QUESTION BANK – HALO ALKANES&HALO ARENES

 Account for the following:

a) Haloarenes are extremely less reactive towards nucleophilic
substitution reactions.
b) Allyl chloride shows high reactivity towards SN1 reaction.
c) Haloalkanes react with AgCN to form isocyanide as the main
product.

ANS: a. C—Cl bond acquires a partial double bond character due to

resonance.

b. The carbocation thus formed gets stabilised through resonance

c. AgCN is mainly covalent, and nitrogen is free to donate electron

pairs

 a) Complete the following equation:

b) Arrange the compounds in order of increasing boiling points.

1-Chloropropane, Isopropyl chloride, 1-Chlorobutane
c) What are enantiomers? How do they differ from each other?
OR c) Butan-2-ol is chiral or achiral. Justify your answer.

ANS: a)

b. Isopropyl chloride<1-Chloropropane
c. stereoisomers related to each other as non-superimposable mirror images
are called enantiomers. They differ by optical rotation.

OR c. Chiral + Asymmetric carbon

 Assertion (A): OH is an ambident nucleophile.

 Reason (R): The nucleophiles which have two different electron donor
atoms and can attack through two different sites are called ambident
nucleophiles.

ANS: (d) A is false but R is true

 Give reasons for the following statements.

(a) Chloroethane is insoluble in water.
(b) Thionyl chloride method is preferred for preparing alkyl chlorides
from alcohols.

ANS: (a) In order to dissolve haloalkane in water, energy is required to

overcome the attractions between the haloalkane molecules and break the
hydrogen bonds between water molecules. Less energy is released when
new attractions are set up between the haloalkane and the water molecules
as these are not as strong as the original hydrogen bonds in water. (b) In this
reaction alkyl halide is formed along with gases SO2 and HCl. The two
gaseous products are escapable, hence, the reaction gives pure alkyl
halides.

 (a) Write the IUPAC name of the following. CH3CH=C(CH3)CH2Br

(b) What happens when (write chemical equations to support your
answer) (i) 2-Bromobutane is treated with alcoholic KOH? (ii) Ethyl
chloride is treated with AgNO2?

ANS: (a) 1-Bromo-2-methylbut-2-ene

(b)
  (a) Predict the reagents and conditions required for the following
conversions.

ANS:

(a) (i) NaOH,368K, (ii) H+ (ii) CH3COCl, An AlCl3

(b) Choose the incorrect statement.
(i) The C—X bond length in haloalkane is shorter than in
haloarene. Hence haloarenes are less reactive towards
nucleophilic substitution than haloalkane.
(ii) Reactivity of electrophilic substitution in haloarene is controlled by the
stronger inductive effect and orientation is controlled by resonance effect.
(iii) In Grignard reagents, the carbon-magnesium bond is covalent but highly
polar.
(iv) In case of optically active alkyl halides, SN1 reactions are accompanied by
racemisation.
(c) Among the isomers of C4H9Br, choose which is/are optically active.

(i) 1−Bromobutane. (ii) 2−Bromobutane (iii) 1−Bromo−2−methylpropane and 1−Bromobutane. (iv)

2−Bromo−2−methylpropane.

OR (c) Among the isomers of C4H9Br, choose the one which undergoes faster SN2 reaction. (i) 1−
Bromobutane. (ii) 2−Bromobutane. (iii) 1−Bromo−2−methylpropane. (iv) 2−Bromo−2−
methylpropane.

 Which of the following is not an allylic halide?

(A) 4-Bromopent-2-ene (B) 1-Bromobut-2-ene
(C) 4-Bromobut-1-ene (D)
3-Bromo-2-methylbut-1-ene
 Alkyl halides are immiscible in water though they are polar because
(A) they react with water to form alcohols.
(B) they cannot form hydrogen bonds with water.
(C) C-X bond cannot be broken easily.
(D) they are stable compounds and are not reactive.
 How do you convert: (a) Chlorobenzene to Toluene (b) 2-
Bromopropane to 1- Bromopropane
ANS: (a) Chlorobenzene to Toluene Wurtz-Fittig reaction- Reaction
with Methyl chloride and Na in presence of ether.

