UNIT HALOALKANES AND

HALOARENES
(QUESTIONS & ANSWERS)

10.1 Write structures of the following compounds:

(i) 2-Chloro-3-methylpentane (ii) 1-Chloro-4-ethylcyclohexane (iii) 1,4-Dibromobut-2-ene
(iv) 4-tert. Butyl-3-iodoheptane (v) 1-Bromo-4-sec. butyl-2-methylbenzene.
Cl
1
1 2 3 4 5 2 1 2 3 4
Ans. (i) CH 3  CH  CH  CH 2CH3 (ii) 6
(iii) BrCH 2  CH  CH  CH 2 Br
| | 5 3 1,4-Dibromobut-2-ene
Cl CH3 4
2-Chloro-3-methylpentane CH2CH3
1-Chloro-4-ethylcyclohexane

Br
1 CH3
1 2 3 4 5 6 7
(iv) CH3CH 2 — CH — CH — CH 2CH 2CH3 (v) 2
| |
I H3C  C  CH3 4
| CH3 – CH – CH2 – CH3
CH3 1-Bromo-4-sec. butyl-2-methylbenzene.
4-tert. Butyl-3-iodoheptane
10.2 Why is sulphuric acid not used during the reaction of alcohols with KI ?
Ans. H2SO4 is an oxidising agent. It oxidises HI produced during the reaction to I2 and thus presents the reaction
between an alcohol and HI to form an alkyl iodide. To overcome this difficulty, a non-oxidizing acid such as
H3PO4 is used instead of H2SO4.
For example, CH3CH2OH + KI + H3PO4 –– CH3CH 2  I  KH 2PO 4  H 2O
Iodoethane
10.3 Write structures of different dihalogen derivatives of propane.
Ans. BrCH 2  CH 2  CH 2 Br BrCH 2  CH  CH3 Br  CH  CH 2  CH3 CH3 – C – CH3
1,3-Dibromopropane | |
Br Br Br Br
1,2-Dibromopropane 1,1-Dibromopropane 2,2-Dibromopropane

10.4 Among the isomeric alkanes of molecular formula C5H12, identify the one that on photochemical chlorination
yields.
(i) A single monochloride. (ii) Three isomeric monochlorides. (iii) Four isomeric monochlorides.

STUDY MATERIAL: XII CHEMISTRY 1 HALOALKANES AND HALOARENES (Q & A)

 CH3
|
Ans. (i) CH3  C  CH 3
|
CH3
All the hydrogen atoms are equivalent and replacement of any hydrogen will give the same product.
(ii) CaH3 – CbH2 – CcH2 – CbH2 – CaH3
The equivalent hydrogens are grouped as a, b and c. The replacement of equivalent hydrogens will give the
same product.

(iii) Ca H3  Cb H  Cc H 2  Cd H3
|
Ca H 3
Similarly the equivalent hydrogens are grouped as a, b, c and d. Thus, four isomeric products are possible.

10.5 Draw the structures of major monohalo products in each of the following reactions:
OH CH2CH3


Br heat or
2
(i) + SOCl2 ––– (ii) UV light
O2N
CH2OH CH3
+ HCl 

Heat
(iii) (iv) + HI –––
OH

(v) CH3CH2Br + NaI ––– (vi) + Br2 

Heat

uv light

OH Cl
Ans. (i) + SOCl2 ––– + SO2 + Cl2
Cyclohexanol Chlorocyclohexane

Br

CH2CH3 CHCH3



2Br heat or
(ii) O2N UV light O2N
4-Ethylnitrobenzene
4-(1-Bromoethylnitrobenzene)

CH2OH CH2Cl

+ HCl 

Heat
(iii)
OH OH
4-Hydroethylphenol 4-Chloroethylphenol

CH3 CH3
I
(iv) + HI 
Mark. addn

1-Methylcyclohexane 1-Ido-1-methylcyclohexane

STUDY MATERIAL: XII CHEMISTRY 2 HALOALKANES AND HALOARENES (Q & A)

 (v) CH 3CH2Br + NaI   CH3CH 2  I  NaBr
Oxyacetone 
Iodoethane

Br

3 2
(vi) + Br2 
Heat
 + HBr
uv light 1
3-Bromocyclohexane
10.6 Arrange each set of compounds in order of increasing boiling points.
(i) Bromomethane, Bromoform, Chloromethane, Dibromomethane.
(ii) 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane.
Ans. (i) Chloromethane < Bromomethane < Dibromomethane < Bromoform
Boiling point increases with increases in molecular mass.
(ii) Isopropyl chloride < 1-Chloropropane < 1-Chlorobutane
Isopropyl chloride being branched has lower boiling point than 1-Chloropropane .

