Haloalkanes and Halo

IUPAC
Q1

Name the following compounds according to

IUPAC system. (i) (CH3)3CCH2CH(Br)C6H5 (ii)
CH3C(C2H5)2CH2Br
(iii) CH3CH=CHC(Br)(CH3)2 (iv) o-BrC6H4CH(CH3)CH2CH3
(v) m-ClCH2C6H4CH2C(CH3)3
(vi) CH3C(p-ClC6H4)2CH(Br)CH3
(vii) (CH3)3CCH=CClC6H4I-p

(iv)
benzene

(v)

1Chloromethyl3(2, 2dimethylpropyl)

1Bromo2(1methylpropyl) benzene

Answer

(vi)

2Bromo3, 3bis(4chlorophenyl)

(i)
1Bromo3,
3dimethyl1phenylbutane

butane (vii)
1chloro1(4iodophenyl)3,3dimethylbut1ene
(ii)

1Bromo2ethyl2methylbutane

Q2

Write the structures and IUPAC name of the

following organic halogen compounds
(i)isobutyl bromide (ii)tertiarybutyl bromide (i)
2Bromo2methylpropane

(iii)

4Bromo4methylpent2ene
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(iii) 3-Bromocyclohexanol
(iv) Hex-1-en-3-ol
(v) 2-Bromo-3-methylbut-2-en-1-ol
(vi) 4-Bromo-3-methylpent-2-ene
(ii)

1Bromo2methylpropane

Q4

Q3
Name the following compounds according to
IUPAC system.

Write the structures of the following organic

halogen compounds (i) 2-(2-Chlorophenyl)-1iodooctane
(ii) 1-Bromo-4-sec-butyl-2-methylbenzene

Answer

(i)
(i)
(ii)
(ii)
Q5

(iii)

Write IUPAC names of the following compounds:

(iv)
(i)
(v)
(ii)
(vi)
Answer (i) 3-Chloromethyl-2-isopropylpentan-1-ol
(ii) 2, 5 Dimethylhexane-1, 3-diol
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(iii)

(iii)
(v)

(iv)

Answer1

(v)
(vi)
(vii)
Answer

(i)

(i) 2, 2, 4-Trimethylpentan-3-ol
(ii) 5-Ethylheptane-2, 4-diol
(iii) 1-Methoxy-2-methylpropane
(iv) 2, 6-Dimethylphenol
(v) 2-Ethoxybutane
(vi) 1-Phenoxyheptane
(vii) Ethoxybenzene

(ii)

INCOMPLETE

(iii)

Q1 Draw the structures of major monohalo

products in
each of the following reactions:
(iv)
(i)

(ii)

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(iv)
(vi)

(v)

(vi)
Q2

Identify A, B, C, D, E, R and R1 in the following:

When an alkyl halide is treated with Na in the presence

of ether, a hydrocarbon containing double the number
of carbon atoms as present in the
original halide is obtained as product.
This is known as Wurtz reaction.
Therefore, the halide, R1X, is
Therefore, compound D is-And,
compound E is

Answer2

Since D of D2O gets attached to the carbon atom to which

MgBr is attached, C is

Q3

Therefore, the compound R Br is

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Write the products of the following reactions:

(ii)

Answer 3
(iii)

Q4 Predict the products of the following

reactions:

(iv)
Q5 Predict all the alkenes that would be formed
by dehydrohalogenation of the following
halides with sodium ethoxide in ethanol and
identify the major alkene:

(i)

(ii)

(iii)

(i) 1-Bromo-1-methylcyclohexane
(ii) 2-Chloro-2-methylbutane
(iii) 2,2,3-Trimethyl-3-bromopentane.
Answer 5

(iv)
(i)

Answer 4

1bromo1methylcyclohexane
In the given compound, all -hydrogen atoms are
equivalent. Thus, dehydrohalogenation of this
compound gives only one alkene.

