UNIT 06

HALOALKANES AND HALOARENES

1 MARK QUESTIONS:

1) Write the structure of 2, 4-dinitrochlorobenzene. Delhi 2017

2) Out of and which is an example of allylic halide? All India 2017

3) Write the structure of 1-bromo-4-chlorobut-2-ene. Delhi 2017
4) Write the structure of 3-bromo-3-methylprop-1-ene. Delhi 2017
5) Draw the structure of 2-bromopentane. Delhi 2014C
6) Write the IUPAC name of the (CH3)2 CH.CH (Cl) CH3. Delhi 2013
7) Write the IUPAC name of

Delhi 2013
8) Write the IUPAC name of

Delhi 2013
9) Write the IUPAC name of the following compound:

All India 2013

10) Write the IUPAC name of the following compound:

All India 2013

11) Write the IUPAC name of the following compound:

All India 2013

12) A hydrocarbon C5H12 gives only one monochlorination product. Identify the
hydrocarbon. Delhi 2013C
13) Give the IUPAC name of the following compound:

Delhi 2012
14) What happens when bromine attacks CH2=CH ─CH2─C≡CH All India 2012
15) Write the IUPAC name of the following compound (CH3)3CCH2Br. Delhi 2011
16) Write the IUPAC name of the following compound: CH2=CHCH2Br. AI 2011
17) Draw the structure of 1, 4-dibromobut-2-ene. Delhi 2011C, AI 2010C
18) Draw the structure of 2-(2-bromophenyl) butane. Delhi 2011C
19) Draw the structure of 2-(2-chlorophenyl)-1-iodooctane. All India 2011C
20) Draw the structure of the following compound:
1-bromo-4-sec-butyl-2-methylbenzene. All India 2011C
21) Draw the structure of the following organic compound:
2-chloro-3-methylpentane. All India 2011C
22) Draw the structure of the following compound:
3-(4-chlorophenyl)-2-methylpropane. Delhi 2011C
23) Write the IUPAC name of the following compound:

All India 2010

24) Write the IUPAC name of the following compound:

All India 2010

25) Draw the structure of the compound: 4-tert-butyl-3-iodoheptane. AI 2010C
26) Write the IUPAC name of the following compound:

All India 2010C

27) Draw the structure of the compound, 1-chloro-4-ethylcyclohexane. AI 2010C
28) Draw the structure of following compound: 4-bromo-3-methylpent-2-ene.
Foreign 2010

29) Out of and ,

Which will react faster in SN1 reaction with OH-? All India 2020
30) Out of CH3CH2CH2Cl and CH2=CH─CH2─Cl, which one is more reactive
towards SN1 reaction? All India 2020
31) Why is t-butyl bromide more reactive towards SN1 reaction as compared to n-
butyl bromide? All India 2019
32) Predict the major product formed when sodium ethoxide reacts with tert.butyl
chloride. CBSE 2018C
33) Out of chlorobenzene and benzyl chloride, which one gets easily hydrolysed by
aqueous NaOH and why? CBSE 2018
34) Write the structure of an isomer of compound C4H9Br which is more reactive
towards SN1 reaction. All India 2016
 35) Out of and ,
Which is more reactive towards SN1 reaction and why? Delhi 2016
36) Which would undergo SN1 reaction faster in the following pair?

and All India 2015

37) Which would undergo SN2 reaction faster in the following pair and why?

and Delhi 2015, Foreign 2015

38) Which would undergo SN2 reaction faster in the following pair and why?
and Foreign 2015
39) Identify the chiral molecule in the following pair.

and
All India 2014, Delhi 2014
40) What happens when CH3─Br is treated with KCN? Delhi 2013
41) What happens when ethyl chloride is treated with aqueous KOH? Delhi 2013
42) Which compound in the following pair undergoes faster towards SN1 reaction?

(i) (ii)
Delhi 2013
43) How methyl bromide be preferentially converted to methyl isocyanide?
Delhi 2013C
44) Predict the order of reactivity of four isomeric bromobutanes in S N1 reaction.
Delhi 2012C
45) Which will react faster towards SN2 reaction, 1-bromopentane or
2-bromopentane and why? Foreign 2011, 2010
46) A solution of KOH hydrolyses CH3CHClCH2CH3 and CH3CH2 CH2 CH2Cl.
Which one of these is more easily hydrolysed? Foreign 2010, Delhi 2010
47) Explain the following reaction with an example: Friedel-Crafts reaction.
Delhi 2010

