Level-I

Chapter 11

Haloalkanes and Haloarenes

Solutions (Set-1)

Very Short Answer Type Questions :

1. Draw the structure of an optically active isomer of C3H6Cl2. Give its IUPAC name.

H
|
Sol. CH3 — C* — CH2Cl
|
Cl
1,2-Dichloropropane (IUPAC name)

2. What happens when n-propyl bromide is treated with alcoholic KOH?

Sol. Propene is formed
alc. KOH
CH3 — CH2 — CH2Br ⎯⎯⎯⎯⎯
→ CH3 — CH = CH2 + KBr + H2O

3. What are (i) vicinal dihalides and (ii) gem dihalides?

Sol. (i) Vicinal dihalides are dihaloalkanes in which the two halogen atoms are attached to adjacent carbon atoms.
(ii) Gem dihalides are dihaloalkanes in which the two halogen atoms are attached to the same carbon atom.
4. How will you distinguish between ethyl chloride and vinyl chloride?
Sol. Ethyl chloride reacts with alcoholic AgNO3 to give white ppt. of AgCl. Vinyl chloride does not give this test.
CH3CH2Cl + AgNO3 + C2H5OH ⎯⎯→ AgCl↓ + CH3CH2OC2H5 + HNO3
5. What happens when chloroform is exposed to light and air?
Sol. A deadly poisonous gas called phosgene (COCl2) is formed.
hν
2CHCl3 + O2 ⎯⎯⎯
→ 2COCl2 + 2HCl

6. Comment on the stereochemistry of the product obtained by the reaction of trans but-2-ene with Br2(CCl4).

CH3 H CCl4 CH3 H

Sol. C C + Br2 Br C C Br
H CH3 H CH3
(Meso)

The product obtained in the given reaction is meso 2,3-dibromobutane. It is optically inactive which cannot be
resolved.

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 2 Haloalkanes and Haloarenes Solutions of Assignment (Level-I) (Set-1)

7. What happens when ethanol is treated with bleaching powder?

Sol. Bleaching powder oxidises ethanol to calcium formate along with the formation of chloroform.
8. How is Freon-12 prepared?
Sol. Carbon tetrachloride reacts with HF in presence of SbF5 to form dichlorodifluoromethane (Freon-12)
SbF
CCl4 + 2HF ⎯⎯⎯→
5
CCl2F2 + 2HCl

9. How will you synthesise ethylene glycol from ethyl chloride?

alc. KOH cold aq.

Sol. CH3 — CH2 — Cl ⎯⎯⎯⎯⎯
→ CH2 = CH2 ⎯⎯⎯⎯⎯⎯
→ CH2OH — CH2OH
alk. KMnO4

10. Optically active 2-iodobutane on treatment with NaI in acetone undergoes racemisation. Explain.
Sol. The reaction of optically active 2-iodobutane with NaI undergoes multiple Walden inversion and the product contains
equimolar mixture of dextro and laevo isomers.

CH3 CH3 CH3

| | |
Acetone
H — C — I + I− ⎯⎯⎯⎯⎯ →I — C — H + H — C — I
| | |
C2H5 C2H5 C2H5

Short Answer Type Questions :

11. (i) Arrange alkyl halides, alkane and water in the decreasing order of density.
(ii) Arrange chloromethane and water in the decreasing order of density.
Sol. (i) RI > RBr > H2O > RCl > RF > RH
(ii) CCl4 > CHCl3 > CH2Cl2 > H2O > CH3Cl
12. Point out the difference between
(i) Chirality and chiral centre
(ii) Enantiomers and diastereomers.
Sol. (i) Property of a molecule containing a carbon attached to four different atoms or group of atoms is called
chirality. The carbon atom which is bonded to four different atoms or group of atoms is called chiral centre.
(ii) The non superimposable mirror image isomers of a compound are called enantiomers. They have same
physical and chemical properties. They have optical rotation equal in magnitude but opposite in sign. The non
superimposable and non mirror image isomers of a compound are called diastereomers. They have different
physical properties and different optical rotation.
13. Starting from bromoethane, how will you prepare (i) nitroethane and (ii) ethylnitrite?
Sol. (i) CH3 — CH2 — Br + AgNO2 ⎯⎯→ CH3CH2 — NO2 + AgBr
(ii) CH3 — CH2 — Br + KNO2 ⎯⎯→ CH3CH2 — O — N = O + KBr
14. Write IUPAC names of the following compounds:

(i) Cl OCOCH2CH3

Br
|
(ii) BrCH2 — CH— CH— CH2Cl
|
OH

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Solutions of Assignment (Level-I) (Set-1) Haloalkanes and Haloarenes 3
Sol. (i) 4-chlorophenyl propanoate
(ii) 1,3-Dibromo-4-chlorobutan-2-ol
15. How will you synthesise vinyl bromide from ethyl alcohol?

Br
|
conc. H2SO4 Br2 alc. KOH
Sol. CH3 CH2OH ⎯⎯⎯⎯⎯⎯ → CH2 = CH2 ⎯⎯⎯⎯ → CH2 — CH2 ⎯⎯⎯⎯⎯ → CH2 = CH — Br
Δ (CCl4 )
|
Br
16. Complete the following reaction by identifying (A) to (D) products.

