2PBCBDC–Haloalkanes and Haloarenes(S)

10. Haloalkanes and Haloarenes

Exercise

Unit I
Very short answer questions (VSA)
1. Name the following alkyl halides according to IUPAC system and classify them as primary, secondary
and tertiary alkyl halides:
(i) (CH3)2CHCHClCH3 (ii) CH3C(C2H5)2CH2Br
(iii) CH3C(Cl)(C2H5)CH2CH3 (iv) CH3CH2CH(CH3)CH(C2H5)Cl
(v) CH3CH(CH3)CBr(CH2CH3)2 (vi) (CH3)3CCH2CH(Br)C2H5
(vii) CH3CH2C(CH3)2CH2I
Solution
(i) 2-Chloro-3-methylbutane:
methylbutane: secondary alkyl halide
(ii) 1-Bromo- 2-ethyl-2-methylbutane:
methylbutane: primary alkyl halide
(iii) 3-Chloro-3-methylpentane:
methylpentane: tertiary alkyl halide
(iv) 3-Chloro-4-methylhexane:
methylhexane: secondary alkyl halide
(v) 3- Bromo-3-ethyl-2-methylpentane:
methylpentane: tertiary alkyl halide
(vi) 4-Bromo-2,2-dimethyl
dimethyl hexane: secondary alkyl halide
(vii) 1-Iodo-2,2-dimethylbutane:
dimethylbutane: primary alkyl halide
2. Write the structures for the following compounds:
(i) 2-Chloro-3-methylpentane (ii) 4-tert-butyl-3-iodoheptane
Solution
(i) CH3 CH CH CH2 CH H3 (ii) CH3 CH2 CH CH C 2 CH2
CH CH3

Cl CH3 I CH3 C CH3

CH3

3. What happens when ethanol is heated with conc. HCl and anhydrous ZnCl2?
Solution
Chloroethane (C2H5Cl) is formed
4. Mention the product formed when 2-propanol
2 is heated with PCl5.
Solution
2-chloropropane
chloropropane (or isopropyl chloride)
5. CH3Br + AgF → CH3F + AgBr. Name the reaction. [March 2014, July 2016, March 2018]
(or)
Solution
Swarts reaction
acetone
6. CH 3Cl + NaI  → CH 3 I + NaCl
Name the above reaction. [July 2015, July 2018]
Solution
Finkelstein reaction

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CBDC–Haloalkanes and Haloarenes(S)

7. Write the structure of the major organic compound formed in each of the following reactions:
pyridine
(i) CH3CH2CH2CH2OH + SOCl2 (ii) CH3 CH C CH3 + HBr
H

CH3
peroxide
(iii) CH3 CH2 CH CH2 + HB
Br (iv) CH3 CH CH2 + HI
Cl
HNO3
(v)

Solution
(i) CH3CH2CH2CH2Cl
Br

(ii) CH3 CH2 C CH3

CH3
(iii) CH3 CH2 CH2 CH2Br
I
(iv) CH3 CH CH3
Cl Cl
NO2
(v)
+

NO2

8. Arrange the following in the order of increasing boiling points:

(i) CH3CH2Cl, CH3CH2Br, CH3CH2I, CH3CH2F
(ii) 1-chloropropane, 2-chloropropane,
chloropropane, 1-chlorobutane
1
Solution
(i) CH3CH2F, CH3CH2Cl, CH3CH2Br, CH3CH2I
(ii) 2-chloropropane, 1-chloropropane,
chloropropane, 1-chlorobutane
1
9. Complete the reaction:
∆
CH3CH 2 Br + AgCN  → [July 2015, March 2020]
(Alc)

Solution
CH3CH2NC
10. Complete the following reactions:
acetone water
(i) CH3CH2CH2Cl + NaI (ii) CH3CH(Br)CH2CH3 + NaOH
N
heat heat
ethanol ethanol
(iii) (CH3)3CBr + KOH (iv) CH3CH2CH2Cl + KCN
heat heat
Solution
(i) CH3CH2CH2I (ii) CH3CH(OH)CH2CH3
CH3

