HALOALKANES AND

HALOARENES

UNIT-6
 INTRODUCTION
 The replacement of hydrogen atom(s) in a
hydrocarbon, aliphatic or aromatic, by
halogen atom(s) results in the formation of
alkyl halide (haloalkane) and aryl halide
(haloarene), respectively.
 Haloalkanes contain halogen atom(s)
attached to the sp3 hybridized carbon atom
of an alkyl group whereas haloarenes
contain halogen atom(s) attached to sp2
hybridized carbon atom(s) of an aryl group.
 USES
 Many halogen-containing organic compounds are
used as solvents for relatively non-polar compounds
and as starting materials for the synthesis of a wide
range of organic compounds.
 Chlorine containing antibiotic, chloramphenicol,
produced by soil microorganisms is very effective for
the treatment of typhoid fever.
 Our body produces the 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 anesthetic during surgery.
 Certain fully fluorinated compounds are being
considered as potential blood substitutes in surgery.
 CLASSIFICATION
On the Basis of the Number of Halogen Atoms
 Haloalkanes and haloarenes may be classified
as mono, di, or polyhalogen (tri-,tetra-, etc.)
Monohalocompounds may further be classified
according to the hybridization of the carbon atom
to which the halogen is bonded.
 COMPOUNDS CONTAINING sp3 C-X BOND
(a) Alkyl halides or haloalkanes (R—X)
 In alkyl halides, the halogen atom is bonded to an alkyl
group (R).
 They form a homologous series represented by
CnH2n+1X.
 They are further classified as primary, secondary, or
tertiary according to the nature of the carbon to which
halogen is attached.
(b) Allylic halides
These are the compounds in which the halogen atom is
bonded to an sp3 hybridized carbon atom next to
carbon-carbon double bond (C=C).IUPAC name for allyl
bromide is 3-Bromopropene.

(c) Benzylic halides

These are the compounds in which the halogen atom is
bonded to an sp3-hybridized carbon atom next to an
aromatic ring. Benzyl chloride- Chlorophenylmethane
Compounds Containing sp2 C—X Bond

(a) Vinylic halides: the halogen atom is bonded to an sp2-hybridized carbon

atom of a carbon-carbon double bond (C = C). IUPAC name for
vinylchloride is Chloroethene.

(b) Aryl halides: the halogen atom is bonded to

the sp2-hybridized carbon atom of an aromatic ring.
BOARD Qns: 2023-24
Alkyl halides
Nomenclature
 Common names are derived by naming the alkyl group followed by the
halide.
 In the IUPAC system they are named as halo-substituted hydrocarbons
The dihalo-compounds having the same type of halogen atoms are further
classified as geminal halides (halogen atoms are present on the same carbon
atom) and vicinal halides (halogen atoms are present on the adjacent carbon
atoms).
In the common name system, gem-dihalides are named alkylidene halides
and vic-dihalides are named alkylene dihalides.
In the IUPAC system, they are named dihaloalkanes.
 Aryl halides
 Haloarenes are the common as well as IUPAC
names .
 For dihalogen derivatives, the prefixes o-,
m-, p- are used in common system. In IUPAC
system, the numerals 1,2; 1,3 and 1,4 are
used.
 Give IUPAC names of the following compounds

1-Chloro-1-phenyl ethane 2, 2- Dicyclohexyl -1, 1, 1-

Trichloro ethane

4, 4-
2-Choloro-3-ethyl-2-methyl
dibromobiphenyl
pentane
TEST YOUR UNDERSTANDING:
1.The IUPAC name of tertiary butyl chloride is:
a) 4-chlorobutane
b) 2-chlorobutane
c) 1-chloro-3-methylpropane
d) 2-chloro-2-methylpropane

2. The IUPAC name of the given compound is:

e) 2,2-Dimethyl-3-chloropropane
f) 1-Chloro-2,2-dimethylpropane
g) 1-Chloro-2,2-dimethylbutane
h) 2,2-Dimethyl-3-chlorobutane

3. The IUPAC name of the given compound is:

i) 2,4,6-Tribromobenzene
j) 1,3,5-tribromobenzene
k) Tribromobenzene
l) Benzene tribromide
 Nature of C-X Bond
 Since halogen atoms are more electronegative than
carbon, the carbon halogen bond of alkyl halide is
polarized; the carbon atom bears a partial positive
charge whereas the halogen atom bears a partial
negative charge.
 Since the size of the halogen atom increases as we
go down the group in the periodic table,
consequently, the carbon-halogen bond length also
increases from C—F to C—I.
Properties based on the nature of the C-X bond
Remember that iodine is a larger atom. So, bond length in C-X
increases as we go from F to I. Bond length and dipole moment
are the opposite. Use the diagram below as a visual aid.
Compare the dipole moments of the following.
CH3F,CH3Cl,CH3Br, CH3I.
Dipole moment = Partial charge on atom x Bond length

Even though F is more electronegative, CH3Cl has greater

dipole moment because
a) the bond length in this case is far more than that in
the case of CH3F since F is highly electronegative
and it attracts the electron pair very strongly.
b) the electron affinity of chlorine is greater than that
of fluorine.
c) The charge separation is larger in CH3Cl compared
to CH3F.

Dipole moment is not just about charge, it is the product of

charge and the bond length.
Thus, the charge and distance factors are opposite to each
Electronegativity is the determining factor for the others.
other, in this case, the charge factor dominates. CH3Cl
(1.94D) has more dipole moment than CH3F (1.82D),. This is
due to greater C−Cl bond length than C−F bond length.
Haloalkanes have higher boiling points than
alkanes containing the same number of
carbons. exhibit an increase in surface area due to the
Haloalkanes
substitution of a halogen for hydrogen. The increase in surface area
leads to an increase in London dispersion forces, which then results
in a higher boiling point. Dipole-dipole interaction is the second
type of force that contributes to a higher boiling point

Arrange the alkyl halides in decreasing order of polarity:

CH3F,CH3Cl,CH3Br and CH3I

Why are alkyl halides insoluble in water?