FeBr
3 →(A) ⎯⎯⎯⎯⎯ 3 Mg2 ⎯ CH CN H+ /H O
C6H6 + Br2 ⎯⎯⎯⎯ →(B) ⎯⎯⎯⎯→(C) ⎯⎯⎯⎯ →(D)
Dry ether

Br Mg—Br H3C C NMgBr CO—CH3

+
FeBr3 Mg CH3CN H / H2O
Sol. + Br2
Dry ether
(A) (B) (C) (D)

17. Convert chlorobenzene to 2,2-bis(4-chlorophenyl)-1,1,1-tri-chloroethane.

H Cl Cl
conc. H2SO4
Sol. Cl3C — CH O –H2O
Cl3C — CH
H Cl Cl
(DDT)

18. Outline synthesis of the following compounds by using nucleophilic substitution reaction.
(i) C6H5 — CH2 — NC
(ii) CH3CH2C ≡≡ CCH2CH3
Sol. (i) C6H5 — CH2 — Cl + AgCN ⎯⎯→ C6H5—CH2—NC + AgCl
(ii) CH3CH2C ≡≡ CH + NaNH2 ⎯⎯→ CH3CH2C ≡≡ C–Na+ + NH3
CH3CH2C ≡≡ C–Na+ +CH3CH2 — Cl ⎯⎯→ CH3CH2C ≡≡ CCH2CH3 + NaCl
19. Give all the products formed in the following reaction and indicate the major product.

CH3
|
alc. KOH
CH3 — C — CH2 — Cl ⎯⎯⎯⎯⎯ →
Δ
|
CH3

Sol. The given reaction follows E1 mechanism forming alkenes.

CH3 CH3 CH3
—

CH3 — C — CH2 — Cl CH3 — C — CH2 CH3 — C — CH2 — CH3

—

CH3 CH3

CH3 CH3
—

+
–H
CH3 — C CH — CH3 + CH2 C — CH2 — CH3
(major)

The major product is 2-methylbut-2-ene according to Saytzeff rule.

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 4 Haloalkanes and Haloarenes Solutions of Assignment (Level-I) (Set-1)

20. Give the products formed in the following displacement reactions.

(i) (R)-CH3CHBrCH2CH3 + CH3O–
(ii) cis-4-iodoethylcyclohexane + OH–

CH3
|
(iii) (S)- Br — C — COOC2H5 + CN−
|
H

Sol. All the three given reactions proceed by SN2 mechanism which is accompanied by inversion of configuration.
Change in configuration from (R) to (S) and vice-versa will be observed only when the nucleophile and nucleofuge
have the same order of priority. The products formed are
(i) (S)-CH3CH(OCH3)CH2CH3
(ii) trans-4-ethylcyclohexanol

CH3
|
(iii) (S)- C2H5 COO — C — CN
|
H

21. Account for the rapid rate of ethanolysis of CH3OCH2Cl with respect to CH3CH2Cl although it is a primary halide.
Sol. Ethanolysis of CH3OCH2Cl proceeds by SN1 mechanism in which the carbocation is stabilised by +R effect of
O-atom.

⊕ + C2H5OH
CH3 — O — CH2 — Cl ⎯⎯→ CH3 — O — CH2 CH3 — O CH2

+ +
–H
CH3 — O — CH2 — O — C2H5 CH3 — O — CH2 — O — C2H 5
H

22. Hydrolysis of 2-bromo-3-methylbutane yields only 2-methyl-2-butanol. Explain why.

Sol. The reaction involves rearrangement of 2° carbocation to 3° carbocation by 1, 2-hydride shift followed by attack by
H2O molecule.

CH3 CH3 CH3 CH3

H2O H2O
CH3 CH CH CH3 –Br
– CH3 CH C CH3 CH3 CH2 C CH3 –H
+ CH3 CH2 C CH3
Br H OH

−
OH
23. Discuss the reaction Cl — CH2 — CHCl2 ⎯⎯⎯→ CH2 = CCl2
Δ

Sol. The –I effect of two Cl-atoms is more than that of one Cl-atom. Thus the H-atom of CHCl2 is more acidic than that of
CH2Cl. Hence OH– removes the more acidic hydrogen to give the corresponding alkene.

H
– –
CH2 CCl2 + OH CH2 CCl2 + H2O + Cl
Cl

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Solutions of Assignment (Level-I) (Set-1) Haloalkanes and Haloarenes 5
24. What happens when
(i) Phenol reacts with methyl iodide in alkaline medium?
(ii) Phenol reacts with chloroform and aqueous NaOH?

OH O– OCH3
CH3–I
Sol. (i) + OH– –H2O
+ I–

— — —
(ii) CHCl3 + OH –H2O
CCl3 CCl2 + Cl

H
OH O— O O— O— OH
— H CHCl2 — CH—O CHO
OH CCl2 — OH
CCl2 + Cl—
–H2O Cl

25. When t-butyl alcohol is treated with an equimolar mixture of HBr and HCl, a mixture of t-butyl bromide and t-butyl
chloride is formed in which the former predominates. Explain.

Sol. Tert butyl alcohol is protonated by either HBr or HCl, preferably with HBr since it is a stronger acid, with the
elimination of H2O molecule to form t-butyl carbocation in a slow rate determing step. This is followed by attack of
Br– or Cl– on carbocation in a fast step. Since Br– is a better nucleophile than Cl–, its attack predominates forming
t-butyl bromide as a major product.