(iii) CH3 C CH2 (iv) CH3CH2CH2CN

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 2PBCBDC
2PBCBDC–Haloalkanes and Haloarenes (S)

11. Give the reaction of ethyl bromide with magnesium in dry ether.
Solution
C2H5Br + Mg dry ether
C2H5MgBr
Ethyl magnesium bromide

12. Between CH3Br and CH3I, which reacts faster with OH ion by SN2 mechanism?
Solution
CH3I
13. What is chirality? [March 2014]
Solution
superimposable on their mirror image are said to be chiral and this property is
The objects which are non-superimposable
known as chirality
14. What is an asymmetric carbon or chiral carbon? [March 2017]
Solution
Carbon bonded to four different atoms or groups
15. What are enantiomers? [July 2015]
Solution
Stereoisomers which form a pair of non
non-superimposable mirror images.
16. What is racemisation? [March 2020]
Solution
Process of conversion of enantiomer into a racemic mixture
17. What is racemic mixture? [June 2019]
Solution
Equimolar mixture of a pair of enantiomers
18. What happens when bromoethane is heated with sodium in
in the presence of dry ether?
Solution
Butane is formed
19. Name the reagent used in the dehydrohalgenation of haloalkanes.
(or)
What is the reagent used in the conversion of alkyl halide into alkene? [July 2015, March 2018]
Solution
Alcoholic KOH or alcoholic potash
20. Name the major organic product formed when 22-bromopentane
bromopentane is heated with alcoholic potassium
hydroxide solution. [June 2019]
Solution
Br
H3C CH2 CH CH2 CH3 + KOH(alc) H3 C CH2 CH CH CH3 + KBr + H2O
2-Bromopentane Pent-2-ene
(Major product)

21. Write the general

ral formula of Grignard reagent or what is Grignard regent? [March 2016]
Solution
RMgX (or) Organometallic compounds which contain carbon
carbon-metal bond

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 2PBCBDC
CBDC–Haloalkanes and Haloarenes(S)

22. Mention the major product formed in the following reactions:

Dry ether
(i) C6 H5 Br + Mg  →
alc. KOH, ∆
(ii) 2-Bromopentane →
dry acetone
(iii) CH3Cl + NaI  → [July 2014]
(iv) CH 3 MgBr + H 2 O 
→
Solution
(i) C6H5MgBr
(ii) Pent-2-ene
(iii) CH3I
(iv) CH3MgBr + H2O → CH4 + Mg(OH)Br
23. Write the general equation for Wurtz reaction. [March 2019]
Solution
dry ether
2R X + 2Na R R + 2NaX
Alkyl halide Higher alkane

Short answer questions (SA)

24. Explain the order of reactivity of hydrogen halides towards alcohols.
Solution
The order of reactivity of hydrogen halides is HI > HBr > HCl as reactivity is inversely proportional to
bond dissociation enthalpy.
25. What is the order of reactivity of alcohols with a given halogen acid? Explain.
Solution
The order of reactivity of alcohols with a halogen acid is tertiary alcohol > secondary alcohol
a > primary
alcohol. This is because, more the number of electron releasing groups on the α-carbon atom of the
alcohol, higher the polarity of the C−OH bond and easier the bond breakage.
26. Write the reaction of 1-propanol
propanol with red phosphorous and bromine.
bromi
Solution
Red P + Br2
3CH3CH2CH2OH + PBr3 3CH3CH2CH2Br + H3PO3
heat

27. Write the reaction of 2-propanol

propanol with KBr and conc. H2SO4.
Solution
KBr +
conc. H2SO4
CH3 CH CH3 + HBr CH3 CH CH3 + H2O
heat
OH Br
28. What is the action of KI and orthophosphoric acid on alcohols? Give an example.
Solution
Alcohols react with KI and H3PO4 on heating to form respective alkyl iodides.
Example: KI + H3PO4 HI + KH2PO4
ROH + HI 
→ RI + H 2 O