Alkyl halides are insoluble in water because they can neither form
H-bonds with water nor they can break H-bonds between water
molecules.
Assertion( A) The boiling points of alkyl halides decrease in the order
RI > RBr > RCl > RF
Reason (R) The boiling points of alkyl chlorides, bromides and iodides are
considerably higher than that of the hydrocarbon of comparable
molecular mass.
A. Assertion and reason both are correct, and reason is correct explanation of
assertion
B. Assertion and reason both are wrong statements
C. Assertion is correct, but reason is wrong statement
D. Assertion and reason both are correct statements, but reason is not correct
explanation of assertion

Correct Answer - D Assertion and reason both are correct statements, but reason is
not the correct explanation of assertion. For the same hydrocarbon part boiling point
depends upon the atomic mass of halogen atom. Higher the mass of the halogen
atom, higher will be the boiling point. The boiling points of alkyl halides are directly
proportional to van der Waal's forces of attraction which in turn, depend upon the
molecular size.
 Methods of Preparation
1.From Alcohols
LUCAS TEST – 1° 2° and 3° alcohol
are tested by Lucas reagent. Lucas
reagent is the mixture of conc. HCl
and ZnCl2.
When Lucas reagent is added to
unknown alcohols 3°–alcohol
forms turbidity immediately. 2°
alcohol produces turbidity within
five minutes.1° alcohol does not
produce turbidity at room
temperature.

Two main disadvantages of converting alcohols to alkyl halides

using hydrogen halides:
1) The strong acidic conditions are often not suitable for organic
molecules.
2) The SN1 mechanism lacks the stereochemical control, and
rearrangements lead to different products.
1.Why is Thionyl chloride preferred in the preparation of alkyl
halide using alcohol?

Thionyl chloride is preferred because when alkyl halide is

prepared using thionyl chloride the by-products are SO2 and
HCl. These are both gases and they escape leaving behind the
desired product which is an alkyl chloride.
2.The preparation of ethyl chloride from ethyl alcohol with thionyl chloride
is carried in the presence of pyridine. Here, pyridine is used because:

Pyridine absorbs HCl (formed) and the

reaction goes forward.
3.Assertion: Phosphorus chlorides (tri and penta) are
preferred over thionyl chloride for the preparation of alkyl
chlorides from alcohols.
Reason: Phosphorus
Both A and R are false chlorides give pure alkyl halides.
4. Why do the reactions of primary and secondary
alcohols with HCl require the presence of catalyst ZnCl2?
Acid protonates the alcohol hydroxyl group, making it a good
leaving group. Because the chloride ion is a weaker nucleophile
than bromide or iodide ions, hydrogen chloride does not react
with primary or secondary alcohols unless zinc chloride or a
similar Lewis acid is added to the reaction mixture as well. Zinc
chloride, a good Lewis acid, forms a complex with the alcohol
through association with an unshared pair of electrons on the
oxygen atom. This enhances the hydroxyl’s leaving group
potential sufficiently so that chloride can displace it.
5. Which alcohol will give immediate turbidity on shaking
with HCl at room temperature?/ From amongst the
following alcohols the one that would react fastest with
conc. HCl and anhydrous ZnCl2 (LUCAS REAGENT) :
2-methylpropan-2-ol is a tertiary alcohol. It
will give immediate turbidity on shaking with
2
HCl at room temperature. This is the basis for
​ the Lucas test which is used to distinguish
, is primary, secondary, and tertiary alcohols

Lucas reagent forms carbocation as intermediate with all three

alcohols. But the stability of carbocation intermediate differs in
all three reactions. Tertiary alcohol gives instant results with
Lucas reagent as its carbocation is highly stable. While
secondary alcohol gives results with Lucas reagent after 3-5mins
as its carbocation intermediate is moderately stable and primary
alcohol don’t give any result with Lucas reagent at room
temperature because its carbocation is highly unstable. Thus, we
can write stability of carbocation intermediate of primary,
6. Aryl halides cannot be prepared by the replacement of the
hydroxyl group of phenol by a halogen atom. Why? /Why can
aryl halides not be prepared by the reaction of phenol with HCl
in the presence of ZnCl2?/Why phenols are not useful for the
preparation of haloarenes?

The C—O bond in phenols is more stable due to the resonance

effect and it has a double bond character, hence breaking this
bond is difficult. Therefore, the C-O bond in phenols is
stronger than the carbon-oxygen single bond in alcohols.
2. From Hydrocarbons:
(a) By
free radical halogenation: Chlorination/bromination of alkanes gives a mixture of
isomeric mono- and polyhaloalkanes.Therefore, the yield of a single compound is low.

(b) Byelectrophilic substitution:

Aryl chlorides and bromides are prepared using Lewis acid catalysts like iron or
iron(III)chloride.

o-and p-isomers can be separated due to large differences in M.Pts. reactions are reversible
with I2 and require HNO3/HIO4 to oxidize HI formed to I2. Fluoro compounds are not
prepared due to the high reactivity of fluorine.
Explain why alkyl halides are generally not prepared in the
laboratory by free radical halogenation of alkanes.

(i) It gives a mixture of isomeric monohalogenated

products whose boiling points are so close that they cannot
be easily separated in the laboratory.

(ii) Polyhalogenation may also occur to some extent

thereby making more complex and hence more difficult to
separate.
(c) Sandmeyer’s reaction:
When a primary aromatic amine, dissolved in cold aqueous mineral acid,
is treated with sodium nitrite, a diazonium salt is formed. Mixing
diazonium salt with cuprous chloride or bromide results in the
replacement of the diazonium group by –Cl or –Br. Sandmeyer reaction takes
place in two steps, forming the diazonium salts and transforming diazo intermediates
into aryl halides.
Copper isn’t necessary for substitution to occur if a strong enough
nucleophile is present, or if the mixture is heated enough.

Example: Aryl iodides can also be obtained from aryl diazonium salts,
through treatment with potassium iodide (KI).
7.Write a chemical reaction in which an iodide ion
displaces the diazonium group from diazonium salt.
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.