(i)

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hydrogen atoms labelled as a and b. Thus,

dehydrohalogenation of the compound yields two
alkenes.
(ii)
(iii) In the given compound, there are two different sets
of equivalent -hydrogen atoms labelled as a and b.
Thus, dehydrohalogenation of the compound yields two
alkenes.

According to Saytzeffs rule, in dehydrohalogenation

reactions, the alkene having a greater number of alkyl
groups attached to the doubly bonded carbon atom is
preferably formed.

Saytzeffs rule implies that in dehydrohalogenation

reactions, the alkene having a greater number of alkyl
groups attached to a doubly bonded carbon atoms is
preferably produced.
Therefore, alkene (I) i.e., 2-methylbut-2-ene is the major
product in this reaction.

1 How will you bring about the following conversions?

(i)
(ii)

Ethanol to but-1-yne
Ethane to bromoethene
(iii)
(iv)

(iii)
2,2,3-Trimethyl-3-bromopentane
In the given compound, there are
two different sets of equivalent 6

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(v)
(vi)
(vii)
(viii)
(ix)

alcohol
Propene to propyne
Ethanol to ethyl fluoride
Bromomethane to propanone
But-1-ene to but-2-ene
1-Chlorobutane to n-octane

Propene to 1nitropropane
Toluene to benzyl

(x)

Benzene to biphenyl.

(i)

(v)

(ii)
(vi)

(vii)

(iii)

(iv)

(viii)
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(xiv) Isopropyl alcohol to iodoform

(xv) Chlorobenzene to p-nitrophenol
(xvi) 2-Bromopropane to 1-bromopropane
(xvii) Chloroethane to butane
(xviii) Benzene to diphenyl
(xix) tert-Butyl bromide to isobutyl bromide
(xx) Aniline to phenylisocyanide
Answer (i)
(ix)

(x)
(ii)

How the following conversions can be carried out?

(i) Propene to propan-1-ol
(ii) Ethanol to but-1-yne
(iii) 1-Bromopropane to 2-bromopropane

(iii)

(iv) Toluene to benzyl alcohol

(v) Benzene to 4-bromonitrobenzene
(vi) Benzyl alcohol to 2-phenylethanoic acid
(vii) Ethanol to propanenitrile
(viii) Aniline to chlorobenzene
(ix) 2-Chlorobutane to 3, 4-dimethylhexane
(x) 2-Methyl-1-propene to 2-chloro-2-methylpropane
(xi) Ethyl chloride to propanoic acid
(xii) But-1-ene to n-butyliodide
(xiii) 2-Chloropropane to 1-propanol
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(iv)

(v)
(ix)

(vi)

(x)

(xi)

(vii)

(xii)

(viii)

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(xvi)
(xiii)

(xiv)

(xvii)

(xviii)
(xv)

(xix)

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(iii) When ethyl magnesium chloride is treated with methanal, an

adduct is the produced which gives propan-1-ol on hydrolysis.

(xx)

Q3

How are the following conversions carried out?

(i) Propene Propan-2-ol
(ii)Benzyl chloride Benzyl alcohol
(iii) Ethyl magnesium chloride Propan-1-ol.
(iv) Methyl magnesium bromide 2-Methylpropan-2-ol.

(iv) When methyl magnesium bromide is treated with propane, an

adduct is the product which gives 2-methylpropane-2-ol on hydrolysis.

Answer
(i) If propene is allowed to react with water in the presence of an acid
as a catalyst, then propan-2-ol is obtained.

(ii) If benzyl chloride is treated with NaOH (followed by acidification)

then benzyl alcohol is produced.