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2PBCBDC–Haloalkanes and Haloarenes (S)

29. Explain Darzen’s reaction with an example.

Solution
An alcohol reacts with thionyl chloride in the presence of pyridine to give a chloroalkane. This reaction
is called Darzen’s reaction.
pyridine
Example: CH3CH2OH + Cl.SO.Cl CH3CH2Cl + SO2 + HCl
Ethanol (SOCl2) Chloroethane

30. Explain Finkelstein reaction with an example.

Solution
Iodoalkanes can be obtained by treating bromoalkanes or chloroalkanes with a solution of sodium iodide
in dry acetone. This reaction is known as Finkelstein reaction.
acetone
C2 H5Cl + NaI  → C2 H5 I + NaCl
chloroethane Iodoethane

31. Give a method of preparation of an alkyl fluoride from an alkyl halide with an example. Name the
reaction.
Solution
An alkyl chloride or bromide reacts with metal fluorides such as silver fluoride or mercurous fluoride on
heating to form the alkyl fluoride. This is Swarts reaction.
Example: CH3Br + AgF CH3F + AgBr
Methyl bromide Methyl fluoride

32. A hydrocarbon, C5H12 reacts with chlorine in the presence of sunlight to give a single monochloro
compound C5H11Cl. Identify
ify the hydrocarbon and write the reaction.
Solution
CH3
The hydrocarbon is neopentane, CH3 C CH3
CH3
CH3 CH3
light
CH3 C CH3 + Cl2 CH3 C CH2 Cl + HCl

CH3 CH3
Neopentane Neopentyl chloride
Since all H–atoms
atoms are equivalent, only one monochloro compound is formed.
33. Explain Kharasch or peroxide effect with an example.
Solution
Addition of HBr to an unsymmetrical alkene in the presence of organic peroxide takes place in the
manner opposite to that of Markownikov’s rule to form a primary alkyl halide as a major product.
product
benzoyl peroxide
CH3 CH CH2 + HBr CH3 CH2 CH2Br
Propene 1-Bromopropane
(major product)

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 2PBCBDC
CBDC–Haloalkanes and Haloarenes(S)

34. What are ambident nucleophiles? Give an example.

Solution
Species which attack an electron deficient carbon atom through different nucleophilic centers are called
ambident nucleophiles. Examples: CN− , NO −2
35. What happens when bromoethane is heated with
(i) aqueous KOH (ii) ethanolic solution of sodium ethoxide
(iii) alcoholic KCN (iv) alcoholic AgCN
(v) alcoholic ammonia (vi) ethanolic AgNO2
(vii) alcoholic silver acetate (viii) LiAlH4 in dry ether
(ix) Methyl lithium
Solution
heat
(i) C2H5Br + KOH C2H5OH + KBr
(aq)
Ethanol
ethanol
(ii) C2H5Br + C2H5ONa+ C2 H 5 O C2H5 + NaBr
heat
Diethyl ether
(iii) C2H5Br + KCN heat
C2H5CN + KBr
(alcoholic) Ethyl cyanide
heat
(iv) C2H5Br + AgCN C2H5NC + AgBr
(alcoholic) Ethyl isocyanide
heat
(v) C2H5Br + NH3 C2H5NH2 + HBr
(alcoholic) Ethyl amine
heat
(vi) C2H5Br + AgNO2 C2H5 NO2 + AgBr
(ethanolic) Nitroethane
O O
heat
(vii) C2H5Br + CH3 C OAg CH3 C O C2H5 + AgBr
(ethanol) Ethyl acetate
ether
(viii) 4C2H5Br + LiAlH4 4C2H6 + LiBr + AlBr3
Ethane
(ix) C2H5Br + CH3Li CH3 CH2 CH3 + LiBr
Propane