The replacement of the diazonium ion is a nucleophilic

substitution where the iodide ion (from KI) is a strong
nucleophile, so the presence of cuprous halide is not required.
In this reaction, catalysis by copper(I) is not mandatory, as
iodide itself is easily and reversibly oxidizable and, thus,
performs the function which copper(I) ions do in the Sandmeyer
reaction.
INTEXT Questions:
1. Why sulphuric acid is not used during the reaction of
alcohols with KI?
(d) From alkenes
(i) Addition of hydrogen halides:

(ii) Addition of halogens:

Which of the following on reaction with HBr will yield
2,2-dibromopropane?

a) CH3−CH=CH2
b) CH3C≡CH
c) CH3CH=CHBr
d) CH≡CH
3.Halogen Exchange
 Alkyl iodides are often prepared by reacting
alkyl chlorides/bromides with NaI in dry
acetone. This reaction is known as the
Finkelstein reaction

 The synthesis of alkyl fluorides is best

accomplished by heating an alkyl
chloride/bromide in the presence of a
metallic fluoride such as AgF, Hg2F2, CoF2,
or SbF3. The reaction is known as Swarts
reaction
 Dry acetone is used in the reaction of RX with NaI.
R - Cl + NaI - →R - I + NaCl↓

Acetone is used as the solvent because NaI is soluble in acetone whereas

NaCl is not (form a glassy precipitate), thus (via Le Chatelier's principle)
shifting the equilibrium towards the right, as NaCl precipitates out of the
reaction mixture
i) To have a single mono-chloride, there should be only one type of
H−atom. This is because the replacement of any H−atom leads to the
formation of the same product.
∴ The
ii) isomer
To have C5 H12 mono-chlorides,
3 isomeric that leads to a single mono-chloride
the isomer is neo-3
should contain
pentane. types of H−atoms.
different
∴ The isomer should be n−pentane.
iii) To have 4 isomeric mono-chlorides, the isomer should contain 4
different types of H−atoms.
∴ The isomer is 2−methylbutane.
HOME WORK:
Draw the structures of major monohalo products in each of the
following reactions :
 The reaction between cyclohexene and bromine in presence
of light gives 3-bromocyclohexene. Why is 1,2-
dibromocyclohexane
The not formed instead?
formation of 3-bromocyclohexene is an example of the
substitution of alkanes, which requires the free-radical mechanism:

In the first step of the upper mechanism, which is also the rate-
determining step, a stable allyl radical is generated, which is stabilized
by resonance:

As a result, the activation energy of the first step is significantly

lowered.
Convert
(i). 1 – Butene to 1 —
chlorobutane

ii) Benzene to o- chlorotoluene.

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

Solubility:Alkyl halides have little solubility in water

in spite of the polar carbon-halogen bond. The
attraction between the alkyl halide molecules is
stronger than the attraction between the alkyl
halide and water.
 The haloalkanes are only very slightly soluble in water. In order
for a haloalkane to dissolve in water, energy is required to
overcome the attractions between the haloalkane molecules
and break the hydrogen bonds between water molecules. As a
result, the solubility of haloalkanes in water is low.
 However, haloalkanes tend to dissolve in organic solvents
because the new intermolecular attractions between
haloalkanes and solvent molecules have much the same
strength as the ones being broken in the separate haloalkane
and solvent molecules.
INTEXT:
10.6. Arrange each set of compounds in order of
increasing boiling points.
(i) Bromomethane, Bromoform, Chloromethane,
Dibromomethane.
i) For alkyl halides containing the same alkyl group, the boiling point
(ii) 1-Chloropropane,
increases Isopropyl
with an increase in the atomicchloride,
mass of the1-Chlorobutane.
halogen atom. Since
the atomic mass of Br is greater than that of Cl, the boiling point of
bromomethane is higher than that of chloromethane. Further, for alkyl
halides containing the same alkyl group, the boiling point increases with
an increase in the number of halides. Therefore, the boiling point of
Dibromomethane is higher than that of chloromethane and
bromomethane, but lower than that of bromoform. Hence, the given set
of compounds can be arranged in the order of their increasing boiling
points as:
ii) For alkyl halides<containing
Chloromethane the same
Bromomethane < halide, the boiling point
Dibromomethane < increases
with an increase in the size of the alkyl group. Thus, the boiling point of 1-
Bromoform
chlorobutane is higher than that of isopropyl chloride and 1-
chloropropane. Further, the boiling point decreases with an increase in
branching in the chain. Thus, the boiling point of isopropyl alcohol is
lower than that of 1-chloropropane. Hence, the given set of compounds
can be arranged in the increasing order of their boiling points as:
Isopropyl chloride < 1-Chloropropane < 1-Chlorobutane
Which of the following has the highest m.pt? CBSE 2023
SET-2
a) o-Dichlorobenzene
b) m-Dicholorbenzene
c) p-Dichlorobenzene
d) All have the same m.pt

Which of the following belongs to the class of alkyl halides? SET-

3
a) CH2 = CH-Cl
b) CH2 = CH-CH2-CH2-Cl
c) CH2 = CH-CH(Cl) –CH3
d) CH ≡ C-CH2-Cl (Alkenyl group)
 Alkenes have more of an s character,
so they tightly hold the
electronegative chloride ions towards
themselves making the C-Cl bond
length shorter than alkyl chlorides. In
aryl halides, the ring produces strain
on the Cl atom because of resonance
and shows a double bond character
so it has the shortest C-Cl bond
length. Hence, the correct order is A
In CH3 −Cl the carbon atom is sp3 hybridized while
in chlorobenzene the carbon atom is sp2 hybridized.
The sp2 hybridized carbon is more electronegative
due to greater s-character and holds the electron
pair of the C-Cl bond more tightly.
 Chemical Reactions
Reactions of Haloalkanes
(i) Nucleophilic substitution reactions: A nucleophile reacts
with haloalkane having a partial positive charge on the carbon
atom bonded to halogen. A substitution reaction takes place and
halogen atom, called leaving group departs as halide ion.

 Groups like cyanides and nitrites possess two nucleophilic centers

 and are called ambident nucleophiles. cyanide group is a
hybrid of two contributing structures and therefore can act as a
nucleophile in two different ways, linking through carbon atom
resulting in alkyl cyanides and through nitrogen atom leading to
isocyanides.
 Similarly, nitrite ion also represents an ambident nucleophile. The
linkage through oxygen results in alkyl nitrites while through
nitrogen atoms, it leads to nitroalkanes.
Haloalkanes react with KCN to form alkyl cyanides as
the main product while with AgCN, they form
isocyanides
KCN is ionic in as the and
nature chief product.
provides Give ions
cyanide reason.
in solution.
Although both carbon and nitrogen atoms are in a position to
donate electron pairs, the attack takes place mainly through
the carbon atom and not through the nitrogen atom since the
C−C bond is more stable than the C−N bond.

