Haloalkanes and Haloarenes 195

Previous Years' CBSE Board Questions

10.1 Classification 11. Write the IUPAC name of the following
compound:
VSA (1mark) CHy-CH-CH-CH-CH (AI 2013)
Br C
12. Write the IUPAC name of the following:
1. Out
of and which is an

CH-C-CH,OH
example of allylic halide? (AI 2017)
CH3 Br
(AI 2013C, 2012C, Foreign 2011)
Out ofa n d which is an 13. Give the IUPAC name of the following
compound:
example of vinylic halide? (AI 2017) CH=C-CHBr
3. Outof and CHCH,C CH (Delhi 2012, AI 2011)
14. Write the IUPAC name of the following
which is an example of a benzylic halide?
compound:
(AI 2017) (CH3),CCH,Br (Delhi 2011)
10.2 Nomenclature 15. Write the IUPAC name of the following
compound
VSA (1 mark) CH=CHCH,Br (AI 2011)
4. Write the structure of 1-bromo-4-chlorobut- 16. Write the structure of the following
2-ene. (Delhi 2017) compound:
5. Write the structure of 3-bromo-2-methylprop- 1,4-dibromobut-2-ene (Delhi 2011C)
1-ene. (Delhi 2017) 17. Write the structure of the following
6. Draw the structure of 2-bromopentane. compound:
(Delhi 2014C) 2-(2-Bromophenyl)butane (Delhi 2011C)
7. Write the IUPAC name of 18. Give IUPAC name of the following organic
CH3-CH-CH2-CH=CH2 compound:
a (Delhi 2013) CHCH-C-CH-CH
8. Write the IUPAC name of CH, Br (Delhi 2011c)
CH 19. Write the structure of the following
Compound:
CH,CH-CH-C-CH (Delhi 2013)
2-(2-chlorophenyl)-1-iodooctane
Br (AI 2011C)
9. Write the IUPAC name of (CH,),CHCH(CI)CH. 20. Write the structure of the following
(Delhi 2013) compound:
10. Write the IUPAC name of the following 1-bromo-4-sec-butyl-2-methylbenzene
Compound: (AI 2011C)
CH3 21. Write the structure of the compound:

CH--CH-CH 4-tert-butyl-3-iodoheptane (AI 2010C)

22. Write the IUPAC name of the following
CHCl (AI 2013)
compound:
196 wtGCBSE Champion Chemistry Class 12

CH3 31.
Draw thein structure
product the
of major monohal ogen
followingreaction:
HC-C-CH,CI (AI 2010C)
CH3
23. Write the structure of the compound
B (Delhi 2012C)
32. Draw the structure of major monohalo
1-chloro-4-ethylcyclohexane. (AI 2010C)
product in the following reaction:
SAL (2marks)
24. Write the IUPAC of the
+Ch Dk (Delhi 2012C)
names following 33. What happens when bromine attacks
compounds:
CH=CH-CH-CECH? (AI 2012)
(i) CH=CHCH,Br (i) (CCl,),CCl
(AI 2014C SAI (2 marks)
34. Draw the structure of major monohalo
SAI 3 marks) product in each of the following reactions:
25. Give the IUPAC names of the following
compounds: OH
) CH-CH-CHCH3
B
() CH-CHCH, +HBreroxide
(Delhi 2014)
35. Write the mechanism of the following
reaction:
Br
CH,CHOH CH,CH,Br + H,O
(ii) CH=CH-CH-Ca (AI 2015C) (AI 2014)
10.4 Methods of Preparation 36. Complete the following reaction equations:
VSA (1 mark) 0 OH+SOCh
26. How do you convert: CHOH
Propene to 1-iodopropane? (1/3, Al 2016) +HCI
i)
27. Write the major products in the following: HO
(Delhi 2009)
CH2-CH3 37. Complete the following reaction equations:
Br.UV light
CH3
(1/3, AI 2016) o HI
28. Write the structure of the major product in (i) CH,CH,CH=CH, + HBr
the following reaction : (AI 2009)
CH-CH=C-CH3+HBr SAII (3 marks)
CH3 (1/3, AI 2015) 38. Compute
thefollowing reaction equations:
29. A hydrocarbon CHi2 gives only one
CH3
monochlorination product. Identify the
(Delhi 2013C)
+HI
hydrocarbon.
30. Draw the structure of major monohalogen
product formed in the following reaction
**+HBr
+HI>> (Delhi 2012C) (ii) CH,CH,CH=CH2 + HBr-
(Foreign 2011)
Haloalkanes and Haloarenes 197