+

 − + slow −
(CH3 )3 C − OH + HBr 
 (CH3 )3 C − OH2Br ⎯⎯⎯→ (CH3 )3 C + H2O + Br

+

 − slow + −
(CH3 )3 C − OH + HCl 
 (CH3 )3 C − OH2Cl ⎯⎯⎯→ (CH3 )3 C + H2O + Cl

fast
(CH3 )3 C+ + Br − ⎯⎯⎯→ (CH3 )3 C − Br
major

fast
(CH3 )3 C+ + Cl− ⎯⎯⎯→(CH3 )3 C − Cl

26. Explain the following with the help of suitable examples giving all the steps involved in the reaction.
(i) Carbylamine reaction
(ii) Hunsdicker reaction
Sol. (i) When a primary amine, aliphatic or aromatic is treated with CHCl3 and alcoholic KOH, a bad smelling compound
called isocyanide is formed which can easily be detected by its offensive smell. The reaction involves the
formation of dichlorocarbene, an electrophile, which attacks the H-atom of primary amine with the elimination
of two HCl molecules.
— — —
CHCl3 + OH –H2O
CCl3 CCl2 + Cl

H
Cl –H+, –Cl– –H+, –Cl–
CH3CH2 – NH2 + CCl2 CH3CH2 – N – C CH3CH2 – N C CH3CH2 – N C
Cl
H H Cl

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 6 Haloalkanes and Haloarenes Solutions of Assignment (Level-I) (Set-1)

(ii) When silver salt of a carboxylic acid is treated with Br2 in presence of carbon tetrachloride, alkyl bromide
having one C-atom less than that present in silver salt will be formed. The reaction follows free radical
mechanism.

O
||
CCl4
CH3 CH2COOAg + Br2 ⎯⎯⎯→ CH3 CH2 — C— O — Br + AgBr

O O
|| ||
slow
CH3 CH2 — C— O — Br ⎯⎯⎯→ CH3 CH2 — C— O• +Br •

O
|| •
CH3 CH2 — C— O• ⎯⎯→ CH3 CH2 + CO2

• •
CH3 CH2 + Br ⎯⎯→ CH3 CH2 — Br

27. Which one in the following pairs of substances undergoes SN2 substitution reaction faster and why?

(i) CH2Cl or Cl

(ii) I or Cl

Sol. (i) Chloromethylcyclohexane is a primary alkyl halide and will undergo SN2 substitution reaction faster than
chlorocyclohexane which is a secondary alkyl halide. The steric hindrance at the nucleophilic site in primary
alkyl halide is less than in secondary alkyl halide which is responsible for the faster rate of reaction.

δ– δ–
CH2 — Cl + OH
—
HO CH2 Cl HO CH2
(nucleophile)

(transition state)

(ii) 1-Iodopentane reacts faster than 1-Chloropentane towards SN2 substitution reaction due to lower bond
dissociation energy of C-I bond than C – Cl bond.

I + CH3O
– OCH3
(nucleophile)

28. Complete the following reactions

5 PCl 2 ⎯ AgCN H+ /H O
(i) (CH3 )2 CH — OH ⎯⎯⎯→(A) ⎯⎯⎯⎯
→(B) ⎯⎯⎯⎯ →(C) + (D)

(ii) CH3CH2CH2Br + CH3COOAg ⎯⎯→ (A) + (B)

⊕ 
−
PCl AgCN H+ /H O
Sol. (i) (CH3 )2 CH — OH ⎯⎯⎯→
5
→ (CH3 )2 CH — N ≡ C ⎯⎯⎯⎯→
(CH3 )2 CH — Cl ⎯⎯⎯⎯ 2

(A) (B)

(CH3 )2 CH — NH2 + HCOOH

(C) (D)

(ii) CH3COOAg + CH3CH2CH2 — Br ⎯⎯→ CH3COOCH2CH2CH3 + AgBr

(A) (B)

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Solutions of Assignment (Level-I) (Set-1) Haloalkanes and Haloarenes 7
29. Write chemical equations and reaction conditions for the conversion of
(i) Chloroform to Ethene
(ii) Chloroform to chloretone

Δ
Sol. (i) 2CHCl3 + 6Ag ⎯⎯→ HC ≡ CH + 6AgCl

Pd−BaSO
HC ≡ CH + H2 ⎯⎯⎯⎯⎯⎯
4
→ H2C = CH2

CH3 KOH CH3 OH

(ii) C O + CHCl3 C
CH3 CH3 CCl3
Chloretone

30. What mass of propene is obtained from 42.5 gm of 1-iodopropane on treating with alcoholic KOH if yield is 60%?

Sol. CH3 CH2CH2 — I+ alc. KOH ⎯⎯→ CH3 — CH = CH2 + KI + H2O

Mol. mass = 170 Mol. mass = 42

170 gm of 1-iodopropane gives 42 gm of propene

42 × 42.5
42.5 gm of 1-iodopropane gives = 10.5 gm of propene
170

60
If yield is 60%, the amount of propene formed = 10.5 × = 6.30 gm
100

Long Answer Type Questions :

31. Identify the major products (A) to (D) formed in the following sequence of reactions. Also give the mechanism for
the conversion (A) to (B).