KCN + C2H5Cl → C2H5CN

+ KCl
AgCN is mainly covalent in nature. Here only nitrogen is free to
donate electron pair, hence it forms isocyanide as the main
product.
AgCN + C2H5Cl → C2H5NC +
AgCl
 Mechanism:
 (a) Substitution nucleophilic bimolecular (SN2)
 Follows second-order kinetics, the rate depends upon the
concentration of both reactants.(substrate and the nucleophile).
The incoming nucleophile interacts with the 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. Inversion of the configuration
happens during the reaction. Order of reactivity: Primary
halide > Secondary halide > Tertiary halide.
SN2 reaction mechanism requires the attack of
nucleophiles from the back side of the carbon atom. So,
the product assumes a stereochemical position opposite
to the leaving group originally occupied. This is called
the inversion of configuration. SN2 reaction is the most
common example of Walden inversion where an
asymmetric
The rate ofcarbon atom
this type ofundergoes inversion
reaction is of by
affected configuration.
the following
factors:
1. The unhindered back of the substrate makes the formation of the
carbon-nucleophile bond easy. Therefore, methyl and primary
substrates undergo nucleophilic substitution easily.

2. Strong anionic nucleophiles speed up the rate of the reaction

.
3. Polar aprotic solvents do not hinder the nucleophile, but polar
solvents form hydrogen bonds with the nucleophile. A good solvent
for this reaction is acetone.

4. Stability of the anion of the leaving group and the weak bond
strength of the leaving group’s bond with carbon help increase the
The nucleophile donates a pair of electrons into the most accessible
empty orbital, which is the antibonding (σ*) orbital of the C-(LG)
bond, which resides at 180° to the bond. Donation of a pair of
electrons into the antibonding orbital results in the fission of the
bond. It’s kind of like an “eject button” in that way.
(b) Substitution nucleophilic
unimolecular(S N )
1
 S 1 reactions are generally carried out in polar protic solvents.
N

 Follows the first-order kinetics, the rate of reaction depends

upon the concentration of only one reactant.
 Step I: the polarized C—Br bond undergoes slow fission to
produce a carbocation and a bromide ion.(reversible)
 Step II: The carbocation thus formed is then attacked by
nucleophiles.
 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 ions.
 Order of reactivity: R–I> R–Br>R–Cl>>R–F. And 3o ˃ 2o ˃ 1o
Allylic and benzylic halides show high reactivity toward
SN1 reaction. Why?
In allylic and benzylic halides, the carbocation formed
undergoes stabilization through the resonance. Hence, allylic
and benzylic halides show high reactivity towards the SN1
reaction. The resonating structures are:

Resonance stabilization of allylic

carbocation

Resonance stabilization of benzylic

carbocation
In the following pairs of halogen compounds,
which compound undergoes a faster SN1
reaction?
Since 3° carbocation is more stable than 2° carbocation.
2−chloro-2-methylpropane undergoes a faster SN1 reaction than
3-chloropentane.

(ii)

The alkyl halide (I) is 2° while (II) is 1°. 2° carbocation is more stable
than 1° carbocation. herefore 2−chloroheptane, undergoes faster SN1
reaction than 1-chlorohexane
In the following pair of halogen compounds, which would
undergo SN2 reaction faster?

1.Due to steric 2. Iodide is a better leaving group

hindrance, the because of its larger size, it will be
secondary halide is released at a faster rate in the
less reactive compared presence of incoming nucleophiles.
to the primary halide . Hence, (I) is more reactive
towards the SN2 compared to (II) .
reaction. Hence, (I), is
the primary halide and
therefore undergoes
SN2 reaction faster.
The correct increasing order of the reactivity of
halides for SN1 reaction is:

order of the stability of carbocation

formed is:
Among the bromides I-III is given below, the order of
reactivity in the SN 1 reaction is:

Arrange the following isomeric bromides in order of

decreasing reactivity in SN2 ​ displacement.

Due to the presence of substituents, a hindrance to the

approaching nucleophile increases in the following order.

1-Bromopentane < 2-bromopentane < 2-Bromo-2-

methylbutane
Hence, the increasing order of reactivity toward SN 2
displacement is
2-Bromo-2-methylbutane < 2-Bromopentane < 1-Bromopentane
In the following pair of halogen compounds, which would undergo
SN1 reaction faster?

Chlorobenzene will undergo faster SN 1 because of the greater stability of

secondary carbocation.

Assertion: Nucleophilic substitution of iodoethane is easier than chloroethane

Reason: The bond energy of the C-Cl bond is less than the C-I bond
(Less effective bonding 2p of carbon and 5p of iodine compared to 2p of carbon
and 3p of chlorine. A is true R is false) CBSE 2023-SET-1/2/3
Arrange the following compounds in order of decreasing
SN1 reaction rate.

The presence of a benzene ring stabilizes carbocation by

the resonance of charge in the ring. Hence, (IV) is more
reactive than (I).
The stability of carbocation is :

Hence, (II) is more reactive than (III).

The larger alkyl group has a higher +I effect that also stabilizes
carbocation.

Hence the order of reaction rate is:

(c) Stereochemical aspects of nucleophilic
substitution reactions
(i) Plane polarized light and optical activity:
optically active compounds rotate the plane polarized
light (produced by passing ordinary light through Nicol
prism) when it is passed through their solutions.
 If the compound rotates the plane polarized light to the
clockwise direction, it is called dextrorotatory or the d-
form and is indicated by placing a positive (+) sign before
the degree of rotation.
 If the light is rotated towards an anticlockwise direction)
the compound is said to be laevorotatory or the l-form
and a negative (–) sign is placed before the degree of
rotation.
 Such (+) and (–) isomers of a compound are called optical
isomers and the phenomenon is termed optical
isomerism.
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 (ii) Molecular asymmetry, chirality and
 enantiomers:
Crystals of certain compounds exist in the form of mirror images. Aqueous
solutions of both types of crystals showed optical rotation, equal in magnitude
(for the solution of equal concentration) but opposite in direction.
 Arrangement of four groups around a central carbon is tetrahedral and if all the
substituents attached to that carbon are different, such carbon is called
asymmetric carbon/chiral carbon or stereocentre. Chiral molecules are
optically active, while the objects, which are, superimposable on their mirror images
are called achiral. These molecules are optically inactive. The asymmetry of the
molecule is responsible for optical activity. The stereoisomers related to each other
as non-superimposable mirror images are called enantiomers