10.7 Which alkyl halide from the following pairs would you expect to react more rapidly by an SN2 mechanism?
CH 3
|
(i) CH3CH2CH2CH2Br or CH3CH 2CHCH3 (ii) CH3CH 2CHCH3 or CH 3  C  Br
| | |
Br Br CH 3

(iii) CH3CHCH 2 CH 2 Br or CH3CH 2 CH CH 2 Br

| |
CH3 CH 3
Ans. (i) CH3CH2CH2CH2Br is a 1° alkyl halid while CH3CH2 – CHBr – CH3 is a 2° alkyl halide. Since there will
be some stearic hindrance in 2° alkyl halide than in 1° alkyl halide.
Therefore, CH3CH2CH2CH2Br will react faster than CH3CH2CHBr CH3 in SN2 mechanism.
(ii) CH3CH2 – CHBr – CH3 is a 2° alkyl halide while (CH3)3C – Br is 3° alkyl halide.
Since due to lesser stearic hindrance 2° alkyl halide react faster than 3° alkyl halides therefore,
CH3CH2CHBrCH3 will react faster than (CH3)3 CBr in SN2 mechanism.
4 3 2 1 4 3 2 1
(iii) CH3CH CH 2 CH 2 Br CH3CH 2 CH CH 2 Br
| |
CH3 (I) CH3 (II)
Both (I) and (II) are 2° alkyl halides. But in alkyl halide (II) the CH3 group at C2 is closer to Br atom while in
alkyl halide (I) the CH3 group at C3 is little away from Br atom. As a result alkyl halide (I) will suffer greater
stearic hindrance than alkyl halide (II).
Therefore, (CH3)2CHCH2CH2Br will react faster than CH3CH2CH (CH3)CH2Br in SN2 mechanism.

10.8 In the following pairs of halogen compounds, which compound undergoes faster SN1 reaction?
Cl Cl Cl

(i) and (ii) and Cl

Ans. The reactivity in SN1 reaction is governed by stability of carbocations

STUDY MATERIAL: XII CHEMISTRY 3 HALOALKANES AND HALOARENES (Q & A)

 Cl Cl
(i) is a 3° alkyl halides; is a 2° alkyl halides
Since 3° alkyl halides react faster than 2° alkyl halides due to greater stability of 3° carbocations over 2°
carbocations therefore.
Cl Cl
will react faster than in SN1 mechanism.
Cl

(ii) is a 2° alkyl halides Cl is a 1° alkyl halides

Since 2° alkyl halides react faster than 1° alkyl halides due to greater stability of 2° carbocations.
Cl

will react faster than Cl in SN1 mechanism.

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

+ Mg  A 2 
dry ether H O
Br B

R – Br + Mg  C 2 
dry ether D O
CH3CHCH3
|
D
CH3 CH3

 R1  X 
 D 
2 E
CH3 CH3
Na/ether Mg H O

CH3 CH3

Ans. Br + Mg 
dry ether
 MgBr 
2 
H O Mg(OH)Br

Cyclohexanemagnesium
bromide
Br
CH3  CH  Br  Mg  CH3  CH  BrMg 
dry ether CH3  CH  CH 3 + Mg
D 2O

| | | OD
CH3 CH3 D

CH 3 CH3 CH3 CH3

| | | |
CH 3  C  X + 2Na + X  C  CH 3   CH3  C  C  CH3
dry ether
| | | |
CH 3 CH3 CH3 CH3

A= MgBr B= C = RMgBr R = CH3CHCH3

CH3 CH3 CH 3
| | |
R1 = H 3 C  C D = H3C  C  MgX E = H3 C  C  H
| | |
CH3 CH3 CH 3
STUDY MATERIAL: XII CHEMISTRY 4 HALOALKANES AND HALOARENES (Q & A)
10.1 Name the following halides according to IUPAC system and classify them as alkyl, allylic, benzylic (primary,
secondary, tertiary), vinylic or aryl halides :
(a) (CH3)2CHCH(Cl) CH3 (b) CH3CH2CH(CH3)CH(C2H5)Cl
(c) CH3CH2C(CH3)2CH2I (d) (CH3)3CCH2CH(Br) C6H5
(e) CH3CH(CH3)CH(Br)CH3 (f) CH3C(C2H5)2CH2Br
(g) CH3C(Cl) (C2H5) CH2CH3 (h) CH3CH = C(Cl) CH2CH(CH3)2
(i) CH3CH = CHC(Br) (CH3)2 (j) p-ClC6H4CH2CH(CH3)2
(k) m-ClCH2C6H4CH2C(CH3)3 (l) o-Br-C6H4CH(CH3)CH2CH3
Ans. Formula IUPAC name Classification
CH3
|
(a) CH  CH  CH3 2-chloro-3-methylbutane Alkyl, Secondary
| |
CH3 Cl

(b) CH 3  CH 2  CH  CH  Cl 3-chloro-4-methylhexane Alkyl, Secondary

| |
CH3 C2 H5

CH3
|
(c) CH 3  CH 2  C  CH 2 I 1-iodo-2, 2-dimethylbutane Alkyl, Primary
|
CH3

CH 3
| 1-bromo-1-phenyl-3,
(d) CH3  C  CH 2  CH  C6 H5 3-dimethylbutane Alkyl, Secondary
| |
CH 3 Br

CH3
|
(e) CH3  CH  CH  CH3 2-bromo-3, 3-dimethylbutane Alkyl, Secondary
| |
CH3 Br

C2 H5
|
(f) CH3  C  CH 2 Br 1-bromo-2ethyl-2-methylbutane Alkyl, Primary
|
C2 H5

C2 H5
|
(g) CH3  C  CH 2  CH 3 3-chloro-3-methylpentane Alkyl, Tertiary
|
Cl
STUDY MATERIAL: XII CHEMISTRY 5 HALOALKANES AND HALOARENES (Q & A)
 CH3
|
(h) CH3  CH  C  CH 2  CH  CH3 3-chloro-5-methylex-2-ene vinylic, secondary
|
Cl