NAMED REACTIONS
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note :- always write few lines about reaction conditions

and remarkable point
1 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
4 Fittig reaction :
reactions of aryl halides with sodium
reaction.
2Swarts Reaction Preparation of alkyl fluoride by reaction of
metallic
fluoride such as AgF, Hg2 F2, CoF2, or SbF3 with alkyl halides

5 Wurtz-Fittig reaction:-

3 Friedel-Crafts reactions
[1]FriedelCrafts Alkylation
6 Sandmeyers reaction Replacement of
group of
benzene diazonium chloride by halide or cyanide ion is
called Sandmeyer reaction

[ii]Friedel-Crafts Acylation

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Q2

CID -PROBLEM
Q1

A hydrocarbon C5H10 does not react with chlorine in dark

but gives a single monochloro compound C5H9Cl in bright
sunlight. Identify the hydrocarbon.

Answer
hydrocarbon with the molecular formula, C5H10 belongs
to the group with a general molecular formula CnH2n. Therefore, it may
either be an alkene or a cycloalkane.

Primary alkyl halide C4H9Br (a) reacted with alcoholic KOH

to give compound (b).Compound (b) is reacted with HBr
to give (c) which is an isomer of (a). When (a) is reacted
with sodium metal it gives compound (d), C8H18 which is
different from the compound formed when n-butyl
bromide is reacted with sodium. Give the structural
formula of (a) and write the equations for all the reactions.
Answer There are two primary alkyl halides having the
formula, C4H9Br. They are n bulyl bromide and isobutyl
bromide.

Since hydrocarbon does not react with chlorine in the dark, it cannot
be an alkene. Thus, it should be a cycloalkane.
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
Hatoms that are all equivalent. Also, as all Hatoms of a cycloalkane
are equivalent, the hydrocarbon must be a cycloalkane. Hence, the
said compound is cyclopentane.

Therefore, compound (a) is either nbutyl bromide or isobutyl

bromide.
Now, compound (a) reacts with Na metal to give compound (b) of
molecular formula, C8H18, which is different from the compound formed
when nbutyl bromide reacts with Na metal. Hence, compound (a)
must be isobutyl bromide.

Cyclopentane (C5H10) The reactions involved in the question are:

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Step 1 removal of leaving group and formation of

carbocation

Step 2- attack of nucleophile

Thus, compound (d) is 2, 5dimethylhexane.

It is given that compound (a) reacts with alcoholic KOH to give
compound (b). Hence, compound (b) is 2methylpropene.

The increasing order of reactivity

for SN1 is1 halide < 2 halide < 3 halide
Reason Greater the stability of carbocation, more easily the alkyl
halide is formed and hence, faster is the reaction rate. The
increasing order of stability of carbocation is 1 < 2 < 3. Since 1
halide forms 1 carbocation, 2 halide forms 2 carbocation , and 3

halide forms 3 carbocation.

Also, compound (b) reacts with HBr to give compound (c) which is an
isomer of (a). Hence, compound (c) is 2bromo2methylpropane.

1 S N1 unimolecular Nucleophilic Substitution

(S N1)
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resonance.

2 (S N2) bimolecular Substitution nucleophilic

REACTION MECHANISM

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Allylic and benzylic halides are very reactive towards S N1

reaction because of stabilisation of their carbocations through

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Inversion of configuration takes place.

The increasing order of reactivity FOR SN2 is

3 halide < 2 halide < 1 halide

For both SN1 and SN2 reaction, the order of reactivity is
RF << RCl < RBr < RI
Q.1 write the mechanism of SN2 with the following
example

the crystal lattice. Therefore, more energy is required to break the

crystal lattice of p-dichlorobenzene. As a result, p-dichlorobenzene
has a higher melting point and lower solubility than o-and m-isomers.
Q2 Why C-Cl bond is more polar than C-F bomnd
A2

higer bond length of C-Cl

Q3

Explain why
(i) the dipole moment of chlorobenzene is lower than that
of cyclohexyl chloride?

The given reaction is:

(ii) alkyl halides, though polar, are immiscible with water?

(iii) Grignard reagents should be prepared under
anhydrous conditions?

The given reaction is an SN2 reaction. In this reaction, CN acts as the

nucleophile and attacks the carbon atom to which Br is attached. CN
ion is an ambident nucleophile and can attack through both C and N.
In this case, it attacks through the C-atom.