Propan-2-ol (A) does not

contain an asymmetric
carbon, as all the four groups
attached to the tetrahedral
carbon are not different. We
rotate the mirror image (B) of
the molecule by 180°
(structure C) and try to
overlap the structure (C) with
the structure (A), these
structures completely overlap.
 Butan-2-ol has four different groups attached to the tetrahedral carbon
and as expected is chiral. Some common examples of chiral molecules
such as 2-chlorobutane, 2, 3-dihyroxypropanal, (OHC–CHOH–CH2OH),
bromochloro-iodomethane (BrClCHI), 2-bromopropanoic acid (H3C–CHBr–
COOH), etc. The stereoisomers related to each other as non-
superimposable 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 optical isomer plane-polarised is dextro
rotatory, the other will be laevo rotatory.
However, the sign of optical rotation is not necessarily related to the
absolute (actual) configuration of the molecule.
Identify chiral and achiral molecules in each of
the following pairs of compounds.
SN1 reactions are accompanied by racemization
in optically active alkyl halides.

The carbocation formed in the slow step being sp2

hybridized is planar (achiral). The attack of the
nucleophile may be accomplished from either side of
the plane of carbocation. Depending upon the position
of the newly bonded nucleophile two types of products
are possible.one of which has same geometry as that
the reactant, or it retains its original geometry hence
called retention and other will inverse its geometry
called inversion. The 50 % mixture of both inverted
and retained geometry is called racemic mixture and
process is called racemization.
Hydrolysis of optically active 2-Bromobutane forms optically
inactive butan-2-ol. Why?
Optically active 2-Bromobutane is a chiral compound that exists in two
enantiomeric forms (mirror images) that rotate plane-polarized light in opposite
directions.

( ± ) -2 Butanol is a racemic mixture and hence contains equal amounts of the

two enantiomers, i.e, (+)-2- butanol and (-)-2- butanol. (+)-2-butanol rotates
the plane of polarized light toward right, whereas (-)-2-butanol rotates the
plane of polarized light towards left but to the same extent. The overall
rotation is zero and hence ( ± ) -2-butanol is optically inactive.
The carbocation intermediate formed during the reaction is achiral, and
therefore, the product formed from it is a racemic mixture of its enantiomers.
Hence, the optical activity of the initial compound is lost during the hydrolysis
reaction.
(iii) Retention:
 Retention of configuration is the preservation of
integrity of the spatial arrangement of bonds to an
asymmetric centre during a chemical reaction or
transformation.
 If during a reaction, no bond to the stereocentre is
broken, the product will have the same general
configuration of groups around the stereocentre as
that of reactant. Such a reaction is said to proceed
with retention of the configuration.
(iv) Inversion, retention and
racemisation:
for a reaction at an asymmetric carbon atom.
 If (A) is the only compound obtained, the process is called
retention of configuration.
 If (B) is the only compound obtained, the process is called
inversion of configuration.
 If a 50:50 mixture of the above two is obtained then the
process is
 called racemization and the product is optically inactive.
 In the following pairs, which compound
undergoes a faster SN1 reaction?

(i) H3C CH CH2 CH2 Br or H3C CH2 CH CH2 Br

CH3 CH3

Cl
(ii) or Cl

(A) (B)

Ans : (i) B (ii) A

 Elimination reactions
 When a haloalkane with β- hydrogen atom is heated with
an alcoholic solution of potassium hydroxide, there is the
elimination of a hydrogen atom from β-carbon and a halogen
atom from the α-carbon atom.it is often called β-elimination.
 If there is the possibility of the formation of more than one alkene
due to the availability of more than one β-hydrogen atoms,
usually one alkene is formed as the major product.
 The formation of products is governed by the
Zaitsev(Saytzeff) rule -
 “in dehydrohalogenation reactions, the preferred product
is that alkene which has the greater number of alkyl
groups attached to the doubly bonded carbon atoms”
Saytzeff's rule: In dehydrohalogenation reactions, the major
product is the alkene with a lesser number of hydrogen atoms on the
doubly bonded carbon atoms.
'Poor becomes Poorer'. That's because carbon which is poor in hydrogen
becomes poorer by losing hydrogen. So, the major product is the
compound in which carbon with a lesser number of hydrogen atoms loses
more hydrogen atoms.
Assertion :2-Bromobutane on reaction with sodium
ethoxide in ethanol gives 1-butene as a major product.
Reason: 1-Butene is more stable than 2-butene.
 • 1. With magnesium:
Reaction with metals

• An important class of organo-metallic compounds alkyl magnesium halides,

RMgX, referred to as Grignard Reagents. These reagents are obtained by the
reaction of haloalkanes with magnesium metal in dry ether.One of the methods
for converting halides to hydrocarbons.

In the Grignard reagent, the C-Mg bond is covalent but highly polar, with carbon pulling
electrons from electropositive magnesium; the Mg-X bond is essentially ionic.

Grignard reagents are highly reactive and react with any source of proton to give
hydrocarbons. Even water, alcohols, and amines are sufficiently acidic to convert them
to corresponding hydrocarbons. It is therefore necessary to avoid even traces of
moisture and the reaction is carried out in dry ether.

WURTZ REACTION: with sodium in dry ether

WURTZ REACTION: Alkyl halides with sodium in dry ether

2R-X + 2Na → R-R + 2Na+ X–

Wurtz-Fittig reaction: Alkyl and aryl halides react in the presence

of dry ether and sodium metal to give alkyl-aryl substituted product.

