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12th Board Booster (2024)

Haloalkanes & Haloarenes DPP-02

1. Out of 9. Write chemical equations when

(i) ethyl chloride is treated with aqueous KOH.
which will react faster in SN1 reaction OH–? (ii) chlorobenzene is treated with CH3COCl in the
presence of anhydrous AlCl3.
2. Out of CH3CH2CH2Cl and CH2 = CH – CH2 – Cl,
which one is more reactive towards SN1 reaction? 10. Account for the following:
(i) The C–Cl bond length in chlorobenzene is
3. Out of chlorobenzene and benzyl chloride, which one shorter than that in CH3–Cl.
gets easily hydrolysed by aqueous NaOH and why?
(ii) Chloroform is stored in closed dark brown
bottles.
4. Write the structure of an isomer of compound C4H9Br
which is most reactive towards SN1 reaction.
11. Explain why
5. Out of CH 3 – CH – CH 2 – Cl and (i) alkyl halides, though polar, are immiscible with
| water?
CH 3
(ii) Grignard reagent should be prepared under
CH 3 – CH 2 – CH – Cl,
anhydrous conditions?
|
CH 3
Which is more reactive towards SN1 reaction and 12. (i) Identify the chiral molecule in the following
why?
pair.
6. Which would undergo SN2 reaction faster in the
following pair and why?
CH3 – CH2 – Br and CH3 – CH2 – I

7. Which will react faster towards SN2 reaction, 1- (ii) Write the structure of the product when
bromopentane or 2-bromopentane and why? chlorobenzene is treated with methyl chloride in
the presence of sodium metal and dry ether.
8. (i) Which alkyl halide from the following pair is (iii) Write the structure of the alkene formed by
chiral and undergoes faster towards SN2
dehydrohalogenation of 1-bromo-1-
reactions?
methylcyclohexane with alcoholic KOH.

(ii) Out of SN1 and SN2, which reaction occurs with

(a) Inversion of configuration?
(b) Racemisation?
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Note: Kindly find the Video Solution of DPPs Questions in the DPPs Section.
Hints & Solutions
CH 3
1. |
CH 3 – C – Br (2-bromo-2-methylpropane) of
|
CH 3
2. CH2 = CH – CH2 – Cl
compound C4H9Br is most reactive towards SN1
(Allylic halides show high reactivity towards SN1 reactions.
reaction because carbocations formed gets stabilized
through resonance). 5. CH 3 – CH 2 – CH – Cl will undergo SN1 reaction
|
3. C – Cl bond in chlorobenzene is stronger than C – Cl CH 3
bond in benzyl chloride. Therefore, hydrolysis of faster because it is a secondary alkyl halide and forms
benzyl chloride is easy. It is due to the fact that in a secondary carbocation that an stabilize itself more
chlorobenzene, the lone pairs of electrons on halogen than primary carbocation formed by
atom are delocalized as shown below: CH 3 – CH – CH 2 Cl .
|
CH 3

6. As I– ion is a better leaving group than Br– ion,

Due to this C–Cl bond have some double bond therefore iodides are more reactive than bromides.
character, whereas in benzyl chloride C – Cl bond is Therefore, CH3 – CH2 – I is more reactive than CH3–
weak. Cleavage of C–Cl bond in benzyl chloride CH2–Br towards SN2 reaction and hence, CH3–CH2–
forms benzyl cation which is stable due to resonance I would undergo SN2 reaction faster than CH3–CH2–
as shown below: Br.

7. I-bromopentane is a primary alkyl halide, while

2-bromopentane is a secondary alkyl halide. Since,
primary alkyl halides are sterically less hindered
therefore, 1-bromopentane reacts faster towards SN2
reaction.

8. (i) (a) undergoes faster towards SN2

reaction as it is a primary halide.

4. Tertiary (3°) alkyl halides are the most reactive (b) The alkyl halide is chiral as it
towards SN1 reactions followed by secondary (2°) contains asymmetric carbon (*) atom.
and primary (1°) alkyl halides. (ii) (a) SN2 reaction occurs with inversion of
C4H9Br has four isomers: configuration.
(b) SN1 reaction proceeds with racemisation.
CH3 – CH 2 – CH 2 – CH 2 Br
1 bromobutane
As 3° alkyl halides form a more stable 3° carbocation 9. (i) Ethyl chloride undergoes hydrolysis to form ethyl
intermediate than secondary and primary alkyl alcohol (though SN2 nucleophilic substitution).
halides which form 2° and 1° carbocation, C2 H5Cl  KOH(aq)  C2 H5OH  KCl
Ethyl chloride Ethanol
respectively. Hence, the isomer.

(ii)
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10. (i) Due to declocalisation of lone pairs of electrons of 12. (i) A molecule which completely lacks symmetry is
the X atom over the benzene ring, C–X bond in called chiral.
halobenzene acquires some double bond The mirror images of such molecules are non-
character, while in CH3–X, C–X bond is a pure superimposable. Molecule (i) is chiral as its
single bond. Therefore, C–X bond in halobenzene mirror image is non-superimposable.
is shorter than in CH3–X.
(ii) In the presence of air and sunlight, chloroform
gets oxidized to phosgene (carbonyl chloride,
COCl2), a poisonous compound. Thus, to prevent (ii) It is Wurtz-Fitting reaction.
the formation of phosgene, chloroform is stored in
dark brown bottles filled upto brim.
1
CHCl3  O 2  hv
 COCl 2  HCl
Chloroform 2 Carbonyl cghloride
(Phosgene)

(iii)
11. (i) To be miscible with (or soluble in water) water,
the solute-water force of attraction must be
stronger than the solute-solute and water-water
forces of attraction. Alkyl halides are polar
molecules and so held together by dipole-dipole
interactions.
Similarly, strong H-bonds exist between the water
molecules. The new force of attraction between -hydrogen on each side of Br atom are
the alkyl halides and water molecules is weather equivalent, because of which only one alkene will
than the forces of attraction already existing be formed.
between alkyl halide-alkyl halide and water-water
molecules. Hence, alkyl halides (though polar) are
immiscible with (or insoluble in) water.
(ii) Grignard reagents are very reactive. In the
presence of moisture, they react to give alkanes.
  
R – Mg– X  H – OH  R – H  Mg(OH)X
Grignard Alkane
reagent

Therefore, Grignard reagents should be prepared

under anhydrous conditions.

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