36. Explain dehydrohalogenation with an example (or) Explain Zaitsev rule with an example.
Solution
When alkyl halides with β-hydrogen
hydrogen atom are heated with alcoholic KOH, the halogen atom and a
β-hydrogen
hydrogen atom are removed as hydrogen halide forming an alkene.
According to Zaitsev rule, the alkene with more number of alkyl groups attached to doubly bonded
carbon atoms (more substituted alkene) will be formed as the major product.
β α
heat
CH3 CH2 Br + KOH CH2 CH2 + KBr + H2O
Alcoholic Ethene

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2PBCBDC–Haloalkanes and Haloarenes (S)

37. Predict the alkenes that are formed by the dehydrohalogenation of 2-chloro-2-methylbutane.
2 methylbutane.
Solution
CH3
CH3 C CH CH3
CH3
2-methylbut-2-ene (major product)
CH3 C CH2 CH3
HCl
Cl CH3

CH2 C CH2 CH3

2-methylbut-1-ene (minor product)

38. Explain the relative reactivity of primary, secondary and tertiary alkyl halides towards β -elimination.
Solution
β-elimination
elimination proceeds through the formation of carbocation Hence, the order of reactivity of
haloalkanes towards β -elimination
elimination is tertiary > secondary > primary.
39. What is Wurtz reaction? Give an example.
Solution
Haloalkanes react with sodium metal in dry ether
ether to form higher alkanes. This reaction is called Wurtz
reaction.
dry ether
2CH3Cl + 2Na  → H3C − CH3 + 2NaCl
Ethyl chloride Ethane

40. Alkyl chlorides react with aqueous KOH to give alcohols, but react with alcoholic KOH to give alkenes
as major products. Explain.
Solution
There is a competition
ion between nucleophilic substitution and elimination reactions. In the presence of
solvent of high polarity such as water, substitution is favoured resulting in the formation of an alcohol.
In the presence of solvent of low polarity such as ethanol, elimination is favoured forming an alkene as a
major product.
41. How are the following conversions carried out?
(i) Propene to 1-propanol (ii) 1-Bromopropane
Bromopropane to 2-Bromopropane
2
(iii) Ethanol to propanenitrile (iv) 2-Chlorobutane
Chlorobutane to 3,4-Dimethylhexane
3,4
(v) Isopropyl chloride to Isopropyl magnesium chloride
Solution
organic aq. KOH
(i) CH3 CH CH2 + HBr CH3 CH2 CH2Br CH3 CH2 CH2 OH
peroxide heat
KBr
alcoholic KOH
(ii) CH3 CH2 CH2Br CH3 CH CH2 + HBr CH3 CH CH 3
−KBr, −H
− 2O
Br
KBr + Conc. H2SO4 alcoholic KCN
(iii) CH3CH2OH CH3CH2Br CH3CH2CN
heat KBr
dry ether
(iv) CH3 CH2 CHCl + 2Na + Cl CH CH2 CH2 CH3 CH2 CH CH CH2 CH3
heat
CH3 CH3 2NaCl CH3 CH3

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 2PBCBDC
CBDC–Haloalkanes and Haloarenes(S)

dry ether
(v) CH3 CH CH3 + Mg CH3 CH CH3

Cl MgCl

42. (i) Name the product formed for the reaction of isopropyl iodide on alcoholic KOH.
(ii) What is the condition to be satisfied for a compound to be chiral? [March 2019]
Solution
(i) Propene
(ii) Condition for chirality is that the carbon must be bonded to four different atoms or groups in a
molecule.