39. Complete the for the following which is

reactions:
equations CH-CH-CH-C, more

CH
HBr> reactive towards Sl reaction and why?
H H (Delhi 2016)
CH3 48. Write the structure of an isomer of compound
(i) +HI CHBr which is most reactive towards Syl
reaction. (AI 2016)
(ii) -OH +SOCh- 49. Which would undergo Sy2 reaction faster in
(Delhi 2011C) the following pair and why?
CH3
10.5 Physical Properties CH-CH,-Br and CH-C-CH
VSA (1mark) Br
40. Give reason : (Delhi 2015)
n-Butyl bromide has higher boiling point 50. Which would undergo Syl reaction faster in
than t-butyl bromide. (1/3, Delhi 2015) the following pair:
41. Why are alkyl halides insoluble in water? CH3
(1/3, Foreign 2015)
CH3-CH-Br and CH3-C-CH3
42. Why does p-dichlorobenzene have a higher
m.pt. than its o- and m-isomers? Br (AI 2015)
(1/2, Delhi 2013, 1/3, AI 2009C)
51. Which would undergo Sy2 reaction faster in
43. Explain the following: the following pair and why?
Alkyl halides, though polar, are immiscible
with water. (1/3, Delhi 2013C, 1/3, AI 2010C) CH-CH-Br and CH-CH-I
44. Answer the
(Foreign 2015)
following:
Haloalkanes easily dissolve in organic 52. Identify the chiral molecule in the following
solvents, why? (1/3, Delhi 2011) pair
SAL (2 marks) (AI 2014)
45. Explain why
53. Which halogen compound in each of
() the dipole moment of chlorobenzene is
the following pairs will react faster in Sy2
lower than that of cyclohexyl chloride?
(1/3, Delhi 2016, 2013C, 2011 C,
reaction
(i) CHBr or CH,I
1/2, Delhi 2010C, 1/3, AI 2010C) (i) (CH),CCl or CH,Cl
(ii) alkyl halides, though polar, are (Delhi 2014C, AI2014)
immiscible with water?
54. What happens when CH3-Br is treated with
(2/3, AI 2013C, 2012C) KCN? (Delhi 2013)
55. What happens when ethyl chloride is treated
10.6 Chemical Reactions
with aqueous KOH? (Delhi 2013)
VSA (1 mark) 56. Why is (t)-butan-2-ol is optically inactive?
(1/2, Delhi 2013)
46. Out of chlorobenzene and benzyl chloride,
which one gets easily hydrolysed by aqueous 57. Which compound in the following pair
NaOH and why? (2018) undergoes faster Syl reaction?
CI
47. Out of CH-CHCH-Cl and

CH3 (Delhi 2013, 2013C, 2012C)

