- and p- chloro
substituted derivatives. Due to resonance, electron density increases more at o- and
p- position than at meta. The halogen atom because of its –I effect has tendency to
withdraw electrons from benzene ring. Thus electrophilic substitution reaction in
haloarenes occur slowly and require more drastic condition.
(i) Halogenation

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(ii) Nitration
Cl
Cl Cl

Chlorobenzene 1-chloro-2-nitrobenzene 1-chloro-4-nitrobenzene

(minor) (major)

(iii) Sulphonation

(iv) Friedel-Crafts reaction

3. Reaction with Metals

(i) Wurtz Fittig reaction- a mixture of alkylhalide and aryl halide gives an arylarene
when treated with Na in dry ether and is called wurtz fittig reaction.

CH3-O-CH3
Aryl halide
Acetyl chloride Aryl arene
(iii) Fittig reaction- aryl halides give analogous compounds when treated with Na
in presence of dry ether where 2 aryl groups are joined together called fittig
reaction.

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10.7 Polyhalogen Derivatives - Carbon compounds containing more than one
halogen atom. Many of these compounds are useful in industry and agriculture.
1. Dichloromethane (Methylene chloride)
Uses- i. as a solvent as a paint remover, a propellant in aerosols and process
solvent in the manufacture of drugs.
ii. It is also used as a metal cleaning and finishing solvent.
Physiological effects-
i. Methylene chloride harms the human central nervous system.
ii. Exposure to lower levels of methylene chloride in air can lead to slightly impaired
hearing and vision.
iii. Higher levels of methylene chloride in air cause dizziness, nausea, tingling and
numbness in the fingers and toes.
iv. In humans, direct skin contact causes intense burning and mild redness of the
skin. Direct contact with the eyes can burn the cornea.

2. Trichloromethane (Chloroform)
Uses- i. Chemically, chloroform is employed as a solvent for fats, alkaloids,
iodine and other substances.
ii. The major use of chloroform today is in the production of the freon refrigerant
R-22.
Physiological effects-
i. It was used as a general an aesthetic in surgery but was replaced by less
toxic, safer anaesthetics, such as ether.
ii. Inhaling chloroform vapours depresses the central nervous system.
iii. Breathing about 900 parts of chloroform per million parts of air (900 parts per
million) for a short time can cause dizziness, fatigue, and headache.
iv. 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.
v. Chloroform is slowly oxidised by air in the presence of light to an extremely
poisonous gas, carbonyl chloride, also known as phosgene.
light
2CHCl3 + O2 2 O = CCl2 + 2 HCl
Chloroform Phosgene
It is therefore stored in closed dark coloured bottles completely filled so that air is
kept out.

3. Triiodomethane (Iodoform)
It was used earlier as an antiseptic for dressing wounds, but the antiseptic
properties are due to the liberation of free iodine and not due to iodoform itself.
Due to its unpleasant smell, it has been replaced by other formulations containing
iodine.

4. Tetrachloromethane (Carbon tetrachloride) CCl4

Uses-
i. It is produced in large quantities for use in the manufacture of refrigerants and
propellants for aerosol cans.
ii. It is also used as feedstock in the synthesis of chlorofluorocarbons and other
chemicals, pharmaceutical manufacturing, and general solvent use.

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 iii. Until the mid 1960s, was also widely used as a cleaning fluid, both in
industry, as a degreasing agent, and in the home, as a spot remover and as
fire extinguisher.

Physiological effects-
i. There is some evidence that exposure to carbon tetrachloride causes liver
cancer in humans.
ii. The most common effects are dizziness, light headedness, nausea and
vomiting, which can cause permanent damage to nerve cells.
iii. In severe cases, these effects can lead rapidly to stupor, coma,
unconsciousness or death. Exposure to CCl 4 can make the heart beat
irregularly or stop. The chemical may irritate the eyes on contact.

Environmental effects-
When carbon tetrachloride is released into the air, it rises to the atmosphere and
depletes the 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
The chlorofluorocarbon compounds of methane and ethane are collectively
known as freons (CCl2F2). These are usually produced for aerosol propellants,
refrigeration and air conditioning purposes.

Uses –
i. They are extremely stable, unreactive, non-toxic, non-corrosive and
easily liquefiable gases.
ii. Freon 12 (CCl2F2) is one of the most common freons in industrial use. It is
manufactured from tetrachloromethane by Swarts reaction. By 1974, total
freon production in the world was about 2 billion pounds annually. In
stratosphere, freon is able to initiate radical chain reactions that can upset the
natural ozone balance.

6. DDT (p, p'-Dichlorodiphenyltrichloroethane)

It is the first chlorinated organic insecticide. It is prepared from chloral and
chlorobenzene in the presence of conc. H2SO4·
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.
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; it is deposited and stored in the fatty tissues. The use of DDT was
banned in the United States in 1973.

Freda
7. BHC (Benzene Hexachloride) C6H6Cl6
It is prepared by chlorination of benzene in presence of sunlight. It is an important
agriculture pesticide mainly used for exterminating white ants, leaf hopper, termite and is
commonly called as gammaxene or lindane or 666.