Solution to Long answer questions (LA)

43. Write the equations for the preparation of 1-Iodobutane
1 from
(i) 1-Butanol (ii) 1-Chlorobutane
Chlorobutane (iii) 1-Butene
1
Solution
KI/H3PO4
(i) CH3CH2CH2CH2OH + HI CH3CH2CH2CH2I + H2O
heat
acetone
(ii) CH3CH2CH2CH2Cl + NaI CH3CH2CH2CH2I + NaCl
heat
peroxide
(iii) CH3 CH2 CH CH2 + HB
Br CH3 CH2 CH2 CH2Br CH3 CH2 CH2 CH2 I
NaI

44. Write equations for the steps in SN1 mechanism for the conversion of tertiary butyl alcohol. (or) Explain
the mechanism of SN1 reaction taking 2-Bromo-2-methyl
2 propane (t-butylbromide)
butylbromide)
[March 2015, 2016,6, 2020, July 2014, 2018, June 2019]
Solution
(CH3)3CBr + aq. NaOH → (CH3)3C – OH + NaBr
Step 1: Heterolytic fission of C−Br bond to form a carbocation
CH3 H3C CH3
slow
CH3 C Br C+ + Br −
∆
CH3 CH3
tert-butyl bromide tert-butyl carbocation

Based on the kinetics of the reaction, rate = k[(CH3)3CBr]1

Order of the reaction = 1
Step 2: Attack of nucleophile on the carbocation to form an alcohol
CH3 CH3
fast
CH3 C+ + OH− CH3 C OH
nucleophile
CH3 CH3
tert-butyl bromide tert-butyl alcohol
[2-Bromo-2-methylpropane] [2-Methylpropan-2-ol]

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2PBCBDC–Haloalkanes and Haloarenes (S)

45. Write equations for the step involved in SN2 mechanism for the conversion of methyl bromide to methyl
alcohol. (or) Explain the mechanism of SN2 reaction by taking the example of methyl bromide.
Solution
Hydrolysis of methyl bromide by aqueous sodium hydroxide to give methyl alcohol. The net reaction is
represented as shown below.
CH3Br + OH CH3OH + Br
Substrate Nucleophile
Based on the kinetics of the reaction, r = k[CH3Br]1 [OH−]1
The nucleophile, OH attacks the substrate, methyl bromide from the side opposite to that of the bromine
atom. As a result, a pentavalent transition state is formed in which the formation of C–OH
C bond and the
cleavage of C–Br
Br bond take place simultaneously.
When the formation of C–OH OH bond and the rupture of C–Br C Br are completed, CH3OH and Br − are
obtained as shown below:
H δ+ H H H H H
δ−
OH + C Br HO C Br HO C + Br
H H H
Transition state
The product formed has an inverted configuration with respect to the substrate.
subst
46. Explain the stereochemical consequence of SN1 reaction mechanism by taking the example of 2-
bromobutane.
Solution
2-bromobutane,
bromobutane, an optically active alkyl halide reacts with aqueous NaOH by SN1 mechanism. A
racemic mixture of butan-2-olol is formed (50% inverted and 50% retention of configuration). This is
because the reaction involves the formation of carbocation, which is planar. Hence the nucleophile, OH−
attacks the carbocation from either side of plane with equal ease as shown below:
H3C CH3

+
H Br C + Br
C2 H 5 H C2 H 5
Carbocation (planar)
2-Bromobutane
CH3 H3C
CH3
+
HO C OH HO H + H OH
H C2H5 C2H 5
C 2 H5
(Inversion of (Retention of
configuration) configuration)

(±) or racemic Butan-2-ol

Thus, SN1 reactions of optically active alkyl halides are accompanied by inversion and retention of
configuration resulting in the formation of racemic mixture.

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CBDC–Haloalkanes and Haloarenes(S)