58. How may methyl bromide be preferentially (ii) Sl reactions are accompanied by
converted to methyl isocyanide? racemization in optically active alkyl
(Delhi 2013C) halides. (2/3, Delhi 2016)
59. Account for the following: 70. How do you convert?
Grignard's reagents should be prepared () Chlorobenzene to biphenyl
under anhydrous conditions. i) 2-Bromobutane to but-2-ene
(1/3, Delhi 2013C, 1/3, AI 2012C) (2/3, AI 2016)
60. Predict the order of reactivity of four
71. Write the major product(s) in the following:
isomeric bromobutanes in Syl reaction.
Na
(Delhi 2012C) (0 2CH-CH-CH, Dry ether
61. Predict the order of reactivityofthe following Cl
compounds in Syl reaction.
(i) CHCH-Br (2/3, AI 2016)
CH,CH,Br, CgH,C(CH,)(CH,)Br,
72. Give reasons:
CgH,CH(CH)Br, CHsCH(CH,)Br
(Delhi 2012C) () Racemic mixture is optically inactive.
62. Give a chemical test of distinguish between (i) The presence of nitro group (-NO,)
CHBr and CgH,Br. (AI 2012C) at olp positions increases the reactivity
63. Which will react faster in Sy2 displacement, of haloarenes towards nucleophilic
substitution reactions.
1-bromopentane or 2-bromopentane and
(2/3, Delhi 2015)
why? (Foreign 2011)
64. Which will react faster in SNl displacement 73. Write the structure of the major product in
reaction each of the following reactions:
1-Bromobutane or 2-bromobutane and why? (i) CHCH2-CH-CH-CH3 +KOH
(Foreign 2011) Ethanol
Br Heat
65. A solution of KOH hydrolyses Br
CH,CHCICH,CH, and CH,CH,CH,CH,CI.
Which one of these is more easily hydrolysed?
(Delhi 2010) (i) +CH,CI anhyd. Alcls
66. Explain the following reaction with an
(2/3, AI 2015)
example:
Friedel-Crafts reaction. (1/2, Delhi 2010) 74. (i) Why is butan-1-ol optically inactive but
butan-2-ol is optically active?
67. Why is thefollowing occur: (ii) Although chlorine is an electron
Chloroform is stored in closed dark coloured
withdrawing group, yet it is ortho-,
bottles completely filled so that air is kept
out. (1/2, Delhi 2010C) para-directing in electrophilic aromatic
substitution reactions. Why?
68. Explain why in the pair, (CH),CCl and
(2/3, Foreign 2015, Deilhi 2012)
CH,Cl, CH,Cl will react faster in Sy2
reaction with OH"? (1/3, AI 2010C) 75. (i) Which alkyl halide from the following
pair is chiral and undergoes faster S2
SAL (2 marks) reaction?

69. Give reasons: (a) (b)

Br
Br
) C-CI bond length in chlorobenzene
is shorter than C-Cl bond length in (i) Out of Syl and Sy2, which reaction
CH-CL Occurs with
Haloalkanes and Haloarenes 199
(a) inversion of configuration i) Of the two bromo derivatives,
(6) racemisation? (2/3, Delhi 2014) Cg1CH(CH,)Br and CgH,CH(CHJB,
76. Write chemical equations when which one is more reactive in Syl
() ethyl chloride is treated with aqueous substitution reaction and why?
KOH (2/3, Delhi 2011)
(i) chlorobenzene is treated with CH,COCI
in presence of anhydrous AlCl3. 85. Write the mechanism of the following reaction:
(Foreign 2014) n-BuBr+ KCN- EOH, n-BuCN
77. (i) Which alkyl halide from the following (1/3, Delhi 2011C)
pairs would you expect to react more
86. How are the following conversions carried out?
rapidly by an Sy2 mechanism and why?
(i) Benzyl chloride to benzyl alcohol
CH-CH2-CH-CH3 (i) Methyl magnesium bromide to
Br methylpropan-2-ol. (2/3, Delhi 2010)
CH-CH-CHh-CH-Br 87. Which compound in the following couple
(i) Racemisation occurs in SNl reactions.
will react faster in Sy2 displacement and why?
Why? (Foreign 2014) (i) 1-Bromopentane or 2-bromopentane
78. Write chemical equations when (ii) 1-Bromo-2-methylbutane or
) methyl chloride is treated with AgNO2
(ü) bromobenzene is treated with CH,Cl in
2-bromo-2-methylbutane.
(2/3, Delhi 2010)
the presence of anhydrous AlCl.
(Foreign 2014) 88. (a) Why is sulphuric acid not used during
the reaction of alcohols with KI in the
79. What are ambident nucleophiles? Explain
with an example. (2/3, AI 2014C) conversion of an alcohol to the alkyl
iodide?
80. Chlorobenzene is extremely less reactive
towards a nucleophilic substitution reaction. (b) Why are haloarenes less reactive than
Give two reasons for the same. (Delhi 2013) haloalkanes towards nucleophilic
81. Account for the following: substitution reactions? (Delhi 2010C)
) The C-Cl bond length in How would you account for the
chlorobenzene is shorter than that in
89. following:
() Grignard reagents are prepared strictly
CH-Cl under anhydrous conditions?
(ii) Chloroform is stored in closed dark
brown bottles. (Delhi 2013)
82. Give reasons for the following : ii) undergoes faster Syl
) Ethyl iodide undergoes Sy2 reaction
faster than ethyl bromide. reaction than.
(i) C-X bond length in halobenzene (Delhi 2010C)
is smaller than C-X bond length in
(2/3, AI 2013)
90. Which one in the following pairs of
CH-X.
substances undergoes S2 substitution
83. Haloalkanes undergo nucleophilic substitution
whereas haloarenes undergo electrophilic reaction faster and why?
substitution. Explain.

