HALOALKANES AND HALOARENES
EXERCISE – 3: Previous Year Questions
1. Chloroform is stored in closed dark brown bottles. (ii)
(Delhi 2010)
Sol. In the presence of air and sunlight, chloroform get
oxidised to phosgene which is a poisonous compound.
Thus, to avoid the formation of phosgene, chloroform is
stored in dark brown bottles filled up to brim.
1 (iii)
CHCl3 + O 2 → COCl2 + HCl
Chloroform 2 Carbonyl chloride
( Phosgene )
2. Which one of the following compounds is more easily
hydrolysed by KOH and why?
CH 3 CHClCH 2 CH 3 and CH 3 CH 2 CH 2 Cl 4.
(Al 2012)
Sol. Due to +I and +H effect groups, the 2o carbonium ion
+ Sol.
CH 3 − C H − CH 2 − CH 3 derived from sec. butyl 5.
chloride is more stable than the 1o carbonium ion
+
CH 3 − CH 2 − C H 2 derived from n-propyl chloride.
Therefore sec. butyl chloride hydrolysed more easily
than n-propyl chloride under SN1 conditions.
3. Explain the following :
(i) The dipole moment of chlorobenzene is lower
than that of cyclohexyl chloride.
(ii) Alkyl halides, though polar, are immiscible with
water.
(iii) Grignard’s reagents should be prepared under
anhydrous conditions. Sol.
(Delhi 2012)
Sol. (i) In chlorobenzene, the Cl-atom is linked to a
sp2 hybridized carbon atom. In cyclohexyl
chloride, theCl atom is linked to a sp3 hybridized
carbon. Now, sp2 hybridized carbon has more s- 6.
character than sp3 hybridized carbon atom.
Therefore, the former is more electronegative than
the latter. Therefore, the density of electrons of C-
Cl bond near the Cl atom is less in chlorobenzene Sol.
than in cyclohexyl chloride. As a result, the
polarity of C-Cl bond in chlorobenzene decreases.
Hence, the dipole moment of chlorobenzene is
lower than that of cyclohexyl chloride.
1
Alkyl halides though polar are immiscible with water
because less energy is released when new attractions
are set up between the alkyl halide and the water
molecules as they are not as strong as the original
hydrogen bonds in the water as a result the solubility of
alkyl halides in water is low.
Grignard reagents should be prepared under anhydrous
conditions because Grignard reagents are highly
reactive. In the presence of moisture they react to give
alkanes.
What happens when bromine attacks
CH 2 = CH − CH 2 − C ≡ CH ?
(AI 2012)
The reddish brown colour of bromine is discharged.
Consider the three types replacement of group X by
group Y as shown here.
This can result in giving compound (A) or (B) or both.
What is the process called if
(i) (A) is the only compound obtained ?
(ii) (B) is the only compound obtained ?
(iii) (A) and (B) are formed in equal proportions?
(Foreign 2013)
(i) Retention
(ii) Inversion
(iii) Racemisation
Chlorobenzene is extremely less reactive towards a
nucleophilic substitution reaction. Give two reasons for
the same.
(Delhi 2013)
The two reasons are as follows :
(i) Resonance effect : The electron pair of chlorine
atom is involved in conjugation with the π-electrons
of the benzene ring. As a result, electrons of C—Cl
bond get delocalized and a partial double bond
character develops in the bond and hence, it becomes
2 HALOALKANES AND HALOARENES