47. Explain the stereochemical consequence of SN1 reaction mechanism nism by taking the example of 2- 2
bromooctane.
Solution
2-bromooctane,
bromooctane, an optically active alkyl halide reacts with aqueous NaOH by SN2 mechanism.
ol with an inverted configuration is formed. This is because, the nucleophile, OH− attacks the
octan-2-ol
C−Br bond octan ol with −OH group occupying
nd from the opposite end of the bromine atom forming octan-2-ol
the position opposite to that of Br atom.
H3C CH3
H Br + OH HO H + Br
C6H13 C6H13
2-Bromoctane Octan-2-ol
(inversion of configuration)
Thus, SN2 reactions of optically active alkyl halides are accompanied by inversion of configuration.
48. Mention the factors that favour SN1 and SN2 mechanisms.
Solution
SN1 mechanism SN2 mechanism
• Favoured by low concentration of the • Favoured by high concentration
nucleophilic reagent of the nucleophilic reagent
• Favoured by polar protic solvents • Favoured by non-polar aprotic
solvents
• Weak nucleophile favours SN1 • Strong nucleophile favours SN2
• Order = 1 • Order = 2
49. An alkyl halide C4H9Br (A) is treated with alcoholic KOH to give compound B, which is treated with
HBr to give (C), which is an isomer
isomer of A. (A) is reacted with Na in dry ether to give the compound
C8H18 (D), which is different from the compound obtained from n-butyl
n butyl bromide is reacted with Na in
dry ether. Identify the compound (A) and write all the reactions.
Solution
Compound A is CH3 CH CH H2Br (isobutyl bromide)

CH3
CH3
alcoholic KOH
CH3 CH CH2Br HBr
CH3 C CH2 CH3 C CH3
KBr, H2O
CH3 CH3 Br
(A) (B) (C)
2Na/dry ether
2 CH3 CH CH2Br CH3 CH CH2 CH2 CH CH3
heat
CH3 NaBr CH3 CH3
(A) (D)

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2PBCBDC–Haloalkanes and Haloarenes (S)

50. Identify the products A, B and C in the following equation: [March 2015]
red P NaI C6 H 5 I
CH 3 OH  Cl 2
→ A 
dry acetone
→ B →
Na and dry ether
C
Solution
CH3

red P NaI 6 5 CHI

CH3OH CH3Cl dry CH3I
Cl2 Na and
A acetone B dry ether
C
A=CH3Cl B=CH3I C=C6H5CH3

Unit II Haloarenes
Very short answer questions (VSA)
1. Name the product of the reaction between benzene and bromine in the presence of FeBr3 catalyst.
Solution
Bromobenzene
2. Name the organic compound formed when chlorobenzene is treated with sodium in dry ether.
[March 2015, 2017]
Solution
Diphenyl or Biphenyl
Cl
3. Write the IUPAC name of . [July 2016]
CH 3

Solution
1-Chloro-2-methylbenzene
4. In aryl halides, what is the hybridization of carbon atom to which halogen is attached? [July 2018]
Solution
The hybridization of carbon atom to which halogen is attached in aryl halides is sp2

Short answer questions (SA)

5. Explain Sandmeyer’s reaction.
Solution
When benzene diazonium chloride is heated with cuprous chloride and conc. HCl or cuprous bromide
and conc.HBr forms halobenzene. This reaction is called Sandmeyer’s
Sandmeyer reaction.
N2Cl Cl
Cu2Cl2 / conc.HC
Cl
+ N2
heat
Chlorobenzene

6. Write the preparation of iodobenzene from benzenediazonium chloride.

Solution
Iodobenzene is prepared by shaking benzenediazonium chloride with potassium iodide solution.

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 2PBCBDC
CBDC–Haloalkanes and Haloarenes(S)

N2Cl I
+ KI + N2 + KCl

Benzenediazonium Iodobenzene
chloride

7. How do you convert chlorobenzene to phenol?

Solution
When chlorobenzene is heated with aqueous solution of NaOH under pressure −Cl atom is replaced by
−OH group only to form phenol.
Cl OH
+ NaOH 623 K, 300 atm + NaCl
aqueous
Phenol