REASONI

Q1
p-Dichlorobenzene has higher m.p. and lower solubility
than those of o- and m-isomers. Discuss.

A3
(i) C-Cl bond is shorter in
chlorobenzene because of partial double
bond character than CCl bond In
cyclohexyl chloride
In chlorobenzene, the Cl-atom is linked to a sp2 hybridized carbon
atom. In cyclohexyl chloride, the Cl-atom is linked to a sp3 hybridized
carbon atom. Now, sp2 hybridized carbon has more s-character than
sp3 hybridized carbon atom. Therefore, the former is more
electronegative than the latter.
(ii) To be miscible with water, the solute-water force of attraction must
be stronger than the solute-solute and water-water forces of
attraction. Alkyl halides are not capable of making H-bond with the
water molecules. Hence, alkyl halides (though polar) are immiscible
with water.

A
p-Dichlorobenzene is more symmetrical than o-and misomers. For this reason, it fits more closely than o-and m-isomers in
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(iii) Grignard reagents are very reactive. In the presence of moisture,

they react to give alkanes.

(ii)
Therefore, Grignard reagents should be prepared under anhydrous
conditions.
Q4 Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily
hydrolysed by aqueous KOH?

A4
Hydrolysis by aqueous KOH proceeds through the formation of
carbocation. If carbocation is stable, then the compound is easily
hydrolyzed by aqueous KOH. Now,
while

(iii)

A5
(i)
2-bromobutane is a 2
alkylhalide whereas 1-bromobutane is a 1 alkyl halide. The
approaching of nucleophile is more hindered in 2-bromobutane than in
1-bromobutane. Therefore, 1-bromobutane reacts more rapidly than
2-bromobutane by an SN2 mechanism.

forms 1-carbocation,

forms 2-carbocation, which is more stable

than 1-carbocation. Hence,

easily than

is hydrolyzed more

(ii)

by aqueous KOH.

Q5
Which alkyl halide from the following pairs would you
expect to react more rapidly by an SN2 mechanism? Explain your
answer.

(iii)
Q6
In the following pairs of halogen compounds, which
compound undergoes faster SN1 reaction?

(i)
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Q8
Which compound in each of the following pairs will react
faster in SN2 reaction with OH?

(i)

(i) CH3Br or CH3I

A8
(i) In the SN2 mechanism, the reactivity of halides for the same
alkyl group increases in the order. This happens because as the size
increases, the halide ion becomes a better leaving group.

(ii)
A6

(ii) (CH3)3CCl or CH3Cl

(i)

RF << RCl < RBr < RI

Therefore, CH3I will react faster than CH3Br in SN2 reactions with OH.

The alkyl halide (I) is 3 while (II) is 2. Therefore, (I) forms 3

carbocation while (II) forms 2 carbocation.

(ii)
there are no bulky substituents on the carbon atom bearing the
leaving group in CH3Cl. Hence, CH3Cl reacts faster than (CH3)3CCl in
SN2 reaction with OH.

(ii)
The alkyl halide (I) is 2 while (II) is 1. 2 carbocation is more stable
than 1 carbocation. Therefore, (I), 2chloroheptane, undergoes
faster SN1 reaction than (II), 1-chlorohexane.
Q7
Haloalkanes react with KCN to form alkyl cyanides as
main product while AgCN forms isocyanides as the chief
product. Explain.

Q9
Arrange the compounds of each set in order of reactivity
towards SN2 displacement:
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 3-Bromo2- methylbutane
(iii) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2methylbutane, 1-Bromo-3-methylbutane.
A 9 (i)

A7
KCN is predominantly ionic and provides cyanide ions in
solution. Although both carbon and nitrogen atoms are in a position to
donate electron pairs, the attack takes place mainly through carbon
atom and
not through nitrogen atom since CC bond is more stable than CN
bond. However, AgCN is mainly covalent in nature and nitrogen is free
to donate electron pair forming isocyanide as the main product.
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Due to the presence of substituents, hindrance to the approaching

nucleophile increases in the following order.