84. Answer the following:

(2/3, Delhi 2012C) oCHCle-a
(1) What is known as a racemic mixture? (ii) or
Give an example. (Delhi 2009)
91. Which one in the following pairs undergoes (i) Write the compound which is optically
SNl substitution reaction faster and why? active.
CI (ii) Write the compound which is most
CI
reactive towards B-elimination reaction.
() o (Delhi 2017)

96. Answer the following questions:

C
(ii) or ) What is meant by chirality of a
compound? Give an example.
(AI 2009)
92. for the (ii) Which one of the following compounds
Suggest a possible reason following
observations is more easily hydrolysed by KOH and
() The order of reactivity of haloalkanes is why?
RI> RCl> RBr. CH,CHCICH,CH, or CH,CH,CH,CI
(i) Neopentyl chloride (CH),CCH,CI (ii) Which one undergoes Sy2 substitution
does not follow Sy2 mechanism. reaction faster and why?
(2/3, Delhi 2009C)
or Cl
93. Give reasons for the following observations :
(i) Haloarenes are less reactive than (AI 2012)
haloalkanes towards nucleophilic
substitution reactions. 97. Rearrange the compounds of each of the
(i) The treatment of alkyl chloride with following sets in order of reactivity towards
aqueous KOH leads to the formation of S2 displacement:
alcohol but in the presence of alcoholic
(i) 2-Bromo-2-methylbutane,
KOH, alkene is the major product.
(2/3, AI 2009c)
1-Bromopentane, 2-Bromopentane
(i) 1-Bromo-3-methylbutane, 2-Bromo-2-
SA II (3marks) methylbutane,3-bromo-2-methylbutane
94. (a) ldentify the chiral molecule in the (ii) 1-Bromobutane, 1-Bromo-2, 2-dimethyl
following pair: propane, 1-Bromo-2-methylbutane
(AI 2011)
and
98. (a) Write a chemical test to distinguish
between:
H OH
(i) (ii) () Chlorobenzene and benzyl chloride
(b) Write the structure of the product when (ii) Chloroform and carbon tetrachloride
chlorobenzene is treated with methyl (b) Why is methyl chloride hydrolysed
chloride in the presence of sodium metal more easily than chlorobenzene?
and dry ether. (Delhi 2011C)
()Wirite the structure of the alkene formed 99. Differentiate between Syl and S2
by dehydrohalogenation of 1-bromo-1- mechanisms and give examples. (AI 2010)
methyleyclohexane with alcoholic KOH.
(2018)
10.7 Polyhalogen Compounds
95. Following compounds are given to you:
2-Bromopentane, 2-Bromo-2-methylbutane, VSA (1 mark)_
1-Bromopentane
(i) Write the compound which is most 100. State one use each of DDT and iodoform.
reactive towards Sy2 reaction. (Delhi 2010)
Haloalkanes and Haloarenes 201

Detailed Solutions

16. H2CCH=CH-CH2
Br Br
1. is an allylic halide as the halogen is
17. CH-CH-CH2-CH3
attached to sp3-hybridised carbon atom which is
next to carbon-carbon double bond.
O
is a vinylic halide as the halogen
18. H,CH=¢-CH-H,
is attached to sp-hybridised carbon.
CHCl%
CH, Br
O is a benzylic halide as the 4-Bromo-3-methylpent-2-ene
halide group is attached to sp?-hybridised carbon 19. IH,C-CH-(CH2)s-CH3
atom next to
aromatic ring.
4. Cl-CH2-CH=CH--CH,-Br
1-Bromo-4-chlorobut-2-ene
5. HC-C=CH2 20. CH3-CH2-CH-CH
Br
CH
3-Bromo-2-methylprop-1-ene
6.
HC-CHCH-CH-CH Br
Br
21. HC-CH-CH-CH-CH-CH2-CH
7. 4-Chloropent-1-ene
8.
9.
4-Bromo-4-methylpent-2-ene
2-Chloro-3-methylbutane
iC(CH
10. 3-Chloro-2,2-dimethyilbutane CH3
11. 2-Bromo-4-chloropentane 22.