8. The dipole moment of chlorobenzene is lower than that of chloroethane. Why?

Solution
The C−Cl bond in chlorobenzene is shorter and less polar than that in chloroethane
chloroethane due to resonance
effect.
9. p-Dichlorobenzene
Dichlorobenzene has higher melting point than those of ortho and meta isomers. Give reason.
[July 2016]
Solution
p-Dichlorobenzene
Dichlorobenzene has higher melting point than ortho and meta isomers due to higher symmetry.
10. Aryl halides are less reactive than alkyl halides towards nucleophilic substitution reaction. Explain based
on resonance effect. (or)
Haloarenes are less reactive towards nucleophilic substitution
substitution reactions than haloalkanes. Give reasons.
[March 2014, March 2017]
Solution
Resonance effect
The lone pair of electrons on halogen atoms are in conjugation with π-electrons
electrons of the ring. Due to
resonance, the C−X bond acquires partial double bond character. As a result the C−X C bond is relatively
strong and hence the bond cleavage is difficult.
.. + .. + .. + .. ..
:X : X: X: X: :X :
−
−

Hybridised state of carbon atom

In haloalkanes, the halogen atom is bonded to sp3 hybridised carbon atom, while in haloarenes it is
bonded to sp2 hybridised carbon atom.
sp2 hybridised carbon atom is more electronegative than sp3 hybridised carbon atom. Hence sp2
hybridised carbon pulls the bonding pair of electrons in C–X
C X bond. Hence the C−X
C bond is shorter and
stronger in haloarenes than in haloalkanes.

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2PBCBDC–Haloalkanes and Haloarenes (S)

Polarity of C−X bond

The C−X
−X bond in haloarenes is less polar than that in haloalkanes. This is due to resonance effect in
haloarenes.
Repulsive interaction
The nucleophile being electron rich gets repelled by delocalised electron density in the benzene ring.
Instability of carbocation
Due to the strong C−X
−X bond in haloarenes, the self ionisation to form phenyl carbocation is not possible.
Even if it is formed,
ed, it cannot be stabilised by resonance.
11. Explain the following electrophilic substitution reactions of chlorobenzene:
(i) Chlorination (ii) Nitration (iii) Sulphonation
(iv) Friedel - Crafts methylation (v) Friedel - Crafts acetylation [June 2019]
Solution
(i) Chlorobenzene reacts with Cl2 in the presence of Fe or FeCl3 to form a mixture of
1,2-dichlorobenzene
dichlorobenzene and 1,4-dichlorobenzene.
1,4
Cl Cl Cl
anh. FeCl3 Cl
+ 2Cl2 + + 2HCl
2

Cl
1,2-Dichlorobenzene 1,4-Dichlorobenzene
or or
o-Dichlorobenzene p-Dichlorobenzene
(minor) (major)

(ii) Chlorobenzene reacts with nitrating mixture on heating to form a mixture of

ortho-nitrochlorobenzene
nitrochlorobenzene and para-nitrochlorobenzene.
para
Cl Cl Cl
concc.H2SO4 NO2
2 + 2HO.NO2 + + 2H2O
(conc.HNO3) heat

NO2
Chloro 2 nitrobenzene Chloro 4 nitrobenzene
(o-Chloronitrobenzene) (p-Chloronitrobenzene)
(minor) (major)
(iii) Chlorobenzene reacts with fuming sulphuric acid, on heating to form a mixture of 2-chlorobenzene
2
sulphonic acid and 4-chlorobenzene
chlorobenzene sulphonic acid.
Cl Cl Cl
heaat SO3H
2 + HO.SO3H + + 2H2O
(fuming H2SO4)
SO3H
2-Chlorobenzene 4-Chlorobenzene
sulphonic acid sulphonic acid
(minor) (major)

(iv) Chlorobenzene reacts with methyl chloride in the presence of anhydrous AlCl3 catalyst to form a
mixture of 2-chlorotoluene
chlorotoluene and 4-chlorotoluene.
4

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CBDC–Haloalkanes and Haloarenes(S)

Cl Cl Cl

anhydrous AlCl3 CH3

2 + CH3Cl + + 2HCl

CH3
2-Chlorotoluene 4-Chlorotoluene

(v) Chlorobenzene reacts with acetyl

acet chloride in the presence of anhydrous
ous AlCl3 catalyst to form a
mixture of 2-methylacetophenone
methylacetophenone and 4-methylacetophenone.
4