CH2Cl

KCN C H ONa/C H OH H O+ 1. SOCl

⎯⎯⎯→ (A) ⎯⎯⎯⎯⎯⎯⎯⎯
2 5 2 5
→ (B) ⎯⎯⎯⎯
3
→ (C) ⎯⎯⎯⎯⎯→
2
(D)
DMF C6H5 —CHO/ Δ Δ 2. CH3NH2

CH2—Cl CH2—CN

KCN
Sol. ⎯⎯⎯→
DMF
(A)

Mechanism for conversion of (A) to (B)

–
CN O CN OH
–
CH2—CN CH—CN O
CH—CH—C6H5 CH—CH—C6H5
NC Ph
C6H5–C–H C2H5OH Δ
+ C2H5O– C C
Ph H
(A) (B)

O
NC Ph +
H / H2O HOOC Ph 1. SOCl2 H3C—NH—C Ph
C C C C C C
2. CH3NH2
Ph H Ph H Ph H
(B) (C) (D)

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 8 Haloalkanes and Haloarenes Solutions of Assignment (Level-I) (Set-1)

32. Predict the compounds (A) to (H) in the following sequence of reactions:
HBr NaNH HBr
(i) (A) ⎯⎯⎯→ CH3 — CH— CH3 ⎯⎯⎯⎯
2
→ (B) ⎯⎯⎯⎯⎯⎯ → (C)
+ Peroxide
|
Br

Mg 2 2 ⎯ CO H+ /H O
(ii) CH3Br ⎯⎯⎯⎯⎯
Dry ether
→ (D) ⎯⎯⎯→ (E) ⎯⎯⎯⎯ → (F)

Cl /Fe
2 2 2 → (H) Cu (CN)
(iii) ⎯⎯⎯⎯→ (G) ⎯⎯⎯⎯⎯
P4

→ CH3 —CH=CH2 ⎯⎯⎯⎯⎯

HBr NaNH HBr
Sol. (i) CH3 —CH—CH3 ⎯⎯⎯→ CH3 —CH—CH3 ⎯⎯⎯⎯
2
→ CH3 —CH2 —CH2 —Br
Peroxide
| | (B) (C)
OH Br
(A)

O O
|| ||
Dry O=C=O +
H /H2O
(ii) CH3 — Br + Mg ⎯⎯⎯⎯ → CH3 — MgBr ⎯⎯⎯⎯⎯ → CH3 — C— OMgBr ⎯⎯⎯⎯→ CH3 — C— OH
ether
(D) (E) (F)

Cl CN

Fe Cu2(CN)2
(iii) + Cl2
P4
(G) (H)

33. Complete the following sequence of reactions by providing the unknown compounds.
NO2
Br /Fe H /Pt NaNO +HCl Cu Cl
⎯⎯⎯⎯
2
→ (A) ⎯⎯⎯⎯
2
→ (B) ⎯⎯⎯⎯⎯⎯
2
→ (C) ⎯⎯⎯⎯
2 2
→ (D)
0 − 5 °C

NO2 NO2 NH2 +

N2Cl– Cl

Fe H /Pt NaNO +HCl Cu Cl

Sol. + Br2 ⎯⎯⎯ → ⎯⎯⎯⎯
2
→ ⎯⎯⎯⎯⎯⎯
2
→ ⎯⎯⎯⎯
2 2
→
0-5°C
Br Br Br
(A) (B) (C) (D)

34. How would you synthesise 4-methoxyphenol from bromo benzene in NOT more than five steps? State clearly the
reagents used in each step and show the structures of the intermediate compounds in your synthetic scheme.
Br Br Br OCH3
conc. H2SO4 (i) NaOH fusion CH3ONa
Sol. High temp.
(ii) Acidification
High pressur
SO3H OH OH

Conversion of p-bromophenol to p-methoxy phenol involves the formation 3,4-aryne OH as intermediate.

35. n-Butane is produced by the monobromination of ethane followed by Wurtz reaction. Calculate the volume of
ethane at STP to produce 87 gm of n-butane if the bromination takes place with 80% yield and the Wurtz reaction
with 75% yield.
hν / Δ
Sol. C2H6 + Br2 ⎯⎯⎯⎯⎯⎯⎯⎯
monobromination
→ C2H5Br + HCl

dry ether
2C2H5Br + 2Na ⎯⎯⎯⎯⎯
→ n-C4H10 + 2NaBr

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Solutions of Assignment (Level-I) (Set-1) Haloalkanes and Haloarenes 9
Let the volume of ethane required at STP be x L.

x
Number of moles of ethane =
22.4

80 x
Moles of C2H5Br produced = ×
100 22.4

75 80 x
Moles of n-butane produced from C2H5Br = × ×
100 100 2 × 22.4

0.75 × 0.8 × x × 58
Mass of n-butane produced = = 87
2 × 22.4
On solving, x = 112 L
36. An excess of methyl magnesium halide reacts with 0.6 gm of an organic compound C3H6O3 to evolve 295.7 ml of
methane gas at STP. Calculate the number of active hydrogen atoms in the molecule of the organic compound.
Sol. Molecular mass (M) of organic compound = 90

0.6 0.6
Number of moles of organic compound = = = 6.667 × 10−3
M 90

295.7
Number of moles of CH4 gas formed = = 0.0132
22400

0.0132
Number of active H-atoms in a molecule = 2
6.667 × 10−3
37. Although chlorine is an electron withdrawing group, yet it is ortho para directing in electrophilic aromatic substitution
reactions. Explain.
Sol. Chlorine withdraws electrons through inductive effect but releases electrons through resonance. Through inductive
effect, chlorine destabilises the intermediate arenium ion formed during electrophilic substitution.

Cl Cl
H
+
+E E
–I effect of Cl
destabilises

Cl Cl+
H H
Ortho
Cl attack E E etc.

+ E+ Cl Cl+
Para
attack etc.
E H
However, halogen tends to stabilise the arenium ion by +R and the effect is more pronounced at ortho and para
positions. The –I effect of Cl is stronger than +R effect and causes net electron withdrawal and thus causes
deactivation. The +R effect tends to oppose the –I effect at ortho/para position and hence makes deactivation less
for ortho/para attack.