CH3
|
(i) CH3  CH  CH  C  CH3 4-bromo-4-methylpent-2-ene Allylic, Tertiary
|
Br
CH3
CH2 – CH – CH3

(j) 4-(2-methylpropyl) chlorobenzene Aryl

Cl
CH3
CH2 – C – CH3
(k) CH3 3-(2, 2-dimethyylpropyl) benzylchloride Benzylic, Primary
CH2Cl

CH3
CH – CH2CH3
(l) Br 1-bromo-2-(1-methylpropyl) benzene Aryl

10.2 Give the IUPAC names of the following compounds :

(a) CH3CH(Cl)CH(Br)CH3 (b) CHF2CBrClF (c) ClCH2C  CCH2Br (d) (CCl3)3CCl
(e) CH3C(p-ClC6H4)2CH(Br)CH3 (f) (CH3)3CCH = C(Cl)C6H4I-p

Ans. Formula IUPAC name

(a) CH3  CH  CH  CH3 2-bromo-3-chlorobutane
| |
Cl Br

H Br
| |
(b) F  C  C  F 1-bromo-1-chloro-1,2,2-trifluoroethane
| |
F Cl
(c) ClCH2 – C  C – CH2Br 1-bromo-4-chlorobut-2-yne

STUDY MATERIAL: XII CHEMISTRY 6 HALOALKANES AND HALOARENES (Q & A)

 CCl3
|
(d) Cl3C  C  Cl 2-(trichloromethyl)-1, 1, 1, 2, 3, 3, 3-heptachloropropane
|
CCl3
Cl

CH3 – C – CH – CH3
(e) Br 2-bromo-3-di(4-chlorophenyl) butane

Cl

CH3
(f) CH3 – C – CH = C – –I 1-chloro-1-(4-iodophenyl)-3, 3-dimethylbut-1-ene
Cl

10.3 Write the structures of the following organic halogen compounds.

(a) 2-chloro-3-methylpentane (b) p-bromochlorobenzene
(c) 1-chloro-4-ethylcyclohexane (d) 2-(2-chlorophenyl)-1-iodooctane
(e) 2-bromobutane (f) 4-tert-butyl-3-iodoheptane
(g) 1-bromo-4-sec-butyl-2-methylbenzene (h) 1, 4-dibromobut-2-ene.
Ans. Name Structural formula

5 4 3 2 1
(a) 2-chloro-3-methylpentane CH3  CH3  CH  CH  CH3
| |
CH3 Cl

(b) p-bromochlorobenzene Br Cl

Cl
1
2
(c) 1-chloro-4-ethylcyclohexane 4
3

C2H5

(d) 2 (2-chlorophenyl)-1-iodo octane CH3 – CH2 – CH2 – CH2 – CH2 – CH2 – CH – CH2I

Cl

CH3  CH  CH 2 CH3
(e) 2-bromobutane |
Br I
7 6 5 4 3| 2 1
CH3  CH 2  CH 2  CH  CH  CH 2  CH 3
|
H3C  C  CH3
(f) 4-tert-butyl-3-iodoheptane |
CH3
STUDY MATERIAL: XII CHEMISTRY 7 HALOALKANES AND HALOARENES (Q & A)
 Br
1 CH3
6 2

(g) 1-bromo-4-sec-butyl-2-methylbenzene 5
4
3

CH3CH2CHCH3

H 2C  CH  CH  CH 2
(h) 1, 4-dibromobut-2-ene | |
Br Br
10.4 Which one of the following has the highest dipole moment?
(i) CH2Cl2 (ii) CHCl3 (iii) CCl4
Ans. (i) CH2Cl2 has the highest dipole moment (1.60 D).
The dipole moment of CCl4 is zero whereas that of CHCl3 is 1.03D. In CH2Cl2, the resultant of two
C–Cl dipole moments is reinforced by resultant of two C – H moles.

10.5 A hydrocarbon C5H10 does not react with chlorine in dark but gives a single monochloro compound C5H9Cl
in bright sunlight. Identify the hydrocarbon.
Ans. The hydrocarbon C5H10 which gives a single monochloro compound is cyclopentane, .
Cl

In this compound, all hydrogens are equivalent. + Cl2 

hv
 + HCl

cyclopentane chlorocyclopentane

10.6 Write the isomers of the compound having formula C4H9Br.

Ans. CH3CH 2 CH 2 CH 2 Br CH 3CH 2 CHCH 3 (CH 3 )2 CHCH 2 Br (CH3 ) 2 C(Br)CH3
1 bromobutane | 1 bromo 2 methylpropane
2 bromo  2 methylpropane
Br
2 bromobutane

10.7 Write equations for the preparation of 1-iodobutane from

(a) 1-butanol (b) 1-chlorobutane (c) but-1-ene
Ans. (a) CH3 – CH2 – CH2 – CH2OH + HI(g)  
 CH3 – CH2 – CH2 – CH2I + H2O
butan-1-ol 1-iodobutane
+KOH(aq) HI(g), heat
CH3CH2CH2CH2OH CH3CH2CH2CH2I
–KCl Butan-1-ol 1-iodobutane

(b) CH3CH2CH2CH2Cl
1-chlorobutane
NaI in acetone
CH3CH2CH2CH2I + NaCl(s)
Reflux

(c) CH 3  CH 2  CH  CH 2  HBr 

peroxide
 CH3  CH 2  CH 2  CH 2 Br
but 1 ene 1-bromobutane
Acetone NaI
CH3  CH 2  CH 2  CH 2 I  NaBr(s)
1-iodobutane

STUDY MATERIAL: XII CHEMISTRY 8 HALOALKANES AND HALOARENES (Q & A)

10.8 What are ambident nucleophiles ? Explain with an example.
Ans. The nucleophiles with two nucleophilic centres are called ambident nucleophiles.
* Cyanide ion (– C  N:) has two nucleophilic centres – one at the carbon atom and the second on the
nitrogen atom.
* Nitrite ion (–O – N = O) has two nucleophilic centres – one at oxygen atom and the second on the nitrogen
atom.