Cl Cl O Cl
O
anhydrous AlCl3 C CH3
2 + 2CH3 C Cl + + 2HCl

C
O CH3
2-Chloroacetophenone 4-Chloroacetophenone

12. Explain Wurtz-Fittig

Fittig reaction with an example. [March 2016]
Solution
A mixture of an alkyl halide and aryl halide reacts with sodium in dry ether to form an alkylbenzene.
This is called Wurtz-Fittig
Fittig reaction.
Cl CH3
+ CH3Cl + 2Na dry ether + 2NaCl
heat
Chlorobenzene Chloromethane Toluene

13. What is Fittig reaction? Give an example.

Solution
Chlorobenzene reacts with sodium in dry ether on heating to form biphenyl. This is called Fittig reaction.
dry ether
Cl + 2Na + Cl + 2NaCl
heat

Biphenyl

Long answer questions (LA)

14. Explain the influence of halogen atom in aryl halides towards electrophilic substitution reactions.
Solution
Aryl halides undergo usual electrophilic substitution reactions, but less reactive than benzene. This is
because, the electron withdrawing inductive effect (−I
(−I effect) of the halogen atom decreases the electron
density on the benzene ring. In other words, the benzene
benzene ring is deactivated. As a result, the electrophilic
substitution reactions take place not only slowly but also under drastic conditions as compared to
benzene.

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 2PBCBDC
2PBCBDC–Haloalkanes and Haloarenes (S)

Unit III Polyhalogen compounds

Very short answer questions (VSA)
1. What are polyhalogen compounds?
Solution
Organic compounds containing two or more halogen atoms are called polyhalogen compounds.
2. What are Freons? [July 2014]
Solution
Chloroflorocarbon compounds of methane and ethane are called Freons.
3. Name the poisonous gas formed when chloroform is oxidised? [August 2020]
Solution
Phosgene or COCl2
4. Mention any two applications of each of the following polyhalogen compounds:
(i) Dichloromethane (ii) Chloroform (iii) Carbon tetrachloride
(iv) Iodoform (v) Freons
Solution
(i) Dichloromethane:
(a) As a solvent in paint remover, in the manufacture of drugs, metal cleaning and finishing
(b) As a propellant in aerosols
(ii) Chloroform:
(a) As a solvent for fats, alkaloids, iodine (b) In the production of freon refrigerant
(iii) Carbon tetrachloride:
(a) In the manufacture of refrigerants, propellants for aerosol cans and chloroform
(b) As an industrial solvent
(iv) Iodoform:
(a) As an antiseptic for dressing wounds (b) In the pharmaceuticals
(v) Freons:
Refrigeration, air conditioning units, propellants for aerosol
5. Mention the harmful effects of
(i) Dichloromethane (ii) Chloroform (iii) Carbon tetrachloride (iv) Freons (v) DDT
Solution
(i) Dichloromethane:
(a) Harms the central nervous system
Exposure
posure to methylene chloride in lower levels in air causes slight impairment of hearing and
vision.
(b) Higher levels of methylene chloride in air cause dizziness, nausea, tingling and numbness in
fingers and toes.
(ii) Chloroform:
(a) Harms the central nervous system
(b) Exposure to methylene chloride in lower levels in air can lead to slightly impaired hearing and
vision. Higher levels of methylene chloride in air cause dizziness, nausea, tingling and numbness
in fingers and toes.

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 2PBCBDC
CBDC–Haloalkanes and Haloarenes(S)

(iii) Carbon tetrachloride:

(a) Inhalation of chloroform vapours depresses the central nervous system, causes dizziness, fatigue
and headache.
(b) Damages liver and kidneys
(iv) Freons :
Depletes the ozone layer
(v) DDT:
Not metabolised in animals and gets
gets deposited in fatty tissues and is highly toxic
6. What is the structure of DDT?
Solution
Cl
Cl C CH Cl
Cl

Cl

***

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