‰ ‰ ‰
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 Level-I
Chapter 11

Haloalkanes and Haloarenes

Solutions (Set-2)

[Preparation]
1. Which of the following can be used to prepare 3-bromo propene?
CCl
(1) CH3CH = CH2 + Br2 ⎯⎯ ⎯ →
4
30°C
(2) CH3CH = CH2 + N – bromo succinimide ⎯⎯→

(3) CH2 = CH – CH3 + PBr3 ⎯⎯→ HBr

(4) CH2 = CH — CH3 ⎯⎯⎯→
Sol. Answer (2)
NBS is used for allylic and benzylic bromination.

CH 3 — CH = CH 2 + NBS → CH 2 — CH = CH 2
|
Br 3-bromopropene
2. Which one of the following reactants and reagents will give in the presence of peroxide a product different
from that obtained in the absence of peroxide?
(1) 1-butene, HCl (2) 1-butene, HBr (3) 2-butene, HCl (4) 2-butene, HBr
Sol. Answer (2)
Only in case of HBr, Anti Markownikoff’s addition is observed in unsymmetrical alkene.
HBr
CH3— CH2 — CH — CH3
|
CH3— CH2 — CH = CH2 Br
HBr
Peroxide
CH3— CH2 — CH2 — CH2 — Br

Moreover HCl does not give peroxide effect.

3. Which of the following compounds yields only one product on monobromination?
(1) Neopentane (2) Toluene (3) Phenol (4) Aniline
Sol. Answer (1)
Neopentane is symmetrical alkane and it gives only one product on monobromination.
CH 3 CH 3
| |
hν
CH3 — C — CH3 + Br2 ⎯⎯→ CH3 — C — CH2 — Br
(1 equivalent )
| |
CH 3 CH 3

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Solutions of Assignment (Level-I) (Set-2) Haloalkanes and Haloarenes 11
organic
peroxide
4. The principal organic compound formed in the reaction is CH2=CH(CH2)3COOH+HBr Major product

(1) CH3 – CH(CH2)3COOH (2) CH2 – CH2 – (CH2)3COOH

Br Br
(3) CH2 = CH(CH2)3COBr (4) CH2 = CHCH2 – CH2 – CH – COOH
Br
Sol. Answer (2)
In presence of organic peroxide, HBr gives Anti Markownikoff’s addition.
organic
CH2 = CH (CH2)3 COOH + HBr ⎯⎯⎯⎯
peroxide
→ CH2 — CH2 —( CH2 —
)3 COOH
|
Br (Major)

5. The reaction : Alcohol + HCl Alkyl halide + H2O is reversible for the completion of the reaction we
use
(1) Anhydrous ZnCl2 (2) Conc. H2SO4 (3) CaCl2 (4) Excess of water
Sol. Answer (1)
In this reaction, anhydrous ZnCl2 absorbs H2O and reaction becomes irreversible. Concentrated H2SO4 reacts
with alcohol and alkene may be formed.
6. 3 methyl-2-pentene on reaction with HOCl gives
(1) 3-chloro-3-methyl pentanol-2 (2) 2, 3-dichloro-3-methyl pentane
(3) 2-chloro-3-methyl pentanol-3 (4) 2, 3 dimethyl butanol-2
Sol. Answer (3)
Here H2O + Cl2 ⎯→ HOCl.

In this reaction: Cl2 or Cl+ acts as electrophile. While H2O is Nucleophile (Note that O H is not the nucleophile in
this reaction)
Mechanism :

H H H H
O O OH
CH3 CH3
–H
CH3 CH C CH3 CH C CH 3 CH C CH 3 CH3 CH C CH3
CH3 CH3
Cl Cl Cl CH 3 Cl CH3
2-chloro-3-methylpentanol-3
Cl
7. A chemist plans to prepare 1-bromo-2-pentene by the following reaction
Δ
CH3CH2CH = CHCH3 + NBS ⎯⎯ → CH3CH2CH = CHCH2Br

This plane is not likely to work because

(1) There will be no reaction (2) CH3CH2CH=CHCH3 will also form

Br

(3) CH3CH2CH—CH—CH3 will form (4) BrCH2CH2CH=CH–CH3 will form

Br Br
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12 Haloalkanes and Haloarenes Solutions of Assignment (Level-I) (Set-2)

Sol. Answer (2)

Action of NBS will result into the formation of more stable free radical at C-4.
8. Addition of HOCl to propene proceeds through
(1) Attact of Cl+
(2) Three membered cyclic intermediate
(3) Attack of OH+
(4) Attack of H+
Sol. Answer (2)
–
OH
CH3 CH CH2 + HO Cl CH3 CH CH2 CH3 CH CH2
+
Cl OH Cl
9. CH2 CH NO2 + HBr P
The major product ‘P’ is

(1) CH2 CH2 NO2 (2) CH3 CH NO2 (3) CH2 C NO2 (4) CH 2 CH Br
Br Br Br
Sol. Answer (1)
10. CH3 CH CH2 + HOBr P
The major product ‘P’ is

Br
(1) CH3 CH CH2 (2) CH3 CH CH2 (3) CH2 CH2 CH2 (4) CH3 C CH3
Br OH OH Br Br OH OH
Sol. Answer (2)
+
Br
–
CH3 CH CH2 + HOBr CH3 CH CH2 + OH CH3 CH CH2Br
OH
Secondary carbocation is more stable.