10.9 Which compound in each of the following pairs will react faster in SN2 reaction with OH– ?
(a) CH3Br or CH3I (b) (CH3)3CCl or CH3Cl
Ans. (a) CH3I will react faster than CH3Br in SN2 reaction with OH– because the leaving group I is bigger than Br.
(b) CH3Cl will react faster than (CH3)3CCl in SN2 reaction with OH–, because the CH3– group is smaller
than the (CH3)3C - group. The smaller group offers less steric hindrance.

10.10 Predict all the alkenes that would be formed by dehydrohalogenation of the following halides with sodium
ethoxide in ethanol and identify the major alkene.
(a) 1-bromo-1-methylcyclohexane (b) 2-chloro-2-methylbutane
(c) 2, 2, 3-trimethyl-3-bromopentane
Br CH3 CH3

Ans. (a) + C2 H5ONa (1-methylcyclohex-1-ene) + HBr

in ethanol
1-bromo-1-methyl
cyclohexane

CH3

Cl CH3– CH2– C = CH 2
| 2-methylbut-1-ene

(b) CH3  CH 2  C  CH3  C2 H5ONa

(minor)

|
CH 3 CH3 – CH = C – CH 3
2chloro  2 methylbu tan e
CH3
Br CH3 CH3
2-methylbut-2-ene
(major)
| | |
(c) CH 3  CH 2  C  C  CH3  C2 H 5ONa  CH3  CH 2  C  C  CH3
HBr
| | | |
CH 3 CH 3 CH 3CH3
3-bromo-2,2,3-trimethylpentane 3,4,4-trimethylpent-2-ene

(this compound exists in E and Z forms.

E form is the major product)
10.11 How will you bring about the following conversions ?
(a) Ethanol to but-1-yne (b) Ethane to bromoethene
(c) Propene to 1-nitropropane (d) Toluene to benzyl alcohol
(e) Propene to propyne (f) Ethanol to ethyl fluoride
(g) Bromomethane to propanone (h) But-1-ene to but-2-ene
(i) 1-chlorobutane to n-octane (j) Benzene to biphenyl
Ans. (a) Ethanol to but-1-yne
NaC  CH
CH3CH2OH  CH3 – CH2Cl   CH3 – CH2 – C  CH
2 SOCl /Pyridine

but-1-yne
STUDY MATERIAL: XII CHEMISTRY 9 HALOALKANES AND HALOARENES (Q & A)
 (b) Ethane to bromoethene
hr 520 670K
CH3 – CH3 + Br2(g)   CH3 CH2 – Br
 HBr
KOH (alc),  KOH (alc), 
 CH2 = CH2 
4  BrCH  CH Br
Br /CCl
 2
2 2   CH 2  CHBr
 HBr 1,2 Dibromomethane  HBr Bromoethene
(c) Propene to 1-nitropropane

 CH3 – CH2 – CH2Br   CH3 – CH2CH2NO2

AgNO2 (ethanol)
CH3 – CH = CH2 + HBr 
peroxide
 AgBr
propene
(d) Toluene to benzyl alcohol. When Cl2 is passed into boiling toluene, it gives benzyl chloride, which on
boiling with KOH(aq) gives benzyl alcohol.
CH3 CH2OH
CH2 Cl


Cl , heat

2 KOH (aq)
+ KCl (aq)
 HCl

toluene benzyl alcohol

(e) Propene to propyne
CH 3  CH  CH 2  Br2 CH3  CH  CH 2   CH 3  C  CH
KOH (alc.)
 propyne
propene | | 2HBr
Br Br
(f) Ethanol to ethylfluoride
C2 H 5OH  SOCl2 C 2 H5Cl 
AgF, heat
C2 H5 F  AgCl
ethanol chloroethane fluoroethane
(ethyl fluoride)

(g) Bromomethane to propanone

 CH3CN 
KCN (ethanolic)
 CH 3  C  O  NH 3  Mg(OH)I
CH 3MgI/H 2O
CH3Br
 KBr
bromomethane |
CH3
propanone
(h) But-1-ene to but-2-ene
CH 3  CH 2  CH  CH 2  HBr CH3  CH 2  CH  CH3 
KOH (alc.)
 CH3  CH  CH  CH 3
but 1ene | but  2 ene
Br
(i) 1-Chlorobutane to n-octane
2CH 3  CH 2  CH 2  CH 2 Cl  2Na
1-chlorobutane

 CH3  CH 2  CH 2  CH 2  CH 2  CH 2  CH 2  CH3  2NaCl

dry ether
n-octane
(j) Benzene to biphenyl

2 
3
2 Cl 

2 Cl , FeCl Na (dry ether)
 HCl heat
biphenyl

STUDY MATERIAL: XII CHEMISTRY 10 HALOALKANES AND HALOARENES (Q & A)