12. C--noH CH
1-Chloro-2,2-dimethylpropane
CH3 Br

2-Bromo-3-methylbut-2-en-1-ol
13. CH=-H,Br 23.
CH 4

3-Bromo-2-methyipropene CH,CH3
14. CH3 24. (i) Refer to answer 15.
H,c-c-CH,-Br (i) 2-(Trichloromethyl)-1, 1,1,2,3,3-3-

CH heptachloropropane
1-Broma-2,2-dimethylpropane 25. () 2-Bromobutane

15. CH=HH,Br (ii) 1,3-Dibromobenzene

3-Bromoprop-1-ene (ii) 3-Chloropropene
26. CHCH=CH,+HBrerox CH,CH,CH,Br
Propene Br+CHCH-OH>CH,CH,-Br+ H40
Nal
Acctone CH-CH-CH,I 36. (i) Refer to answer 34 (i).
1- lodopropane
(i)
CH,OH CH,CI
21. +HCI
Br
HO HO
,CH,CH, CH-CH, 4-Chloromethylphenol
Br 37. () Refer to answer 30.
Heat
O,N or O,N (ii) CHCH,CH=CH,+ HBr>>
light 4-(1-bromocthyl)
nitrobenzene
CH,CH-CH-CH3
Br
28. CH-CHC-CH 38. () Refer to answer 30.
Markovnikov's
CH3 H tHBraddition
2-Bromo-2-methylbutane H
(Markovnikov's addition)
H-CH
CH3
29. HC-¢-CH (ii) Refer to answer 37(i).

CH3 39. (i) Refer to answer 38(ii).

2,2-Dimethylpropane (ii) Refer to answer 30.
(i) Refer to answer 34().
+HI
CH3 40. n-Butyl bromide, being a straight chain
30.
molecule have strong intermolecular forces
Br whereas t-butyl bromide being a branched chain
molecule have weaker intermolecular forces due
31. B Heat HBr to smaller surface area.
Light Hence, boiling point of n-butyl bromide is higher
than that of t-butyl bromide.
41. Alkyl halides are polar but are insoluble in
32. C Fe
Dark water because energy required to break thee
intermolecular H - bond among water molecules
33. CH-ÇH-CHCECH is much higher than energy
halide interaction.
released by water

Br Br 42. p-Dichlorobenzene has higher melting point

OH CI than those of o-and m-isomers because it is more
symmetrical and packing is better in solid form.
34.
+soC, J+s0,+HC Hence, it has stronger intermolecular forces of
Chlorocyclohexane attraction than o-and m-isomers.
(i) CH-CH=CH,+ HBr eroxide

-CH-CH-CH-Br
CI
35. CHCH,H + H*> CH,CH,-QH, P
Haloalkanes and Haloarenes 203
43. Refer to answer 4. 49. CH-CH-Brwould undergo S2 reaction
44. Haloalkanes dissolve in organic solvents faster due to formation of less sterically hindered
because the intermolecular attractions between transition state.
haloalkanes and organic solvent molecules have
CH3
the same strength as in the separate haloalkanes
and solvent molecules. 50. CH3-C-CH3 will undergo Sl reaction
45. (i) There are two reasons:
(a) In case of chlorobenzene, carbon to which faster due to the formation of stable carbocation.
chlorine is attached is sp-hybridised and is more 51. Since I is a better leaving group than Br,
electronegative than the corresponding carbon in thus, CH,CH,I undergoes Sy2 reaction faster
cyclohexyl chloride which is sp*-hybridised. So than CH,CH,Br.
the net dipole moment is lower in chlorobenzene.
52. is a chiral molecule.
(b) Inchlorobenzene C-Clbond has some double
Cl
bond character so its bond length is smaller
53. () CHl will give faster S2 reaction.
Hence dipole moment is smaller than cyclohexyl
chloride which has a longer C-Cl single bond. (i) CH,Cl will give faster Sy2 reaction.