March 2008
Q1. With respect to the following, name the compound which undergoes faster
SN1 reaction and give name for the same: (1 mark)
a. Cl
I
CH3 – CH2 – C – CH3
I
CH3
b. Cl
I
CH3 – CH2 – CH – CH2 – CH3
Q2. Complete the following statement by choosing the correct alternative given
below the statement and rewrite the completed statement: (1 mark)
The order of reactivity for SN2 reaction involving replacement of a halide by a
nucleophile in an alkyl halide is _________
a. CH3-X < Primary halide > Secondary halide
b. CH3-X < Primary halide < Secondary halide
c. CH3-X > Primary halide < Secondary halide
d. CH3-X > Primary halide > Secondary halide
Q3. Write Wurtz - Fittig reaction for the preparation of toluene (1 mark)
Q4. Write labeled chemical equations to show the reactions of: (2 marks)
a. Chlorobenzene with methylchloride in presence of anhydrous aluminium
chloride.
b. Sodium tertiary butoxide with chloroethane.

March 2009
Q1. The only chiral molecule in the following is _________ (1 mark)
a. 2-bromobutane c. 2-bromopropane
b. 1-bromobutane d. 1-bromopropane
Q2. Write labeled chemical equations for the following reactions (2 marks)
a. Action of alcoholic KOH on n-butylbromide.
b. Action of metal sodium on chlorobenzene in the presence of dry ether.
Q3. Answer the following: (2 marks)
a. Write the structure of p,p′-dichlorodiphenyltrichloroethane.
b. Write a chemical equation for the preparation of Anisole by Williamson’s
synthesis.

March 2010
Q1. The increasing order of the reactivity of the given three isomeric structure of
bromobutane in SN2 reaction is _________ (1 mark)
a. 1-bromobutane < 2-bromobutane < 2-bromo-2-methylpropane
b. 1-bromobutane < 2-bromo-2-methylpropane < 2-bromobutane
c. 2-bromobutane < 1-bromobutane < 2-bromo-2-methylpropane
d. 2-bromo-2-methylpropane < 2-bromobutane < 1-bromobutane

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Q2. Write the IUPAC name of the following organic compound: (1 mark)
CH3 – CH = C – CH – CH3
I I
CH3 Br
Q3. Write labeled chemical equations for the reaction of (2 marks)
a. Chlorobenzene and methylchloride with sodium metal in presence of dry
ether.
b. 2-bromobutane with alcoholic potassium hydroxide.
March 2011
Q1. C4H9 exists in four isomeric forms. Write the structure and IUPAC name of
the isomer that will have the lowest boiling point. (1 mark)
Q.2. Write the labelled equation to show the action of: (2 marks)
a. Sodium in dry ether on chlorobenzene.
b. Hot alcoholic KOH on 2-iodobutane.
OR
Q.2. How will you convert: (2 marks)
a. Propene to 1-bromopropane.
b. Chlorobenzene to 1-chloro-4-methylbenzene.

March 2012
Q1. SN1 reaction of alkyl halide leads to_________ (1 mark)
a. Retention of configuration
b. Racemisation
c. Inversion of configuration
d. None of the above
Q2. Write the structures of A, B, C and D in the following reactions: (2 marks)
Na
a) CH3CH2Br + NaI A B
Ether
NaNO2 + HCl H3PO2

b)

273 – 283 K H2O

March 2013
Q1. Alkyl halides are prepared from alcohols by treating with ________ (1 mark)
a. Cl2/UV light c. Cu2Cl2 + HCl
b. HCl + ZnCl2 d. KCl + HNO3
Q2. Complete the following chemical equations: (2 marks)
Anhydrous AlCl3
a) C6H5Cl + CH3COCl
Dry Ether
b) C2H5Cl + Na

March 2014
Q1. Identify the structure A and B in the following and rewrite the completed
equation. (3 marks)

HCl, ZnCl2 Na
a. A CH3-CH2-Cl B
Dry Ether

Freda
 NaNO2 + HCl KI
b. A
0 to 5oC

Cl2 , Fe CH3COCl
c. A
Dark Anhydrous AlCl3

March 2015
Q1. The IUPAC name and the class to which the compound
CH3
I
CH3-CH =CH-C-CH3 belongs is _______ (1 marks)
I
Br
A. 2-bromo-2-methylpent-3-ene, an allylic alkylhalide
B. 4-bromo-4-methylpent-2-ene, a vinylic alkylhalide
C. 2-bromo-2-methylpent-3-ene, a vinylic alkylhalide
D. 4-bromo-4-methylpent-2-ene, an allylic alkylhalide
Q2. Identify the main product formed in the following reactions and name the
reactions: (2 marks)
a) CH3-Br + AgF
Ether
b) 2 + 2 Na

March 2016
Q1. Give reason for the following: (1 mark)
2-iodopropane has a higher boiling point than 2-flouropropane although both
have the same alkyl group.
Q.2. Complete the following reactions: alcohol (2 marks)
a) CH3-CH2-CH2-CH-CH3 + KOH
I heat
Br
b) CH3-CH2- CH2I + AgNO2
March 2017
Q1. In the reaction,