10.12 Explain why
(a) The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride.
(b) Alkyl halides, though polar, are immiscible with water.
(c) Grignard reagents should be prepared under anhydrous conditions.
Ans. (a) Benzene molecule (or ring) is flat (planar) with all carbon and hydrogen atoms lying in the same plane.
Therefore, the dipole moment of chlorobenzene is only due to the dipole moment of the C – Cl bond,
benzene ring has zero dipole moment. In cyclohexyl chloride, the ring of cyclohexane is not planar (here, all
C atoms show sp3 hybridisation). It mainly exist in the “chair” form. This leads to a net dipole of the ring in
the same direction as the dipole of the C – Cl bond. Therefore, the dipole moment of chlorobenzene is
lower than that of cyclohexyl chloride.
(b) Alkyl halides (haloalkanes) are polar due to the presence of polar C – X bond. Alkyl halides are immiscribe
with water because(i) Alkyl halides are not able to form hydrogen bonds with water molecules
(ii) Alkyl halides are not able to break hydrogen bonds in water.
(c) Grignard’s reagents should be prepared under anhydrous conditions because they react with water (even
in trace amount) to form the corresponding hydrocarbons.
R – Mg X + H2O RH + Mg(OH)X
Grignard’s reagent water hydrocarbon

10.13 Give the uses of freon 12, DDT, carbon tetrachloride and iodoform.
Ans. Uses of Freon - 12 : Freon-12 (dichlorodifluoromethane, CF2Cl2) is commonly known as CFC. It is used as
a refrigerant in refrigerators and air conditioners. It is also used in aerosol spray propellants such as body
sprays, hair sprays, etc.
Uses of DDT : DDT (p, p-dichlorodiphenyltrichloroethane) is one of the best known insecticides. It is very
effective against mosquitoes and lice.
Uses of carbontetrachloride (CCl4) :
(i) It is used for manufacturing refrigerants and propellants for aerosol cans.
(ii) It is used as feedstock in the synthesis of chlorofluorocarbons and other chemicals.
(iii) It is used as a solvent in the manufacture of pharmaceutical products.
(iv) Until the mid 1960’s, carbon tetrachloride was widely used as a cleaning fluid, a degreasing agent in
industries, a spot reamer in homes, and a fire extinguisher.
Uses of iodoform (CHI3) : Iodoform was used earlier as an antiseptic, but now it has been replaced by other
formulations-containing iodine-due to its objectionable smell. The antiseptic property of iodoform is only due
to the liberation of free iodine when it comes in contact with the skin. It is employed as a solvent for fats,
alkaloids, iodine and other substance.

10.14 Write the structure of the major organic product in each of the following reactions:

(ii) (CH3)3CBr + KOH  

ethanol
(i) CH3CH2CH2Cl + NaI 

acetone
heat heat

(iii) CH3CH(Br)CH2CH3 + NaOH  (iv) CH3CH2Br + KCN  

water aq. ethanol

(v) C6H5ONa + C2H5Cl –––– (vi) CH3CH2CH2OH + SOCl2 ––––

(vii) CH3CH2CH = CH2 + HBr 
peroxide
(viii) CH3CH = C(CH3)2 + HBr ––––
 CH3CH 2CH 2 I  NaCl
(i) CH3CH2CH2Cl + NaI 
acetone
Ans.
heat 1 Iodopropane

STUDY MATERIAL: XII CHEMISTRY 11 HALOALKANES AND HALOARENES (Q & A)

 CH3
|


ethanol
(ii) (CH3)3CBr + KOH CH3  C  CH 2 + KBr + H2O
heat 2 methylpropene

 CH3  CH  CH 2CH3 + NaBr

water
(iii) CH3CH(Br)CH2CH3 + NaOH
|
OH
Butan-2-ol


 CH3CH 2  CN  KBr
aq. ethanol
(iv) CH3CH2Br + KCN
Propanenitrile


 C6 H5  O  C2 H5  NaCl
Williamson 's
(v) C6H5ONa + C2H5Cl
synthesis Phenetole

 CH3CH 2 CH 2 Cl  HCl  SO 2

Nucleophilic
(vi) CH3CH2CH2OH + SOCl2
substitution 1-Chloropropane


peroxide
(vii) CH3CH2CH = CH2 + HBr CH 3CH 2CH 2 Br
1-Bromobutane

CH3
|
  CH3  CH 2  C  CH3
Mark. addn
(viii) CH3CH = C(CH3)2 + HBr
|
Br
2-Bromo-2-methylbutane

10.15 Explain the mechanism of the following reaction : n-BuBr + KCN  EtOH  H 2 O
 nBuCN
Ans. This reaction is a nucleophilic substitution reaction. In this reaction; CN is a stronger nucleophile that displaces
–
Br– by SN2 mechanism.