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

Hence, the increasing order of reactivity towards SN2 displacement is:
2-Bromo-2-methylbutane < 2-Bromopentane < 1-Bromopentane
(ii)

1-Bromobutane < 1-Bromo-3-methylbutane < 1-Bromo-2-methylbutane

< 1-Bromo-2, 2-dimethylpropane

Since steric hindrance in alkyl halides increases in the order of 1 < 2

< 3, the increasing order of reactivity towards SN2 displacement is

Hence, the increasing order of reactivity of the given compounds towards

SN2 displacement is:

3 < 2 < 1.

1-Bromo-2, 2-dimethylpropane < 1-Bromo-2-methylbutane < 1-Bromo-3methylbutane < 1-Bromobutane

Hence, the given set of compounds can be arranged in the increasing

order of their reactivity towards SN2 displacement as:
2-Bromo-2-methylbutane < 2-Bromo-3-methylbutane < 1-Bromo-3methylbutane
[2-Bromo-3-methylbutane is incorrectly given in NCERT]

(iii)

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Q10 Although chlorine is an electron withdrawing group, yet it

is ortho-, para- directing in electrophilic aromatic substitution
reactions. Why?
A10 Chlorine withdraws electrons through inductive effect and releases
electrons through resonance. Through inductive effect, chlorine destabilises
the intermediate carbocation formed during the electrophilic substitution.

A12

Through resonance, halogen tends to stabilise 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
Reactivity is thus controlled by the stronger inductive effectand
orientation is controlled by resonance effect

Q11 In the following pairs of halogen compounds, which

would undergo SN2 reaction faster?

Q23 The treatment of alkyl chlorides with aqueous KOH leads

to the formation of alcohols but in the presence of alcoholic
KOH, alkenes are major products. Explain.
A23

In an aqueous solution, KOH almost completely ionizes to give OH

ions. OH ion is a strong nucleophile, which leads the alkyl chloride to
undergo a substitution reaction to form alcohol.

O
n the other hand, an alcoholic solution encourage removal of a
hydrogen from the -carbon of the alkyl chloride and form an alkene
by eliminating a molecule of HCl.

CHEMICAL
A11 In 1st pair
undergoes SN2reaction faster.

is primary halide and therefore

In 2nd
As iodine is a better leaving group because of its
large size, it will be released at a faster rate in the presence of
incoming nucleophile.
Q12 Predict the order of reactivity of the following compounds
in S N1 andSN2reactions:

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(a) CH CH CH OH
3

SHORT ANSWER TYPE

1. Aryl chlorides and bromides can be easily prepared by electrophilic
substitution of arenes with chlorine and bromine respectively in the
presence of Lewis acid catalysts. But why does preparation of aryl
iodides requires presence of an oxidising agent?
ans Iodination reactions are reversible in nature. To carry
out the reaction in the forward direction, HI formed during
iodination is removed by oxidation. HIO is used as an
oxidising agent.
4

2. Out of o-and p-dibromobenzene which one has higher melting point

and why?
ans p-Dibromobenzene has higher melting point than its oisomer. It is due to symmetry of p-isomer which fits in
crystal lattice better than the o-isomer.
3. Which of the compounds will react faster in SN1 reaction with the OH
ion?
CH CH Cl or C H CH Cl
ans C H CH Cl

3. Why iodoform has appreciable antiseptic property?

ans Due to liberation of free iodine.
4. Haloarenes are less reactive than haloalkanes and haloalkenes.
Explain..
ansC-X bond is partially doubly bonsded and resonance
stabilized
5. Which of the following compounds (a) and (b) will not react with a
mixture of NaBr and H SO . Explain why?
2

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ans b), CO bond is more stable in (b) because of

resonance.
6. Draw other resonance structures related to the following structure
and find out whether the functional group present in the molecule is
ortho, para directing or meta directing.
ans Ortho-para directing due to increase in the electron
density at ortho and para positions. (For resonance
structures