difficult for the nucleophile to cleave the C— Cl

bond.
(ii) Increased electron density : A repulsion is
suffered by the nucleophile due to increased electron
The alkyl halide (a) does not contain a chiral centre and
density on the benzene ring which prohibits the
it also gives faster SN2 reaction as SN2 is more
nucleophile to make a close access for the attack on
favourable in primary alkyl halides.
the molecule.
(ii) (a) SN2 (b) SN1
10. Give reason for the following :
7. Write IUPAC name of the following compound?
(i) Benzyl chloride is highly reactive towards the SN1
(OD 2013)
reaction.
(ii) 2-bromobutane is optically active but 1-
bromobutane is optically inactive.
(iii) Electrophilic reactions in haloarenes occur slowly.
(OD 2015)
Sol. (i) Benzyl chloride is highly reactive towards the SN1
reaction because the intermediate benzyl
Sol. 1, 4-dichloro-3-methylbenzene. carbocation formed in slowest step is stablized
through resonance.
8. Draw the structure of major monohalo product in the (ii) 2-bromobutane is a chiral molecule as it contains
following reaction : an asymmetric carbon atom therefore, it is
optically active whereas 1-bromobutane is an
achiral molecule as it does not contain
asymmertic carbon atom therefore it is optically
(Delhi 2014) inactive.
Sol. (iii) Halogen im haloarenes withdraws electrons
through -I effect and release electrons through +R
effect. The inductive effect is stronger than
resonance effect and causes net electrons.
withdrawal. As a result, the electrophilic
substitution reactions in haloarenes occur slowly.

11. Which would undergo SN2 reaction faster in the

9. (i) Which alkyl halide from the following pair is chiral following pair and why ?
and undergoes faster SN2 reaction ?

(Delhi 2015)
(ii) Out of SN1 and SN2, which reaction occurs with Sol. CH3 — CH2 — Br would undergo SN2 reaction faster as
(a) Inversion of configuration a 1˚ halide it has less steric hindrance than tert - butyl
(b) Racemisation bromide.
(Delhi 2014) 12. How do you convert the following :
Sol. (i) (b) is chiral as all four groups attached to ∗carbon (i) Prop-1-ene to 1-fluoropropane
atom are different (ii) Chlorobenzene to 2-chlorotoluene
(iii) Ethanol to propanenitrile
(OD 2015)
HALOALKANES AND HALOARENES 3

Sol. 15. Out of CH3 — CH2 — CH2— Cl and

(i)

Which is more reactive towards SN1 reaction why?

(ii)
(Delhi 2016)
Sol.

(iii)
is more reactive as being tertiary alkyl halide it forms
more stable carbocation intermediate than primary alkyl
halides.

16. Give reasons:

(Delhi 2016)
13. Give the IUPAC names of the following compounds: (i) C—Cl bond length in chlorobenzene is shorter
than C—Cl bond length in CH3—Cl.
(ii) SN1 reactions are accompanied by racemisation in
optically active alkyl halides.
Sol. (i) In chlorobenzene, C—Cl bond acquires partial
double bond character while in methyl chloride,
C—Cl bond has pure single bond character. As a
result C—Cl bond in chlorobenzene is shorter
(OD 2015) than methyl chloride.
Sol. (i) 2-bromobutane (ii) Carbocations are intermediate in SN1 reactions.
(ii) 1, 3-dibromobenzene Carbocations being sp2 hybridised are planar
species, therefore, attack of nucleophile on it can
14. Write the structure of an isomer of compound C4H9Br occur from both front and rear with almost equal
which is most reactive towards SN1 reaction. ease giving a racemic mixture.
(OD 2016)
Sol. The isomer of compound C4H9Br which is most 17. Which compound in each of the following pairs will
reactive towards SN1 reaction is tert butyl bromide. In react faster in SN2 reaction with –OH ?
general, tertiary alkyl halides have maximum rate (i) CH3Br or CH3I
for SN1 reaction. (ii) (CH3)3CCl or CH3Cl
(Delhi 2016)
Sol. (i) CH3I as I ion is better leaving group than Br– ion.
–

(ii) CH3Cl as 1° alkyl halides are more reactive than

tert-alkyl halides in SN2 reaction with OH–.