2 MARK QUESTIONS:

1) Write the mechanism of the following reaction: Delhi 2014, All India 2014C

CH3CH2OH CH3CH2Br + H2O

2) Draw the structure of major monohalo product in each of the following
reactions:

(i)

(ii) All India 2014

3) Draw the structure of the following organic halogen compounds:
(i) p-bromochlorobenzene
(ii) 1-chloro-4-ethylcyclohexane All India 2014C
4) Draw the structure of the following organic halogen compounds:
(i) 4-tert-butyl-3-iodoheptane
(ii) 4-bromo-3-methylpent-2-ene All India 2014C
5) Write the IUPAC name of the following compounds:
(i) CH2=CHCH2Br (ii) (CCl3)3CCl All India 2014C
6) Which one of the following compounds is more reactive towards SN2 reaction and
why? CH3CH(Cl)CH2CH3 or CH3CH2 CH2Cl CBSE 2018C
7) (i) Which alkyl halide from the following pair is chiral and undergoes faster
towards SN2 reactions?

a) b)
(ii) Out of SN1 and SN2, which reaction occurs with
a) Inversion of configuration?
b) Racemisation? All India 2014
8) Write chemical equations when
(i) Ethyl chloride is treated with aqueous KOH.
(ii) Chlorobenzene is treated with CH3COCl in the presence of anhydrous AlCl3.
Foreign 2014
9) (i) Which alkyl halide from the following pair would you expect to react more
rapidly by an SN2 mechanism and why?

and
(ii) Racemisation occurs in SN1 reactions. Why? Foreign 2014
10) Which compound in each of the following pairs will react faster towards S N2
reaction with ─OH? Why? (i) CH3Br or CH3I (ii) (CH3)3CCl or CH3Cl
Delhi 2014, AI 2014, 2010C
11) Write the chemical equations when, Foreign 2014
(i) Methylchloride is treated with AgNO2.
(ii) Bromobenzene is treated with CH3Cl in the presence of anhydrous AlCl3.
12) What are ambident nucleophiles? Give an example. AI 2013, Foreign 2012
13) Account for the following:
(i) The C─Cl bond length in chlorobenzene is shorter than that in CH 3─Cl.
(ii) Chloroform is stored in closed dark brown bottles. Delhi 2013
 14) Chlorobenzene is extremely less reactive towards a nucleophilic substitution
reaction. Give two reasons for the same. Delhi 2013
15) Explain why
(i) Alkyl halides, though polar, are immiscible with water?
(ii) Grignard reagent should be prepared under anhydrous conditions?
Foreign 2012

3 MARK QUESTIONS:

1) Give the IUPAC name of the following compounds:

(i)

(ii) (iii) All India 2015C

2) Complete the following reactions:

(i)

(ii)
(iii) Foreign 2011
3) (i) Write equation for preparation of 1-iodobutane from 1-chlorobutane.
(ii) Out of 2-bromopentane, 2-bromo-2-methylbutane and 1-bromopentane,
which compound is most reactive towards elimination reaction and why?
AI 2019

(iii) Give IUPAC name of AI 2019

4) Give reasons for the following: AI 2019
(i) The presence of ─NO2 group at ortho or para position increases the reactivity
of haloarenes towards nucleophilic substitution reactions.
(ii) p-dichlorobenzene has higher melting point than that of ortho or meta
isomer.
(iii) Thionyl chloride method is preferred for preparing alkyl chloride from
alcohols.
5) (i) Out of (CH3)3C─Br and (CH3)3C─I, which one is more reactive towards SN1
reaction?
(ii) Write the product formed when p-nitrochlorobenzene is heated with aqueous
NaOH at 443K followed by acidification.
 (iii) Why dextro and laevo-rotatory isomers of butan-2-ol are difficult to separate
by fractional distillation? Delhi 2019
6) (i) Identify the chiral molecule in the following pair:

a) and b)
(ii) Write the structure of the product when chlorobenzene is treated with
methyl chloride in the presence of sodium metal and dry ether.
(iii) Write the structure of the alkene formed by dehydrohalogenation of 1-
bromo-1-methylcyclohexane with alcoholic KOH. CBSE 2018
7) Write the product(s) formed when
(i) 2-bromopropane undergoes dehydrohalogenation reactions.
(ii) Chlorobenzene undergoes nitration reaction.
(iii) Methylbromide is treated with KCN. CBSE 2018C
8) Following compounds are given to you:
2-bromopentane, 2-bromo-2-methylbutane, 1-bromopentane
(i) Write the compound which is most reactive towards SN2 reaction.
(ii) Write the compound which is optically active.
(iii) Write the compound which is most reactive towards β-elimination reaction.
Delhi 2017, AI 2017
9) How do you convert the following?
(i) Chlorobenzene to biphenyl
(ii) Propene to 1-iodopropane
(iii) 2-bromobutane to but-2-ene. Delhi 2015
10) Write the major products in the following: Delhi 2015C