(b)2- Bromopropane to 1- Bromopropane – Dehydrohalogenation

 Give reasons for the following: (a) 2-Bromobutane is optically active
but 1-Bromobutane is optically inactive. (b) Chlorobenzene is
extremely less reactive towards a nucleophilic substitution reaction.

ANS: (a) 2-Bromobutane is chiral - contains asymmetric carbon atom -

optically active. But, 1-Bromobutane is not chiral- no asymmetric
carbon atom- optically inactive.

(c)partial double bond character-resonance- Cl attached to sp2 C –

High bond dissociation energy C-Cl bond.
 Racemisation occurs in (A) SN1 reactions (B) SN2 reactions (C)
Neither SN2 nor SN1 reactions (D) SN2 reactions as well as SN1
reactions
 Draw the structures of major monohalo products in each of the
following reactions:

ANS:

1-Bromo-4-nitrophenylethane

1-Iodo-1-methylcyclohexane
 a) Account for the following: i) The dipole moment of
chlorobenzene is lower than that of cyclohexyl chloride. ii) t-butyl
bromide has lower boiling point than n-butyl bromide.
b) Arrange the following in the increasing order of reactivity towards
SN2 reaction: 1-Bromo-2-methylbutane,
1-Bromo-2,2-dimethylpropane, 1-Bromo-3-methylbutane
ANS: a) i) Due to –I and +R effect in chlorobenzene, net dipole
moment is lower than that of cyclohexyl chloride in which net dipole
moment is due to –I effect only / sp2 hybridised carbon in
chlorobenzene is more electronegative and C-Cl bond length is
shorter as compared to sp3 hybridized carbon in cyclohexyl
chloride. ii) Due to branching, t-butyl bromide has less surface area
and weaker van der Waal forces than n-butyl bromide. b)
1-Bromo-2,2-dimethylpropane < 1-Bromo-2-methylbutane <
1-Bromo-3-methylbutane
 a) Identify A and B in the following reactions:

ANS:
 b) A hydrocarbon C5H10 does not react with chlorine in dark but
gives a single monochloro compound C5H9Cl in bright sunlight.
Identify the hydrocarbon.
 Out of chlorobenzene and benzyl chloride, which one gets easily
hydrolysed by aqueous NaOH and why?
(a) Benzyl chloride; Due to the steric effect, stable benzyl
carbocation cannot be formed.
(b) Chlorobenzene; Due to resonance, stable phenyl carbocation is
formed.
(c) Chlorobenzene; Due to the steric effect, stable phenyl
carbocation cannot be formed.
(d) Benzyl chloride; Due to resonance, stable benzyl carbocation is
formed.


ANS:

ANS:

 An organic compound A with the molecular formula (±)C4H9Br

undergoes hydrolysis to form (±)C4H9OH. Give the structure of A
and write the mechanism of the reaction.
ANS:
 Which among the following has higher boiling point?
 (a) 1-Bromobutane (b) 2-Bromobutane
(c) 1-Bromo-2-methylpropane (d) 2-Bromo-2-methylpropane
 Which of the following is not correct?
(a) Allyl halides show high reactivity towards SN1 reaction.
(b) A racemic mixture has zero optical rotation.
(c) The electrophilic substitution reactions in haloarenes occur
slowly and require more drastic conditions as compared to those in
benzene. (d) The carbon-magnesium bond in Grignard reagent is
ionic.
 Give reasons for the following. (a) Phosgene is stored in closed
dark coloured bottles. (b) Aryl halides are extremely less reactive
towards nucleophilic substitution reactions.
ANS: (a) Chloroform is slowly oxidised by air in the presence of light
to an extremely poisonous gas, carbonyl chloride, also known as
phosgene. (b) (i) Resonance effect (ii) Difference in hybridisation of
carbon atom in C—X bond (iii) Instability of phenyl cation (iv)
Because of the possible repulsion
 Predict the major product.
 ANS:

(a)2-MethylPropene
(b)1-Bromopropane
(c)Butan-2-ol
 What happens when (write equations) (a) Chlorobenzene reacts
with chloromethane and Na in presence of dry ether.
(b) Bromomethane is heated with AgF.
(c) Ethene is treated with Br2 in CCl4.
ANS:

 Choose the correct answer from the following pairs.