10.16 Arrange the compounds of each set in the order of reactivity towards SN2 displacement :
(a) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(b) 1-Bromo-3-methylbutane, 2-bromo-2-methylbutane, 3-Bromo-2-methylbutane
(c) 1-Bromobutane, 1-Bromo-2, 2-dimethylpropane, 1-Bromo-2-methylbutane, 1-Bromo-3-methylbutane.
H H CH3 H H H H H H H H H H H H
| | | | | | | | | | | | | | |
Ans. (a) H  C  C  C  C  H H  C  C  C  C  C  C  Br H  C  C CC C  H
| | | | | | | | | | | | | | |
H H Br H H H H H H H H H H Br H
Since due to steric reasons, the order of reactivity in SN2 reaction is 1° > 2° > 3°.
Therefore, order of reactivity towards SN2 is :
1-Bromopentate > 2-Bromopentane > 2-Bromo-2-methylbutane
(b) 1-Bromo-3-methylbutane > 3-Bromo-2-methylbutane > 2-Bromo-2-methylbutane
(c) 1-Bromobutane > 1-Bromo-3-methylbutane > 1-Bormo-2, 2-dimethylpropane > 1-Bromo-2-methylbutane

10.17 Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolysed by aqueous KOH.
Ans. C6H5.CHCl.C6H5 will be more easily hydrolysed than C6H5CH2Cl because its carbocation is stabilised by
two phenyl groups due to resonance.

STUDY MATERIAL: XII CHEMISTRY 12 HALOALKANES AND HALOARENES (Q & A)

10.18 p-Dichlorobenzene has higher m.p. and solubility than those of o-and m-isomers. Discuss.
Ans. p-dichlorobenzene has higher melting point than o-and m- isomers due to symmetry of the para isomer and
better / close packing in crystal lattice.
Generally p-isomers are less soluble than o- and m-isomers.

10.19 How can the following conversions be carried out ?

(1) Propene to propan-1-ol (2) Ethanol to but-1-yne.
(3) 1-Bromopropane to 2-bromopropane (4) Toluene to benzyl alcohol
(5) Benzene to 4-bromonitrobenzene (6) Benzyl alcohol to 2-phenylethanoic acid
(7) Ethanol to propanenitrile (8) Aniline to chlorobenzene
(9) 2-Chlorobutane to 3, 4-dimethylhexane
(10) 2-Methyl-1-propene to 2-chloro-2 methylpropane (11) Ethyl chloride to propanoic acid
(12) But-1-ene to n-butyl iodide (13) 2-Chloropropane to 1-propanol
(14) Isopropyl alcohol to iodoform (15) Chlorobenzene to p-nitrophenol
(16) 2-Bromopropane to 1-bromopropane (17) Chloroethane to butane
(18) Benzene to diphenyl (19) tert-Butyl bromide to isobutyl bromide
(20) Aniline to phenyl isocyanide.

 CH3 – CH2 – CH2Br  CH3  CH 2  CH 2OH

KOH (aq)
(1) CH3  CH  CH 2 
HBr
Ans.
propene peroxide  KBr propan 1ol

(2) CH 3CH 2OH 

SOCl2
 CH3CH2Cl 
NaC CH
CH3  CH 2  C  CH
ethanol pyridine but 1 yne

(3) CH3  CH 2  CH 2 Br 

KOH (alc.)
 CH3  CH  CH 2 
HBr
 CH 3  CH  CH 3
1 bromopropane  KBr propene |
Br
2 bromopropane

CH3 CH2Cl CH2OH

Cl , 

2 
 
KOH (aq)
(4) + KCl (aq)
 HCl
Toluene Benzyl alcohol

Br Br

(5) conc. HNO  H SO


3 
3 2 4
2 Br , FeBr

Bromobenzene
NO2
4-bromonitrobenzene

CH2OH CH2Cl CH2CN CH2COOH



hydrolysis
(6) 
2 2
SO Cl


KCN (alc.)
H

CH3CH2Cl 
 CH 3CH 2CN
KCN (alc.)
(7) CH 3CH 2OH + PCl3
ethanol  KCl ethanenitrile

(8) This conversion is done through the formation of diazonium salt.

STUDY MATERIAL: XII CHEMISTRY 13 HALOALKANES AND HALOARENES (Q & A)

 NH2 N  NCl Cl

NaNO  HCl

 
2 2
2 Cu Cl
+ N2(g)
273 278K HCl
Aniline Benzene diazonium Chlorobenzene
chloride

Cl
| CH 3  CH 2  CH  CH3
(9) 2CH 3  CH 2  CH  CH3  2Na (ether) |
2 chlorobu tan e CH 3  CH 2  CH  CH3  2NaCl
3,4-dimethylhexane

CH 3 CH3
| |
(10) CH 3  C  CH 2 + HCl CH3  C  CH3
2 methylprop1 ene
|
Cl
2chloro  2 methylpropane

 C2H5CN 

KCN
(11) C2 H5Cl hydrolysis
 C2 H5COOH
ethylchloride  KCl propanoic acid

(12) CH3  CH 2  CH  CH 2  HI  CH 3  CH 2  CH 2  CH 2 I

peroxide
but-1-ene n-butyl iodide

(13) CH3  CH  CH3 

KOH (alc)
 CH3 – CH = CH2
|  KCl

Cl

 CH3 – CH2 – CH2Br   CH3CH 2 CH 2OH

KOH (aq)

HBr, peroxide
 KBr 1 propanol

(14) CH 3  CH  CH 3 
oxidation, [O]
 CH3  C  CH3  H 2O
| ||
OH O
Isopropyl alcohol