7. Classify the following compounds as primary, secondary and tertiary

halides.
(i) 1-Bromobut-2-ene (ii) 4-Bromopent-2-ene
(iii) 2-Bromo-2-methylpropane
ans (i) Primary (ii) Secondary (iii) Tertiary
8 . Compound A with molecular formula C4H9Br is treated with aq.
KOH solution. The rate of this reaction depends upon the concentration
of the compound A only. When another optically active isomer B of
this compound was treated
with aq. KOH solution, the rate of reaction was found to be dependent
on concentration of compound and KOH both.(i) Write down the
structural formula of both compounds A and B.
(ii) Out of these two compounds, which one will be converted to the
product with inverted configuration.

lattice better than other isomers

12. Write down the structure and IUPAC name for neo pentylbromide.
ans
ans i) Compound A :

Compound
; 1-Bromo-2,2-dimethylpropane

B:
(ii) Compound B.
9. Write the structures and names of the compounds formed when
compound A with molecular formula, C H is treated with Cl in the
presence of FeCl .
ans.
7

13. A hydrocarbon of molecular mass 72 g mol gives a single

monochloro derivative and two dichloro derivatives on photo
chlorination. Give the structure of the hydrocarbon.
ans. C H , pentane has molecular mass 72 g mol , i.e. the
isomer of pentane which yields single monochloro
derivative should have all the 12 hydrogens equivalent.
1

12

14. Name the alkene which will yield 1-chloro-1-methylcyclohexane by

its reaction with HCl. Write the reactions involved.
10. Identify the products A and B formed in the following reaction :
(a) CH CH CH==CHCH +HCl A + B
ans
3

11. Which of the following compounds will have the highest melting
point and why?

15. Which of the following haloalkanes reacts with aqueous KOH most
easily? Explain giving reason.
(i) 1-Bromobutane(ii) 2-Bromobutane(iii) 2-Bromo-2-methylpropane
(iv) 2-Chlorobutane
ans (iii); The tertiary carbocation formed in the reaction is
stable.
16. Why can aryl halides not be prepared by reaction of phenol with
HCl in the presence of ZnCl ?
CO bond in phenols is more stable due to resonance
2

ansII, due to symmetry of para-positions; it fits into crystal

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effect and it has double bond character, hence breaking of

this bond is difficult.
17. Which of the following compounds would undergo SN1 reaction

faster and why?

ans (B) Undergoes S 1 reaction faster than (A) because in
case of (B), the carbocation formed after the loss of Cl is
stabilised by resonance, whereas, no such stabilisation is
possible in the carbocation obtained from (A).
18. Allyl chloride is hydrolysed more readily than n-propyl chloride.
Why?
ans Allyl chloride shows high reactivity as the carbocation
formed by hydrolysis is stabilised by resonance while no
such stabilisation of carbocation exists in the case of npropyl chloride.
19. Why is it necessary to avoid even traces of moisture during the
use of a Grignard reagent?
ans Grignard reagents are highly reactive and react with
water to give corresponding hydrocarbons.
RMgX + H O RH + Mg(OH)X
20. How do polar solvents help in the first step in S 1 mechanism?
ans yes because of solvation of carbocation.]
21. Write a test to detect the presence of double bond in a molecule.
(1) Unsaturation test with Br water (2) Bayers test.]
22. Aryl halides are extremely less reactive towards nucleophilic
substitution. Predict and explain the order of reactivity of the following
compounds towards nucleophilic substitution:

ans . III > II > I

23. Predict the major product formed when HCl is added to
isobutylene. Explain the mechanism involved.

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24. Cyanide ion acts as an ambident nucleophile. From which end

it acts as a stronger nucleophile in aqueous medium? Give reason
for your answer.
ans It acts as a stronger nucleophile from the carbon end
because it will lead to the formation of CC bond which is
more stable than the CN bond.