(i)

(ii)
(iii)
11) Give reasons: Foreign 2015
(i) C─Cl bond length in chlorobenzene is shorter than C─Cl bond length in
CH3─Cl.
(ii) The dipole moment of chlorobenzene is lower than that of cyclohexyl
chloride.
(iii) SN1 reactions are accompanied by racemisation in optically active alkyl
halides.
12) How can the following conversions be carried out?
(i) Aniline to bromobenzene
(ii) Chlorobenzene to 2-chloroacetophenone
(iii) Chloroethane to butane. All India 2015C
13) What happens when
(i) Chlorobenzene is treated with Cl2/FeCl3
(ii) Ethyl chloride is treated with AgNO2?
(iii) 2-bromopentane is treated with alcoholic KOH?
Write the chemical equations in support of your answer. All India 2015
14) Give reasons: Delhi 2015
(i) N-butyl bromide has higher boiling point than t-butyl bromide.
(ii) Racemic mixture is optically inactive.
(iii) The presence of nitro group (─NO2) at o/p-positions increases the reactivity
of haloarenes towards nucleophilic substitution reactions.
15) (i) Why are alkyl halides insoluble in water?
(ii) Why is butan-1-ol optically inactive but butan-2-ol is optically active?
(iii) Although chlorine is an electron withdrawing group, yet it is ortho, para-
directing in electrophilic aromatic substitution reactions. Why?
Foreign 2015
16) (i) Draw the structures of major monohalo products in each of the following
reactions:

a)

b)
(ii) Which halogen compound in each of the following pairs will react faster
towards SN2 reaction?
a) CH3Br or CH3I
b) (CH3)3C─Cl or CH3─Cl Delhi 2014
17) (i) Which compound in each of the following pairs will react faster towards S N2
reaction with ─OH group?
a) CH3Br or CH3I
b) (CH3)3CCl or CH3Cl
(ii) Write the product(s) of the following reactions:
a) CH3─Cl + KCN → ?

b) Delhi 2014C
18) 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 CH 3─X.
All India 2013
19) Explain the following:
(i) The dipole moment of chlorobenzene is lower than that of cyclohexyl
chloride.
(ii) Alkyl halides, though polar, are immiscible with water.
(iii) Grignard reagents should be prepared under anhydrous conditions.
 Delhi 2013C
20) Although, chlorine is an electron withdrawing group, yet it is ortho, para-
directing in electrophilic aromatic substitution reactions. Explain, why is it so?
Delhi 2012
21) 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 hydrolysed by KOH
and why?
CH3CHClCH2CH3 or CH3CH2 CH2 CH2Cl
(iii) Which one undergoes SN2 substitution reaction faster and why?
All India 2012
22) Answer the following:
(i) Haloalkanes easily dissolve in organic solvents. Why?
(ii) What is the racemic mixture? Give an example.
(iii) Out of the two bromo derivatives, C6H5CH(CH3)Br and (C6H5)CH(C6H5)Br,
which one is more reactive towards SN1 substitution reaction and why?
Delhi 2011
23) 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, 1-
bromo-3-methylbutane. All India 2011
24) (i) Write the mechanism of the following reaction:

(ii) Why is the dipole moment of chlorobenzene lower than that of cyclohexyl
chloride? Delhi 2011C
25) (i) Write a chemical test to distinguish between
a) Chlorobenzene and benzyl chloride
b) Chloroform and carbon tetrachloride
(ii) Why is methyl chloride hydrolysed more easily than chlorobenzene?
All India 2011C
26) (i) State one use of DDT and iodoform.
(ii) Which compound in the following couples will react faster towards S N2
displacement and why?
a) 1-bromopentane or 2-bromopentane
b) 1-bromo-2-methylbutane or 2-bromo-2-methylbutane Delhi 2020
27) How would you differentiate between SN1 and SN2 mechanism of substitution
reactions? Give an example of each. All India 2010
28) Explain why
(i) The dipole moment of chlorobenzene is lower than that of cyclohexyl
chloride.
(i) Alkyl halides, though polar, are immiscible with water?
(ii) In the pair, (CH3)3C─Cl and CH3─Cl, CH3Cl will react faster in SN2 reaction
with ─OH? All India 2010C