sp sp3 54. CH,CN is formed by nucleophilic

substitution reaction.
CH Br+KCN-CH,CN+KBr
55. When ethyl chloride is treated with aqueous
Chlorobenzene Cyclohexyl chloride
KOH, ethanol is formed,
(i) Refer to answer 41
CH,CH,Cl +KOH(a9) CH,CH,OH + KCI
46. Benzyl chloride gets easily hydrolysed by
56. (t)-Butan-2-ol is optically inactive because
aq. NaOH due to formation of stable benzyl
carbocation. But due to partial double bond it exist in two enantiomeric forms which are
character of C-Cl bond in chlorobenzene, it does non-superimposable mirror images of each other.
not hydrolyse. Both the isomers are present in equal amounts
therefore, it does not rotate the plane of polarized
47. The Sl reaction proceeds through
carbocation formation thus, the compound which light and is optically inactive.
forms more stable carbocation will be more
reactive. CH CH3
CH-ÇH-CH2-C CH-ÇH-H, 10CHCH CHCH,OH
CH3 H3 50%-(+)Butan-2-ol S0% -
() Butan-2-o
1-Chloro-2-methylpropane (1° Carbocation)
CI
CH-CH-CH-CI CH-CH2-H 57. Tertiary halide reacts faster than the

CH CH3 secondary halide because of the greater stability

2-Chlorobutane (2 Carbocation) of tert-carbocation.
As, 2° carbocation is more stable than 1° carbocation
58. AgCN is mainly covalent in nature and
thus, 2-chlorobutane is more reactive towards
nitrogen is free to donate electron pair forming
Sl reaction. isocyanide as main product.
CH3 CH,Br + AgCN CH,NC+ AgBr
48. CH-¢-Br Methyl Methyl isocyanide
bromide

CH3 59. Grignard reagents react with water to form

tert-butyl bromide
or 2-Bromo-2-methylpropane alkanes.
 X 69. (i) In halobenzene C-X bond has partial
R-Mg-X+ H,O>R-H + Mg
double bond character due to resonance while
So, they must be prepared under anhydrous CH-X bond is single bond.
conditions. Thus, bond length of C-X bond in halobenzene
60. (CH3),CBr>CH3CH2ÇH-CH3> is smaller than that in CH-X.

Br
(CH),CHCH,Br> CH,CH,CH,CH,Br
61. CgH,C(CH,)(CH,)Br>CgH,CHCgH,)Br> (i) In Snl reaction carbocation intermediate
CH,CH(CH,)Br > CgHsCH,Br
is formed which is a planar molecule so, an
62. CHBr reacts with AgNO, to give yellow incoming nucleophile can attack from either side
precipitate of AgBr while CHBr will not and a equimolar mixture of two components are
63. 1-Bromopentane is a primary alkyl halide, formed and resulting mixture is optically inactive.
hence reacts faster in Sy2 displacement than 70. ()
secondary halide 2-bromopentane.
2 + 2Na Ether
64. 2-Bromobutane will react faster in Sl
Chlorobenzene Biphenyl
displacement reaction because it will form more
Br
stable secondary carbocation intermediate.
65. CH,CH,CHCH, hydrolyses easily with (i) CH-CH-CH2-CH3
2-Bromobutane CH-CH=CH-CH,+ HBr
CL But-2-ene
KOH because it is secondary halide.
71. (6) CH-CH-CH-CH3
66. Haloarenes can undergo both Friedel-
Craft alkylation (with alkyl halide) or CH, CH3
Friedel-Craft acylation (with acid halide)
(ii) CH,CH,NC
in presence of Lewis acid catalyst to give a
mixture of o and p-haloalkyl benzene or 72. (i) Racemic mixture contains equal amount of
0- and p-haloacylbenzene. d- and 1-forms, hence rotation due to one
enantiomer is cancelled by another.