Br2
(Q) (R)

The products (Q) and (R) are __________ (1 mark)

A. (Q): 4-bromonitrobenzene, (R): 4-bromobenzenamine
B. (Q): 3-bromonitrobenzene, (R): 3-bromobenzenamine
C. (Q): 2-bromonitrobenzene, (R): 2-bromobenzenamine
D. (Q): 2, 4-dibromonitrobenzene, (R): 2,4-dibromobenzenamine

Freda
Q2. Arrange the isomeric compounds given below in the increasing order of their
boiling point. CH3 (1 mark)
I
CH3-CH2-CH-CH3 ; CH3-CH2-CH2-CH2-Br ; CH3-C-Br
I I
Br CH 3
Q3. Write the structures of the major product formed in the following chemical
equation: (2 marks)

a) CH3-CH=CH2 + HBr
alcoholic
b) CH3-CH2-CH-CH2-CH3 + KOH
I
Cl
Dry acetone
c) CH3-CH2- Br + NaI
d) CH3-CH2-CH2Cl + KCN

March 2018
Q1. State why 1,4-dichlorobenzene melts at a higher temperature than
1,2-dichlorobenzene. (1 marks)
Q2. Write chemical equations to show how you will convert: (2 marks)
a. Ethyl chloride to nitroethane.
b. Chlorobenzene to 4-chlorotoluene.
OR
Q2. Write chemical equations to show how you will convert: (2 marks)
a. 2-chloropropane to 2-iodopropane.
b. Benzene diazonium chloride to chlorobenzene.

March 2019
Q1. Write the structures of the compounds ‘A’, ‘B’, ‘C’, ‘D’, ‘E’ and ‘F’ in the
following chemical equations: (3 marks)
CH3
I ∆ HBr
a. CH3 – C – CH3 ‘A’ ‘B’
I alc KOH Peroxide
Br
CH3
/ uv aq KOH
b.
+ Cl2 ‘C’ ‘D’

dry ether H2O

c. CH3 – Cl + Mg ‘E’ ‘F’
March 2020
Q1. Write the structure and name of the major products (L) and (M) formed in the
sequence of chemical reactions given below: (3 marks)
2Na; dry ether KOH; alcoholic
(L) CH3-CH-CH2Br (M)
I ∆
CH3

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a. Arrange the following halides in the decreasing order of reactivity in S N1
reaction:
CH3CH2CH2CH2Cl; (CH3)3C-Cl; CH3CH2CH(Cl)CH3
OH −
b.
(?) + Cl − + H2O

(i) HNO2
c. CH3-CH2-CH2-NH2 (?) + NH2 + HCl
(ii) H2O
(i) H2SO4
d. C6H5NH2 (?)
(ii) 453 – 473 K

Nov 2021
Q.1 CH3-CH-Cl + AgF ----> CH3-CH-F + AgCl
I I
CH3 CH3
The name of the above reaction is _____________. (1 mark)
a. Swartz reaction b. Wurtz reaction c. Williamson’s synthesis d. Finkelstein reaction
Q2. The alkane that gives only monochloro derivative on chlorination with Cl 2 in presence
of diffused sunlight is __________ . (1 mark)
a. Iso-hexane b. Neo-pentane c. n-pentane d. iso-pentane
Q3. Benzene on reaction with Br2 and Fe forms ‘X’. Compound ‘X’ on reaction with sodium
in presence of dry ether forms __________. (1 mark)
a. Naphtahalene b. Benzene c. Diphenyl d. Bromobenzene
Q4. Aniline reacts with nitrous acid at low temperature to form a compound ‘X’. Compound
‘X’ on reacting with potassium iodide forms a compound ‘Y’. Compound ‘Y’ is ______.
(1 mark)
a. Benzene b. Iodobenzene c. o,p-iodobenzene d. p,p-diiodobenzene
Q5. The comparatively high boiling point of HF is due to __________. (1 mark)
a. High reactivity of F b. small size of H atom c. formation of strong H bond
d. small size of F
Oct 2022
1. Arrange the following compounds in increasing order of their boiling points. Propanol,
methoxyethane, propan-1-ol, n-Butane (1)
2. An aromatic hydrocarbon having molecular formula C 6H6 is treated with carbon
monoxide and HCl in the presence of anhydrous aluminium chloride to give compound
(Y), write the structure and name the compound ‘Y’. (1)
March 2024
1. Name reaction-1 and reaction-2 and identify the major product formed in
these reactions: (2)
----AgF------- 1?
CH3-CH2-Br -----------
-----NaI------ 2?
2. In the following reactions, write the name and structure of the major
products ‘E’ and ‘G’ formed: (3)
NaOH; 623 K HNO3
(G) Cl (E)
300 atm, H+ I Conc H2SO4
C6H5
What type of configuration is shown by bimolecular nucleophilic substitution (SN2)
reaction?

Freda