Fittig reaction: Two aryl halides are coupled in presence of sodium

metal in dry ether or tetrahydrofuran to furnish biaryls.
SECTION-C cbse-2023-set2

30 .ii)
SECTION-D (4marks) CBSE-2023-SET-1/2/3
i). What happens when bromobenzene is treated with Mg in the presence
of dry ether?
ii). Which compound among the following pairs will react faster in the SN1
reaction with OH -?
a) CH2=CH-CH2-Cl or CH3-CH2-CH2-Cl
b) (CH3)3C-Cl or CH3Cl
iii) Write the equations for the preparation of 1-Iodobutane from:
a) 1-Chlorobutane
b) But-1-ene (cannot be carried out with HI directly?)
OR
iii) Write the structure of the major products in each of the
following reactions:
a) CH3CH(Br)CH3 +KOH –Ethanol-- Heat--˃
b) C6H5Cl + CH3COCl ---Anhyd.AlCl3---˃
i)

ii) a) CH2=CH-CH2-Cl
b) (CH3)3C-Cl

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

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

of haloarene, the carbon atom attached to halogen is sp2-hybridized.
• With a greater s-character is more electronegative and can hold the
electron pair of C—X bond more tightly than sp3-hybridized carbon in
haloalkane therefore, haloarenes are less reactive than haloalkanes
towards nucleophilic substitution reaction.
(iii) Instability of phenyl cation: In the case of haloarenes, the phenyl cation formed as a
result of self-ionization will not be stabilized by resonance and therefore, the SN1
mechanism is ruled out.
(iv) Because of the possible repulsion, it is less likely for the electron-rich nucleophile to
approach electron-rich arenes

Replacement by a hydroxyl group

Chlorobenzene can be converted into phenol by heating in an aqueous sodium
hydroxide solution at a temperature of 623K and a pressure of 300 atmospheres.
The presence of an electron-withdrawing group (-
NO2) at ortho- and para-positions increases the
reactivity of haloarenes.
The differences between electrophilic and nucleophilic
aromatic substitution
• The electrophilic substitutions are favored by electron-
donating substituents which stabilize the carbocation
intermediate. and replace hydrogen on the ring.
• The nucleophilic substitutions are favored by electron-
withdrawing substitutions, which stabilize a carbanion
intermediate and replace a leaving group, usually a halide ion.
 The effect is pronounced when the (-NO2) group is introduced at o- and p-
positions. However, no effect on the reactivity is observed at the m-position. The
nitro group at o- and p-positions withdraws the electron density from the benzene
ring and thus facilitates the attack of the nucleophile. The carbanion thus formed
is stabilized by resonance. The negative charge at o- and p-positions w.r.t the
halogen substituent is stabilized by the –NO2 group while in the case of m-
nitrobenzene, none of the resonating structures bear the negative charge on the
C- atom bearing the –NO2 group. So, the presence of the nitro group at the m-
position does not stabilize the negative charge.
 Electrophilic •Nitration
substitution reactions
 Halogen atom besides being slightly deactivating is o, p
directing; therefore, further substitution occurs at ortho- and
para positions.
 Halogenation

 Nitration
Sulphonation

Friedel-Crafts reaction
Although chlorine is an electron-withdrawing group, yet it is
ortho-, para-directing in electrophilic aromatic substitution
Chlorine withdraws
reactions. Why? electrons through inductive effect and releases
electrons through resonance. Through inductive effect, chlorine
destabilizes the intermediate carbocation formed during the electrophilic
substitution.

Through resonance, halogen tends to stabilize the carbocation and the

effect is more pronounced at ortho- and para-positions. The inductive effect
is stronger than resonance and causes net electron withdrawal and thus
causes net deactivation. The resonance effect tends to oppose the inductive
effect for the attack at ortho- and para-positions and hence makes the
deactivation less for ortho- and para- attack. Reactivity is thus
controlled by the stronger inductive effect and orientation is
 Polyhalogen Compounds
Dichloromethane (Methylene chloride)
 Dichloromethane is widely used as a solvent as a paint
remover, as a propellant in aerosols, and as a process
solvent in the manufacture of drugs.
 It is also used as a metal cleaning and finishing solvent.
 Methylene chloride harms the human central nervous
system.
 Exposure to lower levels of methylene chloride in the air
can lead to slightly impaired hearing and vision.
 Higher levels of methylene chloride in the air cause
dizziness, nausea, tingling, and numbness in the fingers
and toes. In humans, direct skin contact with methylene
chloride causes intense burning and a mild redness of
the skin. Direct contact with the eyes can burn the
cornea.
 Trichloromethane (Chloroform) CHCl3
 Chemically, chloroform is employed as a solvent for fats, alkaloids,
iodine and other substances. The major use of chloroform today is
in the production of the freon refrigerant R-22.
 Inhaling chloroform vapors depresses the central nervous system.
 Breathing about 900 parts of chloroform per million parts of air for
a short time can cause dizziness, fatigue, and headache. Chronic
chloroform exposure may cause damage to the liver (where
chloroform is metabolized to phosgene) and to the kidneys, and
some people develop sores when the skin is immersed in
chloroform. Chloroform is slowly oxidized 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, but the antiseptic properties
are due to the liberation of free iodine and not due to iodoform
itself. Due to its objectionable smell, it has been replaced by
other formulations containing iodine.
How is iodoform prepared from ethanol? Give a
balanced equation.

The iodoform reaction also produces a yellow solid that precipitates from
the mixture. This yellow solid produced from the iodoform reaction is called
iodoform. Since acetone is a methyl ketone, it can be used to prepare
iodoform.
Freons
 The chlorofluorocarbon compounds of
methane and ethane are collectively known
as freons.
 They are extremely stable, unreactive, non-
toxic, non-corrosive and easily liquefiable
gases. Freon 12 (CCl2F2) is one of the most
common freons in industrial use.
 It is manufactured from tetrachloromethane
by Swarts reaction. These are usually
produced for aerosol propellants,
refrigeration and air conditioning purposes.
 Most freon, even that used in refrigeration,
eventually makes its way into the
 What is freon? How is it prepared from CCl4? Write its
important uses.
The chlorofluoro compounds of methane and ethane are collectively
known as freon. These are unreactive, and is stable even under high
temperature and pressure.
Preparation : When carbon tetrachloride is treated with antimony
fluoride in the presence of antimony pentachloride, freon is formed.