I.CAnbyd.AICl
CH (ii) The presence of nitro group at o-and
CH,a P-positions withdraws electrons from the
benzene ring and thus, facilitates the attack of the
1-Chloro-2-methyl
benzene CH
(Minor) 1-Chloro-4-methy
nucleophile on haloarenes. The carbanion thus
benzen
( M a i o
formed is further stabilised by resonance.

73. i) CH-CH-CH=CH-CH,
67. Chloroform when exposed to air and
Pent-2-ene (Saytzeff rule)
sunlight changes to phosgene which is a poisonous Br

gas.

CHCl+0 COCl +HCl (i) (Friedel-Crafts alkylation)

Phosgene
Thus, it is kept in dark coloured bottles to prevent
CH3
the oxidation. 4-Bromotoluene

68. CHCl will react faster in S2 reaction with 74. (i) Butan-1-ol is achrial, i.e., does not have
OH as CH,Cl is a primary halide and it will give chiral 'C atom which is attached to four different
less sterically hindered transition state groups, therefore, it is opticallyinactive
Haloalkanes and Haloarenes 205

CH-CH-CH-CH,0OH hindrance in 2° alkyl halides, 1 alkyl halide will

Butan-1-ol react faster than 2° alkyl halide in Sy2 reaction.
(Optically inactive) (i) Carbocations are formed in Syl reaction which
(No chiral carbon)
Butan-2-ol is chiral, ie., as chiral C atom, areplanar species, thus, racemisation occurs
attached to four different groups. 78. (i) CH,Cl+ AgNO2 CH,NO2 + AgCl
Br Br Br
CH CH3
(i) (O]+CH,CI AnhyAlCL CH
H- OH H0 -H

CH,CH CH,CH3 CH3

d+) 79. A nucleophile which can attack from
more than one centres, is known as ambident
:Ci: :CI :CI: nucleophil. e.g, CEN: cyanide ion
(i) 80. Haloarenes are much less reactive than
haloalkanes towards nucleophilic substitution
reactions due to the following reasons.
:Cl :Ci: (i) Resonance effect : In haloarenes the electron
pairs on halogen atom are in conjugation
with T-electrons of the ring and the following
resonating structures are possible.
Although Cl is electron withdrawing(-Ieffect) but Cl
still o- and p-directing as due to +R effect, electron
density is maximum at o- and p-positions.

75. (i) (a) Br undergoes faster

Sy2 reaction. C-Cl bond acquires a partial double bond
character due to resonance. As a result, the bond

(b) Br is chiral. cleavage in haloarene is dificult than haloalkane

(ii) (a) SyN2 reaction occurs with inversion of and therefore, are less reactive towards
nucleophilic substitution reaction.
configuration.
(b) Syl reaction occurs with racemisation. (ii) In halorenes, attached to
halogen is
76. (i) Refer to answer 55. sp-hybridised carbon while in haloalkanes,
halogen is attached to sp-hybridised carbon.
(i)
81. (i) Refer to answer 69(i).
(ii) Refer to answer 77.
Anhyd. AlCl CH3
+CH-C-d- 82. (i) Refer to answer 51.
(i) Refer to answer 69).
2-Chloroacetophenone
(Minor) 83. In haloarenes -ve charge gets localised on
CI
arenes using resonance, therefore they undergo
electrophilic substitution.
Haloalkanes have electrophilic carbon centre due
to polarity of C - X bond.
0CH
4-Chloroacetophenone 84. (i) An equimolar mixture of a pair of
(Major) enantiomers is called racemic mixture. A racemic
77. ) 1-Bromobutane is 1° alkyl halide while mixture is optically inactive due to external
2-bromobutane is 2° alkyl halide. Due to steric compensation.
Example (6) Refer to answer 80.
CH3-CH-CH2-CH 89. () Refer to answer 59.
OH
Butan-2-ol (50% mixture of d- and 1-form)
(i) undergoes faster Sl
i) Of the two bromo derivatives, CgH,CH(C,H,)Br reaction as it is a secondary halide and give more
is more reactive than CgHs(CH,)Br for Syl reaction stable carbocation than primary halide.
because its carbocation is resonance stabilised by 90. ( >CH,Ca is pimary halide and
two phenyl groups.
therefore, undergoes Sy2 reaction faster than the
85. Normal butyl bromide will give S2 reaction:
CH,CHCH, secondary halide C.
CHCHCH,
K'CN C-Br NCC-Br (i) As iodide is a better leaving group because
H
H
H H
of its large size, therefore,
undergoes Sy2 reaction faster than

CH,CH,CH CI

-Br
N C

91. (1)*: Tertiary halide reacts faster than

n-Butyl cyanide
secondary halide because of the greater stability of
CH.CI CH,OH tert. carbocation.