Br2/heat
11. P

P is

Br
Br Br Br Br
(1) (2) (3) (4)
Br

Sol. Answer (2)

[Isomerism]
12. The compound C2FCl BrI has
(1) Four isomers (2) Two optical isomers
(3) Two geometrical isomers (4) Six isomers

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Solutions of Assignment (Level-I) (Set-2) Haloalkanes and Haloarenes 13
Sol. Answer (4)
C2FCl Br I

F Br F I F Cl
C C C C C C
Cl I Cl Br Br I

F I F Cl F Br
C C C C C C
Br Cl I Br I I

13. How many chiral carbons are present in following structure?

CH3
OH

(1) 1 (2) 2 (3) 3 (4) 4

Sol. Answer (3)

CH3
OH
*
*
*

Above three indicated carbon are chiral.

14. How many structural isomers are possible for compounds having the molecular formula C5H11Br?

(1) 5 (2) 6 (3) 7 (4) 8

Sol. Answer (4)

Total 8 structural isomers are possible for C5H11Br. In which 3 from n-pentane, 4 from isopentane and 1 from
neopentane.

15. Among the three possible isomers of dibromo benzenes, the highest melting point is possessed by

(1) o-dibromobenzene (2) p-dibromobenzene

(3) m-dibromobenzene (4) All have same melting point

Sol. Answer (2)

More is the symmetry of compound, higher is the melting point of compound. So, p-dibromobenzene has
highest melting point.

16. The two compounds shown in the figure below are

Me Me

(1) Enantiomers (2) Diastereomers (3) Epimers (4) Structural isomers

Sol. Answer (2)
These two isomers are not the mirror images of each other.

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14 Haloalkanes and Haloarenes Solutions of Assignment (Level-I) (Set-2)

[Reaction (SN1, SN2, E1, E2)]

17. Which of the following compound will be most reactive for SN1 reaction?
Cl Cl
Cl CH3 Cl CH3

(1) (2) (3) (4)

Sol. Answer (4)

Alkyl halides which give more stable carbocation are more reactive towards SN1 reaction.

Cl CH3 CH3

solvent
∴
Most reactive Most stable tertiary
allyl carbocation
18. In the SN2 reaction of cis-3-methylcyclo pentyl bromide with alkali, the product formed is
(1) A cis alcohol (2) A trans alcohol
(3) An equimolecular mixture of cis and trans alcohol (4) There is no reaction
Sol. Answer (2)
SN2 reaction gives complete inversion because nucleophile attacks from the back side of leaving group.

CH3 CH 3
OH –
Br S N2 OH
Cis – 3 – Methyl Trans – Alcohol
Cyclo pentyl bromide
19. The reactivity order of alkyl halide is 3°>2°>1° in
(1) Both SN1 and SN2 (2) Both SN2 and E2 (3) Both E1 and SN2 (4) Both SN1 and E2
Sol. Answer (4)
The order of reactivity of alkyl halide in SN1 reaction depends on the stability of intermediate compound. More
is the stability of intermediate compound, higher is the reactivity of compound. In E2 reaction, reactivity of
alkyl halide depends on the stability of product. So, in SN1 and E2 reaction, order of reactivity of alkyl halide
becomes 3° > 2° > 1°. In SN2 reaction, order of reactivity of alkyl halide is 1°> 2° > 3°
20. Arrange the given alkyl halides in the increasing reactivity towards Nucleophilic substitution reactions.

Cl Br Cl Br
(A) (B) (C) (D)
(1) A > B > D > C (2) A > C > B > D (3) B > C > A > D (4) D > A > C > B
Sol. Answer (3)
Weaker the C—X bond greater the reactivity of alkylhalide towards Nucleophilic substitution reaction. Therefore
allyl halides with weaker C—X bond are more reactive than alkyl halides. Because of partial double bond
character in C—X bond in vinyl halides it is practically inert towards nucleophilic substitution reactions.

Partial double
bond chara cter
Br Br Br
Practically unreactive
towards S N2

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Solutions of Assignment (Level-I) (Set-2) Haloalkanes and Haloarenes 15
When we compare Bromoallyl halide and chloroallyl halide order is determined by the leaving group ability of
halide ions and hence, choice (3) is correct.

> > >

Br Cl Cl Br
(C) (A) (D)
(B)
Decreasing order of reactivity.
21. Each of the following reaction is given by tertiary butylbromide, except
(1) SN1 (2) SN2 (3) E1 (4) E2
Sol. Answer (2)
Tertiary butyl bromide doesn’t give SN2 reaction due to presence of bulky group.
22. Which of the following compound will give yellow precipitate on shaking with aqueous solution of NaOH followed
by the addition of AgNO3 solution?
Cl

(1) Me Me (2) — C — CH3

C— C — C
Me H CH3
Cl
Me I Br
(3) C — CH — CH (4)
Me Me
Sol. Answer (3)
Vinyl halides and aryl halides are unreactive towards Ag+. Therefore (1) and (4) will not give any precipitate.
While (2) and (3) will give precipitate.
Cl
+
Ag
C CH3 AgCl↓
White ppt.
CH 3

Cl I
H3C Ag
+

C CH CH Agl ↓
H3C Yellow ppt.
Me
23. When chloroform reacts with NaOH an important reactive intermediate is formed. Type of reaction involved and
formed intermediates are respectively.
..
(1) E2 and Cl — C — Cl (2) β-Elimination and Cl — C:

Cl Cl
.. 2
(3) E2 and Cl — C: (4) α-Elimination and Cl — C:

Cl Cl
Sol. Answer (4)
Cl Cl
OH –Cl
Cl
Cl C H Cl C C
Cl
Cl Cl Dichlorocarbene
Because H and Cl are removed from same C–atom. So, the reaction is α-elimination.