Uses : Freon is used as refrigerant in refrigerators and air

conditioners.
Write the formula of Freon- 11

Trichlorofluoromethane, also called freon-11, CFC-11, or R-11, is a

chlorofluorocarbon. It is a colorless, faintly ethereal, and sweetish-
smelling liquid that boils around room temperature.Formula -
Freon−11=CFCl3
CHClF2
​ is Freon R-22.
CCl 2F2 is freon R-12
CCl3NO2 chloropicrin
4 Tetrachloromethane (Carbon
tetrachloride)
 It is used in the manufacture of refrigerants and
propellants for aerosol cans.
 It is used as feedstock in the synthesis of
chlorofluorocarbons and other chemicals,
pharmaceutical manufacturing, and general solvent use.
 Exposure to carbon tetrachloride can cause liver cancer
in humans. The most common effects are dizziness,
lightheadedness, nausea, and vomiting, which can
cause permanent damage to nerve cells. In severe
cases, these effects can lead rapidly to stupor, coma,
unconsciousness or death. Exposure to CCl4 can make
the heart beat irregularly or stop. The chemical may
irritate the eyes on contact.
 It depletes the ozone layer. Depletion of the ozone
layer increases human exposure to ultraviolet rays,
leading to increased skin cancer, eye diseases and
Dichlorodiphenyltrichloroethane (DDT)C14H9Cl5
IUPAC name of DDT is
1,1'-(2,2,2-Trichloroethane-1,1-
diyl)bis(4-chlorobenzene)
OR
1,1,1-Trichloro-2,2-bis(4-
chlorophenyl)ethane
 DDT was the first chlorinated organic insecticide.
 The use of DDT increased enormously on a worldwide basis after World War
II, primarily because of its effectiveness against the mosquito that spreads
malaria and lice that carry typhus.
 Problems related to the extensive use of DDT began to appear in the late
1940s. Many species of insects developed resistance to DDT, and it was also
discovered to have high toxicity towards fish. The chemical stability of DDT
and its fat solubility compounded the problem. DDT is not metabolized very
rapidly by animals; instead, it is deposited and stored in fatty tissues.
 If ingestion continues at a steady rate, DDT builds up within the animal over
time. The use of DDT was banned in the United States in 1973, although it is
still in use in some other parts of the world.
DDT is prepared by heating chlorobenzene and
chloral in the ratio of 2:1 in the presence of
concentrated sulphuric acid.
Arrange the following halides in decreasing order of
dipole moment
(a)>(d)>(b)>(c)
Optically active 2 -Iodobutane on treatment with Nal in
acetone gives a product that does not show optical
activity. Explain briefly.
This is an example of an SN2 reaction.SN2 reaction involves the product
formation with inversion of configuration. When one molecule of the
original substance undergoes inversion, one molecule of product is
formed with inversion of configuration.
Optically active molecules lose their optical activity due to the
occurrence of racemization i.e. when one molecule is inverted, two
molecules are racemized.
Arrange the following in increasing order of property
indicated

1-Bromo-3-methylbutane, 2-Bromo-2-
methylbutane, 3-Bromo-2-methylbutane. ( SN2 )
1-Bromo-3-methylbutane < 2-Bromo-2-methylbutane < 3-
Bromo-2-methylbutane.

Br OH
Br D and E is isomers
C H -C H 3 CH=CH 2 C H -C H 3 C H -C H 3

a lc. K O H HBr H 2O

(B ) (C ) (B ) (E )

C H 2 -C H 2 -B r CH=CH 2 C H 2 -C H 2 -B r C H 2 -C H 2 -O H

a lc. K O H HBr H 2O
p ero xid e

(A ) (D )
Dehydrobromination of compounds (A) and (B) yield the
same alkene (C). Alkene (C) can regenerate (A) and (B) by
the addition of HBr in the presence and absence of
peroxide respectively. Hydrolysis of (A) and (B) give
isomeric products (D) and (E) respectively. 1, 1-
Diphenylethane is obtained on the reaction of (C) with
benzene in presence of H+. Give structures of (A) to (E)
It is given
with that the compound C (alkene) on treatment with benzene in
reasons.
presence of H+ ion gives 1, 1- diphenylethane. Clearly, compound (C)
must be styrene. It is an example of the Friedel-Craft reaction.
As the
dehydrobromination of
(A) and (B) give the same
alkene (C). Clearly, (A)
and (B) must be isomeric
aralkyl halides. (C) on
treatment with HBr in
the presence and
absence of peroxide
gives (A) and (B)
respectively.
The dipole moment of chlorobenzene is lower than that of cyclohexyl
chloride. Why?

In chlorobenzene C-Cl bond is sp2 hybridised whereas in

cyclohexyl chloride the C − C l bond is sp3 Hybridised . As sp2
has more s character and more electronegative than sp3.
Chlorobenzene is less polar than cyclohexyl chloride.
Chemical distinction:
a) Chlorobenzene and cyclohexyl chloride(AgNO3 test)
b) Allyl chloride and Vinyl chloride (Vinyl chloride does not respond to
NaOH and silver nitrate test because of double bond character due to
resonance. This stops the release of chloride ions.)
c) Allyl/Vinyl chloride and n- propyl chloride
d) Chloroform and carbon tetrachloride(Carbylamine test)
e) chlorobenzene and benzyl chloride

CH2=CH-CH2Br
3-Bromoprop-1-ene

e) AgNO3 test
1. Sandmeyer Reaction :
The Cl , Br and CN nucleophiles can easily be introduced in the benzene ring
of benzene diazonium salt in the presence of Cu(I) ion. This reaction is called
Sandmeyer reaction.

N
+
N X
Cl
C u 2X 2
(where X= C l or B r )
+ N2
.
B en zen e d ia zo n iu m H a lo b en zen e ( H a lo a ren e)
C h lo rid e

Finkelstein Reaction
Alkyl iodides are often prepared by the reaction of alkyl chlorides/ bromides with
NaI in dry acetone. This reaction is known as Finkelstein reaction.
CH 3CH 2 -C  dry
 NaI
  CH 3CH 2 -I + NaC
Acetone
Chloroethane Iodoethane

Note: This reaction in forward direction can be favoured by precipitating

NaX formed in dry acetone (according to Le Chatelier’s principle).
 • Conversion:
CH3 C H2C l CH 2CN C H 2C O O H
alc.KCN H + /H 2 O
Cl 2 / hv
C om plete
-HCl -KCl hydrolysis

Toluene B ez y lc hloride 2-P henylethanenitrile 2-P henylethanoic acid

CH CH
P I3 H3C CH2 C CH
C H 3 -C H 2 -O H C H 3 -C H 2 -I
NaNH2
E th a n o l Io d o e th a n e B u t-1 -yn e
1. Thionyl chloride is preferred for converting alcohol to
haloalkane.
Ans. Thionyl chloride is preferred for converting alcohol to haloalkane
because the by products formed are all gases that escape into the
atmosphere.