CH3  C  CH3  3I2  4NaOH 

warm
 CHI3 + CH3COONa + 3NaI + 3H2O
|| iodoform
O

Cl Cl OH
HNO  H SO NaOH, 
(15) 
3 2 4 
heat  NaCl
Chlorobenzene
NO2 NO2

(16) CH3  CH  CH3 

KOH (alc.)  HBr
 CH3  CH  CH 2   CH 3 CH 2CH 2 Br
| propene peroxide 1 bromopropane
Br
2 bromopropane

STUDY MATERIAL: XII CHEMISTRY 14 HALOALKANES AND HALOARENES (Q & A)

 (17) 2C 2 H5Cl + 2Na C2 H5  C5 H5 + 2NaCl
chloroethane butane


3
Cl  
Cl , FeCl
2 Na (dry ether)
(18) 2 2
 HCl heat
biphenyl

CH 3 CH 2
| ||
(19) CH 3  C  Br 
KOH (alc.)  HBr
 CH 3  C  CH 3   CH3  CH  CH 2 Br
|  KBr peroxide |
CH3 CH3
t  butylbromide isobutyl bromide

NH2
N=C

(20) + CHCl3 + 3KOH(alc.) 

heat
 + 3KCl + 3H2O
Aniline
Phenyl isocyanide
(phenyl carbylamine)
10.20 The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in the presence of
alcoholic KOH alkenes, are the major products. Explain.
Ans. The reaction between an alkyl chloride and aqueous KOH is a nucleophilic substitution reaction leading to the
formation of alcohol.
In the presence of alcoholic KOH, the nucleophile acts as a strong base and extracts a proton to form an
alkene.

10.21 Primary alkyl halide (a) C4H9Br 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 a compound (d)
C8H18 which is different from the compound when n-butyl bromide was reacted with sodium. Give the struc-
tural formula of (a) and write the equations for all the reactions.
Br
 
KOH (alc.)
Ans. CH 3CH 2CH 2 CH 2 Br 
CH3CH2CH = CH2 
HBr |
pri. alkyl halide  KBr CH 3CH 2 CH  CH3
(C4H9Br)

(a) (b) (c)

H H H H
| | | |
  CH 3CH 2 CH  CH3 .
2Na
Thus the structural formula of (a) is H  C  C  C  C  Br
2NaBr
| | | | |
CH 3CH 2 CH  CH3 H H H H
(C8 H18 )
(d)
10.22 What happens when (i) n-butyl chloride is treated with alcoholic KOH. (ii) Bromobenzene is treated with Mg
in the presence of dry ether. (iii) Chlorobenzene is subjected to hydrolysis. (iv) Ethyl chloride is treated with
(aqueous) KOH, (v) Methyl bromide is treated with sodium in the presence of dry ether. (vi) Methyl chlo-
ride is treated with KCN ?
Ans. (i) CH3 – CH2 – CH2 – CH2Cl + KOH(alc.) 
 CH3 – CH2 – CH = CH2 + KCl + H2O

STUDY MATERIAL: XII CHEMISTRY 15 HALOALKANES AND HALOARENES (Q & A)

 Br OH
MgBr Cl

+ NaOH(aq)  
623K, 300K
(ii) + Mg (dry ether) 
 (iii) HCl(aq)
+ NaCl
Bromobenzene Phenyl magnesium Chlorobenzene Phenol
bromide
(iv) C2H5Cl + KOH(aq) 
 C2H5OH + KCl
ethyl chloride ethanol
(v) 2CH3Br + 2Na  CH3 – CH3
dry ether + 2NaBr
methyl bromide ethane
(vi) CH3Cl + KCN   CH3CN + KCl
methyl chloride methyl nitrile

Q.1 During the direct iodination of methane, lodic acid is added to reaction mixture. Why?
Q.2 Out of the chlorobenzene and iodobenzene which has the higher boiling point and why?
Q.3 Out of PCl5 and SOCl2 which one is a better reagent for the conversion of alcohols to alkyl chloride and why?
Q.4 Through haloform reaction CHCl3, CHBr3 and CHI3 can be prepared but not CHF3, why ?
Q.5 C3H6O has three isomers A, B and C. Isomer A gives haloform test, isomer B does not give this test and isomer
C decolourises Br2 water and also gives colour with neutral FeCl3 solution. Identify A, B and C.
Q.6 (a) Allyl chloride is more reactive than n-propyl chloride towards nucleophic substitution reaction. Explain
(b) Haloakanes react with KCN to give alkyl cyanide as main product while with AgCN they form isocyanide
as main product. Give reason.

(i) VERY SHORT ANSWER TYPE

Q.1 Give one chemical test to distinguish chlorobenzene and ethyl chloride.
Q.2 What is the function of anhydrous zinc chloride in the reaction of alcohols and HCl.
Q.3 Out of chlorobenzene and p-nitrochloro benzene which will react with NaOH easily and why?
Q.4 Iodoform does not have free iodine, still it acts as antiseptic. Why?