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16 Haloalkanes and Haloarenes Solutions of Assignment (Level-I) (Set-2)

24. Through SN2 reaction we cannot convert

(1) CH3 — CH2 — Cl into CH3CH2 — CN

CH3 CH3

(2) H3C — C — Br into CH3 — CH — O — C — CH3

CH3 CH3 CH3

(3) CH3 — CH — Br into CH3 — CH — O — C — CH3

CH3 CH3

Br H

(4) D Ph into I D

H Ph
(R) (R)
Sol. Answer (2)

 CH 3 
 | 
 Θ
Conversion No. (2) requires strong hindered base. i.e. Tertiary Butoxide ion  CH 3 — C — O  . This base
 | 
 CH 
 3 
prefers elimination over substitution reaction with alkyl halides except methyl halide.

CH 3

O C CH 3
H
CH 3
CH3 CH CH2 CH3 CH CH2
Strong Hindered base
Major product
Br

25. Suppose that CH3CH2I is added to an enthanol solution containing an excess of EtONa, EtSNa and NaOH
in equimolar amounts. What is the major product that will be isolated from the reaction?

H H
(1) O (2) OH (3) C— C (4) S
H H
Sol. Answer (4)
– is stronger nucleophile than –
In ethanol solution, EtS is the major product.
EtO . So, S
26. Rank the following compounds in order of increasing E2 reaction rate with alcoholic KOH.

Br
Br Br
(A) (B) (C)

(1) A < C < B (2) C < B < A (3) A < B < C (4) B < A < C

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Solutions of Assignment (Level-I) (Set-2) Haloalkanes and Haloarenes 17
Sol. Answer (3)
In (C), conjugated alkene is formed. So, it gives highest E2 reaction rate.
27. R – (–)–2-Bromooctane on treatment with aqueous KOH mainly gives 2-octanol that is
(1) Optically active with R configuration (2) Optically active with S configuration
(3) A racemic mixture (4) A meso compound
Sol. Answer (2)
SN2 involves inversion.
28. In the following reaction,
– + ∆
Br + HC C Na

The substrate is transformed into

(1) C C H (2) CH2 (3) (4) C C CH3

Sol. Answer (2)

Tertiary alkyl halide undergoes elimination reaction rather than substitution reaction with a strong base.

Cl KOH (aq)
29. CH P.
CH3
Product P (major) is

CH3
(1) H (2) (3) (4) OH
OH OH
Sol. Answer (4)
CH3
KOH (alcoholic) HBr/R2O2
30. CH3 C Br (A) (B)
∆
(Major)
CH3
(B) is
CH3 CH3 CH3 CH2 H
(1) CH3 C CH2 Br (2) CH3 C CH3 (3) CH3 C OH (4) CH3 C Br

H Br CH2 Br CH3
Sol. Answer (1)
31. The reaction of tertiary butyl bromide with sodium methoxide gives
(1) Isobutane (2) Tertiary butyl methyl ether
(3) Isobutylene (4) Butene
Sol. Answer (3)
Because of steric hindrene tertiary alkyl halides do not give SN2 reaction and it favours E2 reaction which
results into the formation of 2-methyl propene as the major product.
OH
CH3
H | CH3
E2
CH 2 — C — Br H 2C C
| CH3
CH3 Isobutylene

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18 Haloalkanes and Haloarenes Solutions of Assignment (Level-I) (Set-2)

32. The product obtained by reduction of benzyl bromide with LiAlH4 is

Br CH2Br CH3 CH3

(1) (2) (3) (4)

Sol. Answer (3)

CH2Br CH3
LiAlH4

Benzyl bromide Toluene

33. Which of the following statements is incorrect?

(1) An SN1 reaction proceeds completely with inversion of configuration
(2) An SN2 reaction proceeds with stereochemical inversion

(3) An SN2 reaction follows second-order kinetics

(4) E2 reactions are generally stereoselective
Sol. Answer (1)
In SN1 reaction, 50% inversion of configuration and 50% retention of configuration takes place. Other
statements are correct.
34. Benzal chloride on hydrolysis gives
(1) Benzyl alcohol (2) Benzoic acid (3) Benzaldehyde (4) Benzo tri alcohol
Sol. Answer (3)

CHCl2 CH(OH)2 CHO

2H2O –H2 O
Benzaldehyde
–2HCl
Benzal Chloride

35. For the reaction R – Br → R – O – N = O ,

(2º) (major)

the suitable reagent is

(1) NaNO2 + HCl (2) HNO2 (3) AgNO2 (4) KNO2
Sol. Answer (4)

NO Θ
2 is an ambident nucleophile.

O N O

When o-acts as donor atom nitritester is obtained as major product. When N acts as a donor atom Nitroalkane
is the major product. For the chemoselectivity of the reaction. Different reagents are used.

AgNO2 KNO2
i.e., R — NO2 ←⎯⎯⎯ ⎯ R — Br ⎯⎯⎯⎯ → R — O — NO
major major

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Solutions of Assignment (Level-I) (Set-2) Haloalkanes and Haloarenes 19

36. Which of the following substrate is most reactive towards methoxide ion ( Me – O )?

(1) CH3 — I (2) CH3 — O — SO2 — — CH3

(3) CH3 — O — SO2 — CF3 (4) CH3 — F

Sol. Answer (3)
That substrate is most reactive which has best leaving group (weakest base). CH3 – O – SO2 – CF3 is most
reactive substrate because it has – O – SO2 – CF3 (weakest base) group.
37. On the basis of the given reaction sequence, find out the final product.