2. Phenol cannot be converted to chlorobenzene by reacting with

HCl.
Ans. In phenol, due to resonance, the carbon–oxygen bond has a partial
double bond character and is difficult to break is stronger than a single
bond. Therefore it can not be converted to chlorobenzene by reacting
3. HNO3
with HCl. is added during the iodination of benzene.
Ans. When benzene is reacted with iodine, the reaction is reversible in
nature. It leads to the formation of reactants back. Therefore an oxidizing
agent like HNO3 oxidizes the HI formed in the reaction and keeps the
reaction
4. in the forward direction.
p- dichlorobenzene has higher melting point than meta –
dichlorobenzene.
p- dichlorebenzene has a symmetrical
structure therefore it can fit better
into the crystal lattice which
increases its melting point.
5. The boiling points of isomeric haloalkenes decrease with an
increase in branching.
Ans. The boiling points of isomeric haloalkanes decrease with branching
due to a decrease in surface areas with branching. As branching
increases, the structure becomes more spherical and the surface area
decreases. e.g. the boiling points of isomers of C4H9Br follow the order.

6. Hydrolysis of optically active 2- bromobutane forms optically

inactive butan – 2 – ol.

The compound undergoes hydrolysis by SN1

mechanism via the formation of carbocation
which is planar
The attack of nucleophiles can result in a product which is a mixture of
compounds both with the same configuration and inverted
configuration.

Therefore it results in the formation of a racemic mixture that is

optically inactive.
7. Chlorobenzene is less reactive towards nucleophilic
substitution reaction.
Ans. Chlorobenzene is less reactive towards nucleophilic substitution
due to –
a) resonance, C- Cl bond acquires a double bond character and
becomes stronger than a single bond.
b). The hybridization in C of the C-X bond, the carbon becomes more
electronegative and holds the electron pair of the C-X bond more
tightly decreasing the bond length.
c). Instability of phenyl cation.
d). Repulsion for incoming nucleophiles from the electron-rich ring.
8. Chloroform is stored in dark-colored bottles.
Ans. Chloroform gets oxidized slowly by air in the presence of light to
extremely poisonous gas phosgene. Therefore to avoid any exposure to
air and sunlight, it is kept in dark-colored bottles.

9. The order of boiling points is RCl < RBr < RI.

Ans. The boiling points of alkyl halides depend on the dipole and van-
der-waal’s interaction. These attractions get stronger as the molecules
get bigger in size and have more electrons. As the size of halogens
increases in the order –

The boiling points also follow the order:RCl < RBr <RI
10. Vinyl chloride is less reactive than allyl chloride.
Ans. Due to resonance C- Cl bond gets double bond character and
becomes stronger than a single bond, making vinyl chloride less
reactive than allyl chloride.
11. What happens when
a) Thionyl chloride acts upon I – propanol.
b) Ethanol reacts with PBr3
Ans. (a) When thionyl chloride acts upon 1- propanol chloropropane is
formed .

b) When ethanol reacts with PBr3, bromoethane is formed.

12. How many aromatic isomers are possible for the formula ? Write the
structure and names.
Ans. -Three aromatic isomers are possible
13. How is chlorobenzene
prepared by
(a) direct chlorination
(b) diazotization method?
Ans. (a) by direct chlorination-

b) by diazotization method.
14. How can we distinguish between an alkyl halide and aryl
halide?

3 Mark Questions
Further, the hydrocarbon gives a single monochloro
compound C5H9Cl, by reacting with chlorine in bright
sunlight. Since a single monochloro compound is formed,
the hydrocarbon must contain H-atoms that are all
equivalent. Also, as all H-atoms of a cycloalkane are
equivalent, the hydrocarbon must be a cycloalkane. Hence,
the said compound is cyclopentane.
11. Write the equations for the preparation of 1-iodobutane from
(i) 1-butanol
(ii) 1-chlorobutane
(iii) but-1-ene.
12. What are ambident nucleophiles? Explain with an example.
Ans. Ambident nucleophiles are nucleophiles having two nucleophilic sites. Thus,
ambident nucleophiles have two sites through which they can attack.
For example, nitrite ion is an ambident nucleophile.

Nitrite ions can attack through oxygen resulting in the formation of alkyl nitrites. Also, it
can attack through nitrogen resulting in the formation of nitroalkanes.
 5 Mark Questions

1. Write structures of the following compounds:

(i) 2-Chloro-3-methylpentane
(ii) 1-Chloro-4-ethylcyclohexane
(iii) 4-tert. Butyl-3-iodoheptane
(iv) 1,4-Dibromobut-2-ene
(v) 1-Bromo-4-sec. butyl-2-methylbenzene
Since D of D2O gets attached to the carbon atom to which MgBr
is attached, C is
Name the following halides according to IUPAC system and
classify them as alkyl, allyl, benzyl (primary, secondary, tertiary),
vinyl or aryl halides:
(i) (CH3)2CHCH(Cl)CH3
(ii) CH3CH2CH(CH3)CH(C2H5)Cl
(iii)CH3CH2C(CH3)2CH2I
(iv)(CH3)3CCH2CH(Br)C6H5
(v) CH3CH(CH3)CH(Br)CH3
(vi)CH3C(C2H5)2CH2Br
(vii) CH3C(Cl)(C2H5)CH2CH3
(viii) CH3CH=C(Cl)CH2CH(CH3)2
(ix) CH3CH=CHC(Br)(CH3)2
(x) p-ClC6H4CH2CH(CH3)2
(xi) m-ClCH2C6H4CH2C(CH3)3
(xii) o-Br-C6H4CH(CH3)CH2CH3
How will you distinguish between the following (give
one chemical test):
(a) Chlorobenzene and chlorocyclohexane
(b) Chlorobenzene and benzyl chloride
(c) Ethyl chloride and vinyl chloride
(d) Chlorobenzene and n-hexylchloride
(e) Chloroethane and bromoethane
(f) 3-Bromopropene and 1-bromopropane.
CONVERSIONS:
Chlorobenzene to phenol.

Methyl bromide to acetic acid.

2- Chlorobutane to sec- butyl

ethyl ether
Chlorobenzene to benzyl alcohol

Chlorobenzene to Benzene

1- chloropropane to 2-
iodopropane.
THANK
YOU