(ii) SHORT ANSWER TYPE

Q.5 Discuss the reaction and given the names of the product, when ethylbromide reacts with (i) Li, (ii) Zn, (iii) Mg
Q.6 How phosgene formed from chloroform ? How its formation is preserved ?
Q.7 Which among the following compounds on reaction with a solution of iodine in sodium hydroxide solution gives
iodoform : methanol, ethanol, acetone, formaldehyde, acetaldehyde. Write balanced chemical equations.
Q.8 C2H4Cl2 (A) on hydrolysis gives C2H4O (B) which gives iodoform test. Identify A and B ?
Q.9 Give two examples of molecules which contain chirality centres but possess achrial structure.
H3C H

H
Q.10 (a) State the IUPAC name of the following compound :
H Br
H

(b) Complete the following chemical equation : CH3CH2CH = CH2 + HBr   .............
Peroxide

(iii) LONG ANSWER TYPE

Q.11 Write the formula of main product formed in the following chemical reactions :

STUDY MATERIAL: XII CHEMISTRY 16 HALOALKANES AND HALOARENES (Q & A)

 
Na 
(i) (CH3)2CH – CH – Cl dry ether
(ii) CH3Br + AgF 


N2Cl

(iii) CH3CH2Br + NaI 


dry acetone
(iv) CuCl

Q.12 How would you distinguish : (a)Chlorobenzene and benzyl chloride (b) Chlorobenzene & cyclohexyl chloride
(c) Ethyl chloride and Ethyl bromide
Q.13 Although chlorine is an electron withdrawing group, yet it is ortho-para-directing in electrophilic aromatic
substitution reactions. Why ?

CHAPTER REVIEW TEST

(PREVIOUS CBSE QUESTIONS)

Q.1 Write balanced equation for the following :

(i) When chloroform is oxidised by air (ii) Chloroform reacts with chlorine.
Q.2 Write the structural formula of 1-phenylpentan-1-one.
Q.3 Give the IUPAC name of the following compound : CH3  C  C  CH 2OH
| |
CH3 Br
CH3 – CH – CH2 – CH3
Br
Q.4 Write the IUPAC name of

Q.5 Write the IUPAC name of ClCH2C CCH2Br

Q.6 Identify the presence of chirality if any, in the following molecule 3-bromo-pent-1-ene. How many sterioisomers
are possible for those containing chiral centres ?
Q.7 Complete the following reaction equations :
CH3
(i) + HI –––– (ii) CH3CH2CH = CH2 + HBr ––––

Q.8 Given one example of each of the following reactions : (i) Wurtz reaction (ii) Wurtz-Fitting reaction
Q.9 Complete the following reaction equation :
H H
(i) C6H5N2Cl + KI –––– ............. (ii) C=C + Br2 
CCl4
 .............
H H
Q.10 Point out the difference between : (i) Chirality and chiral centre. (ii) Diastereoisomers and Enantiomers.
Q.11 Does the presence of two chiral carbon atoms always make the molecule optically active ? Explain giving an
example.
Q.12 How are the following conversions carried out?
(i) Benzyl chloride to benzyl alcohol, (ii) Methyl magnesium bromide to 2-methylpropan-2-ol.

STUDY MATERIAL: XII CHEMISTRY 17 HALOALKANES AND HALOARENES (Q & A)

Q.13 (i) State one use each of DDT and iodoform.
(ii) Which compound in the following couples will react faster in SN2 displacement and why?
(a) 1-Bromopentane or 2-bromopentane (b) 1-Bromo-2-methylbutane or 2-bromo-2-methylbutane.
Q.14 Complete the following, chemical reaction equations:
(i) I2 + HNO3 (conc.) ––– (ii) HgCl2 + PH3 –––
Q.15 How would you differentiate between SN1 and SN2 mechanisms of substitution reactions? Give one example
of each.
Q.16 Write the IUPAC name of the following compound: (CH3)3CCH2Br
Q.17 Answer the following:
(i) Haloalkanes easily dissolve in organic solvents, why?
(ii) What is known as a racemic mixture ? Give an example.
(iii) Of the two bromo derivatives, C6H5CH(CH3)Br and C6H5CH(C6H5) Br, which one is more reactive in
SN1 substitution reaction and why?
Q.18 Write the IUPAC name of the following compound: CH2 = CHCH2Br
Q.19 Rearrange the compounds of each of the following sets 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-Bromo-2-methylbutane
(iii) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2-methylbutane
Q.20 Answer the following questions :
(i) What is meant by chirality of a compound ? Give an example.
(ii) Which one of the following compounds is more easily hydrolyzed by KOH and why ?
CH3CHClCH2CH3 or CH3CH2CH2Cl
(iii) Which one undergoes SN2 substitution reaction faster and why ?
I Cl
or

Q.21 Write the IUPAC name of the following compound : CH3  CH  CH 2  CH  CH3
| |
Br Cl
Q.22 Which aerosol depletes ozone layer ?
Q.23 How are interhalogen compounds formed ? What general compositions can be assigned to them ?
Q.24 Give reasons for the following:
(i) Ethyl iodide undergoes SN2 reaction faster than ethyl bromide.
(ii) (±) 2-Butanol is optically inactive.
(iii) C – X bond length in halobenzene is smaller than C – X bond length in CH3 – X.
Q.25 Identify the chiral molecule in the following pair:

Cl
Cl
Q.26 (a) Draw the structures of major monohalo products is each of the following reactions :

CH2OH 
5
(i) PCl (ii) CH2 – CH = CH2 + HBr

(b) Which halogen compound in each of the following pairs will react faster in SN2 reaction :
(i) CH3Br or CH3I
(ii) (CH3)3C – Cl or CH3 – Cl

STUDY MATERIAL: XII CHEMISTRY 18 HALOALKANES AND HALOARENES (Q & A)