18. Write the structure of 1-Bromo-4-chlorobut-2-ene.

(Delhi 2017)
Sol. BrCH2CH = CHCH2Cl.
4 HALOALKANES AND HALOARENES

19. Write the structure of 2,4-dinitrochlorobenzene. (i) Write the compound which is most reactive towards
(Delhi 2017) SN2 reaction.
Sol. (ii) Write the compound which is optically active.
(iii) Write the compound which is most reactive
towards β-elimination reaction.
(Delhi 2017)
Sol.
(i) 1-Bromopentane as primary alkyl halides are most
reactive for SN2.
(ii) 2-Bromopentane as it contains unsymmetrical
carbon atom.
20. Write the structure of 3-Bromo-2-methylprop-1- ene. (iii) 2-Bromo-2-methylbutane as tertiary alkyl halide is
(Delhi 2017) most reactive for elimination.
Sol. Br − CH 2 − C = CH 2
|
CH 3 24. How will you carry out the following conversion :
(i) 2-Bromopropane to 1-bromopropane
21. Out of
(ii) Benzene to p-chloronitrobenzene
(OD 2017)

Sol. (i)
alc KOH
and CH3 − CH ( Br ) − CH3 → CH3 − CH = CH 2
Which is example of allylic halide? HBr, Peroxide
 → CH 3 − CH 2 − CH 2 − Br
(AI 2017)
Sol. (ii)

22. Out of
25. Out of chlorobenzene and benzyl chloride, which one
gets easily hydrolysed by aqueous NaOH and why?
(Delhi 2018)
Sol. Benzyl chloride gets easily hydrolysed by aqueous
NaOH as chlorobenzene possesses partial double bond
Which is an example of benzylic halide?
character in the C–Cl bond. The lone pairs delocalised
(AI 2017)
in the ring strengthens C–Cl bond reducing its
Sol.
reactivity. Whereas benzyl chloride undergoes SN1
reaction to form stable benzyl carbocation.

26. Give reasons:

Thionyl chloride method is preferred for preparing
23. Following compounds are given to you : alkyl chlorides from alcohols.
2-Bromopentane, 2-Bromo-2-methylbutane, (OD 2019)
1-Bromopentane
HALOALKANES AND HALOARENES 5

Sol. The byproducts of the reaction, i.e., SO2 and HCl being Sol. Due to higher stability of tertiary carbocation than
gases escape into the atmosphere leaving behind alkyl primary carbocation.
chlorides in almost pure state.
30. Write the Mechanism of the following SN1 reaction :
27. Give reasons: Aq. NaOH
( CH3 )3 C − Br  → ( CH 3 )3 C − OH + NaBr
(i) n-Butyl bromide has higher boiling point than t-butyl
(Delhi 2019)
bromide.
Sol. The reaction mentioned is SN1 (Unimolecular
(ii) Racemic mixture is optically inactive.
nucleophilic substitution reaction) This reaction
(Delhi 2015, 2019)
proceeds through two step mechanism. First step is
Sol. (i) n-Butyl bromide being a straight chain alkyl halide
formation of carbocation and the second step is the
has larger surface area than tert.butyl bromide.
attack of the nucleophile OH to the carbocation.
−
Larger the surface area, larger the magnitude of the
van der Waal’s forces and hence higher is the
boiling point.
(ii) A racemic mixture contains the two enantiomers d
and l in equal proportions. As the rotation due to
one enantiomer is cancelled by equal and opposite
rotation of another enantiomer, therefore, it is
optically inactive.

28. Out of chlorobenzene and cyclohexyl chloride, which

one is more reactive towards nucleophilic substitution
reaction and why?
(Delhi 2019)
Sol. Cyclohexyl chloride is more reactive than
chlorobenzene towards nucleophilic substitution
reactions. Due to resonance the C–Cl bond in
chlorobenzene acquires partial double bond character
which makes the substitution of chlorine more difficult
in chlorobenzene than in cyclohexyl chloride where the
C–Cl bond has pure single bond character. The slow i.e., the first step is the rate determining step.

29. Why is t-butyl bromide more reactive towards SN1

reaction as compared to n-butyl bromide?
(Delhi 2019)