H H 1. LiNH2(Excess)
NH3 Na / NH3
Br — C — C — Br [A] [B]
2. Et-Br (2 eq)
H H

Et Et Et H
(1) Et — C —
— C — Et (2) Et — C —
— C—H (3) C— C (4) C— C
H H H Et
Sol. Answer (4)

H— H 1. LiNH2(Excess) Et— H
—
— C —Et Na/NH3 —
Br —
— C — C — Br
— Et — C —
— — C—
—C —
H H 2. EtBr (2 eq.) H Et
[A] [B]

From [A] to [B] is the Birch reduction.

38. PhMgBr (Grignard reagent) cannot be used to prepare the compound?

(1) — C — OH (2) — CH2 — CH2 — OH

O CH3

(3) — C — CH3 (4) — C — CH3

CH3

Sol. Answer (4)

PhMgBr with Tertiarybutyl bromide gives, Elimination (E2) product as the major product.

H CH3
CH 3
MgBr + CH2 C Br H + H2C C
CH 3
CH3
Tertiary alkyl halide
(prefers E 2 over S N2)

39. (R)-2-Bromobutane is allowed to react with NaI in acetone. The product formed is
(1) (R)-2-Iodobutane (2) S-2-Iodobutane (3) (±)-2-Iodobutane (4) 2-Butane
Sol. Answer (2)
This reaction goes through SN2 mechanism.

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20 Haloalkanes and Haloarenes Solutions of Assignment (Level-I) (Set-2)

40. The reaction of phenylacetylene with one equivalent of methyl magnesium bromide followed by reaction with
benzaldehyde provides

OH Me H

OH Me Ph
(1) Ph—C C— (2) Ph (3) Ph (4) Ph Me
Ph
Ph H OH
Sol. Answer (1)
Action of Grignard reagent on terminal alkyne will result into the formation of alkynide Grignard reagent.
+
41. PI3 KCN H2O/H
CH3OH (A) (B) (C)
The compound (C) is
(1) CH3CN (2) CH3CH2NH2 (3) CH3COOH (4) CH3CH2COOH
Sol. Answer (3)
+
PI KCN H2O / H
CH 3 OH ⎯ ⎯
⎯3
→ CH 3I ⎯ ⎯ ⎯→ CH 3 CN ⎯ ⎯ ⎯⎯→ CH 3 COOH
(A ) (B ) (C )

42. What would be the major product of the given reaction?

MeO

I Cu
I

MeO

MeO HO

(1) (2) I (3) (4)

I

MeO HO

Sol. Answer (1)

Here, major product is formed according to Ullmann’s reaction. The reaction is expected to proceed through
free radical mechanism.
43. Which chloroderivative of nitrobenzenes among the following would undergo hydrolysis, most readily with
aqueous NaOH?

O2N O2N NO2 NO2 O2N Cl

(1) O2N Cl (2) Cl (3) O2N Cl (4) Cl

O2N O2N NO2 O2N Cl

Sol. Answer (3)

As the –NO2 group is attached at ortho and para position w.r.t. Cl atom in benzene ring, the replacement
–NO2
of Cl atom becomes easier. So, O 2N – – Cl undergo hydrolysis with aqueous NaOH most readily.
–
NO2
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Solutions of Assignment (Level-I) (Set-2) Haloalkanes and Haloarenes 21
Cl
Liq. NH3
44. + KNH2 (P). Product (P) is

Cl Cl Cl NH2
NH2
(1) (2) (3) (4)
NH2
NH2
Sol. Answer (4)

NC
NH2
R
45. ; R is

(1) N2 (2) CHCl3/KOH (alcoholic) (3) NH3 (4) KCN

Sol. Answer (2)
Carbylamine test.

Cl
HNO3/H2SO4 NaOH
46. A B ; B is
433 K

NO2 NO2 NO2

OH Cl
(1) (2) (3) (4)
OH
NO2 OH

Sol. Answer (4)

CH2 OH
+
SOCl2 KCN H
47. (A) (B) (C), the compound (C) is

COOH CH3 CH2 COOH CH3

(1) (2) (3) (4)

COOH
COOH

Sol. Answer (3)

CH2 Cl CH2 CN CH2 COOH

A= B= C=

48. Arrange the following in the increasing order of ease of nucleophilic substitution reaction.
Chlorobenzene (I), 2,4,6 trinitrochlorobenzene (II), 2, 4 dinitro-chlorobenzene (III) and 4-nitrochloro benzene (IV)
(1) I < IV < III < II (2) I < III < IV < II (3) II < III < IV < I (4) IV < III < II < I

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22 Haloalkanes and Haloarenes Solutions of Assignment (Level-I) (Set-2)

Sol. Answer (1)

As the number of electron withdrawing group increases on ortho and para position w.r.t. halogen atom, the
nucleophilic substitution becomes faster.

Anhydrous
49. Compound X in the reaction is + ICl AlCl3
X

I
Cl I Cl

(1) (2) (3) (4)

Cl Cl

Sol. Answer (2)

δ( + ) δ( − )
AlCl
3 → I+ + AlCl −
I — Cl ⎯ ⎯ ⎯ 4

I I
–H
I H
σ-complex

In this reaction, only I+ is obtained as electrophile.

‰ ‰ ‰

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