86. +aq. KOH| (ii) reacts faster than

Benzyl alcohol
C
Benzyl chloride because of greater stability of
secondary carbocation than primary.
92. () Among the various halides with same
(i1) CH,MgBr +CH--CH alkyl group the order of reactivity is RI> RBr> RC.
Methyl magnesium
bromide Due to increasing bond strength of C-I, C-Br
DH OMgBr and C-Cl the reactivity decreases.

CH--CH, H,O CHC-CH (ii) Neopentyl chloride being a primary halide

reacts slowly through Sl and the carbon carrying

CH CH halogen is sterically more hindered Hence it does

2-Methylpropan-2-ol not follow Sn2 mechanism.
87. (a) 1-Bromopentane, as it is a primary alkyl 93. (i) Refer to answer 80.
halide. i) In aqueous solution, KOH is almost completely
(b) 1-Bromo-2-methylbutane, as it is a primary involved to give OH ion which being a better
alkyl halide. nucleophile gives a substitution reaction on alkyl
88. (a) H,SO, is an oxidant. KI reacts with halides to form alcohol. But an alcoholic solution of
KOH containing alkoxide (RO") ions which being
HSO, and gives HI and H,$O, oxidises HI to I,
a much stronger base than OH ion preferentially
2KI +HS0, 2KHS0, + 2HI
snatches a H' ion from an alkyl chloride to form
2HI+ HS0 2H,0 +12 + SO, alkenes.
Thus, HI will not be available for reaction with
alcohol to form alkyl iodide. 94. (a)
This is why sulphuric acid is not used during the OH
reaction of alcohols with KI. )
Haloalkanes and Haloarenes 207

Cl (ii) CHCly with aniline in presence of alc. KOH

(b) +2Na+Cl-CH, gives foul smelling isocyanides whereas CCl does
Methyl chloride
not.
Chlorobenzene
Dry Ether
(b) CH,Cl is hydrolysed easily than CH,Cl as
-CH,+2NaCl chlorobenzene has partial double bond character
between C-Cl bond which is difficult to break.
Toluene
99.
/Br alc. KOH
(c) Sl mechanism S2 mechanism
CH3
1-Bromo-1-methylcyclohexane 1. It is two step It is single step
process, carbocation process. No
intermediate is intermediate is
(major) (minor)
formed. formed.
95. (i)1-Bromopentane
2. It obeys 1 order|It obeys 2d order
(ii) 2-Bromopentane
(i) 2-Bromo-2-methylbutane
kinetics. kinetics.
Rate k [Reactant] Rate = k[Reactant
96. (i) The molecules which are not superimposable Nucleophilel
on their miror images are called chiral molecules. 3.
Order of reactivity Order of reactivity
The property of non-superimposability of a 3°> 2°> 1°. 1°>2°>3.
structure on its mirror image is called chirality. Optically inactive |Inversion of
Mirror
H,C CH product is formed confguration takes
C-OH OH-C (racemic mixture). place.
HC H H
C.H, 5. eg e.g
Non superimposable mirror image of 2-butanol (CH,)CBr+ OH OH Cl
i) Refer to answer 65. 2-Bromo-2-methyl
propane
(i) Refer to answer 90.
97. ) 1-Bromopentane >2-Bromopentane (CH,),COH + Br
2-Bromo-2-methylbutane. 2-Methylpropan-2-o
(ii) 1-Bromo-3-methylbutane > 3-Bromo-2
methylbutane > 2-Bromo-2-methylbutane
(ii) 1-Bromobutane > 1-Bromo-2-methylbutane
OH+CT
>1-Bromo-2,2-dimethylpropane H H
98. () () Benzyl chloride gives white precipiate
100. DDT is used as an insecticide and iodoform
with AgNO, solution while chlorobenzene does not.
is used as a mild antiseptic.