(a) (CH3)3CBr or CH3Br (more reactive towards SN2 mechanism)
 (b) CH3CH2CH2CH2Cl or CH3CH(Cl)CH2CH3 (Chiral compound)
(c) CH3CN or CH3NC (when CH3Br reacts with KCN)
ANS:
(a)CH3Br primary alkyl halide is more reactive towards SN2 due to
less steric hindrance
(b) CH3CH(Cl)CH2CH3 asymmetric carbon which is stereo centre is
optically active( Chlorine attached to carbon is surrounded by
four different groups)
(c)CH3CN as KCN is ionic which generates CN ion in which carbon
bears negative charge and act as nucleophile. Bond between C-C
is stronger.
 Sulphuric acid is not used for the preparation of alkyl iodide from
alcohols with KI. This is because (A) Sulphuric acid is a strong
oxidising agent (B) Sulphuric acid is a strong dibasic acid (C)
Sulphuric acid is a strong reducing agent (D) None of these
 Among the isomeric alkanes of molecular formula C5H12, identify
the one that on photochemical chlorination yields three isomeric
monochlorides.
(A) Cyclopentane (B) n- Pentane (C) 2-Methylbutane (D)
2,2-Dimethylpropane
 Identify the product obtained when isobutyl chloride is reacted with
sodium in presence of dry ether.
(A) 3,4-Dimethylhexane (B) 3,4-Dimethyloctane
(C) 2,2,3,3-Tetramethylbutane (D) 2,5-Dimethylhexane.
 Assertion: Finkelstein reaction takes place in presence of dry acetone.
Reason: NaX formed during the reaction is precipitated in dry acetone
and it facilitates the forward reaction.
ANS: (A) Both A and R are true and R is the correct explanation of A.
 An alkyl halide (A), C3H7Br reacted with alcoholic KOH to give
compound (B). Compound (A) when reacted with aq. NaOH gives (C)
which on oxidation with CrO3 gives a ketone (D), Give the structures of
A, B, C and D.
ANS:
 How will you obtain Chlorobenzene from aniline?
 ANS:

 Write the major mono halogen derivative of:

ANS:

3-Bromocyclohexene
 a) Which of the following has lower boiling point and why?

ANS:
 b) Which of the following is more reactive towards SN1 reaction and
why? 1-Bromopentane or 2-Bromo-2-methylbutane
ANS: 2-Bromo-2-methylbutane It is a tertiary alkyl halide. It forms a
more stable tertiary carbocation.
c) Which of the following molecules is chiral in nature and why?

ANS:

 a) The electrophilic substitution reactions in Chlorobenzene occur

slowly, Why?
b) How would you prepare Phenol from Chlorobenzene?
c) Chlorobenzene is extremely less reactive towards nucleophilic
substitution reactions. Write any two reasons.
OR
c) Name the reagents needed for the preparation of 4-Nitrophenol
starting from Chlorobenzene. Also, write chemical equations.
ANS:
a) This is due to the electron withdrawing nature of chlorine (-I effect).
It deactivates the benzene ring.
c) (i)Resonance effect: C—Cl bond acquires a partial double bond
character due to resonance.
(ii) Difference in hybridisation of carbon atom in C—X bond: In
haloalkane, the carbon atom attached to halogen is sp3 hybridised
while in case of haloarene, the carbon atom attached to halogen is sp2
hybridised.
(iii)Instability of phenyl cation: In case of haloarenes, the phenyl cation
formed as a result of self-ionisation will not be stabilised by
resonance.
(iv) Because of the possible repulsion, it is less likely for the electron
rich nucleophile to approach electron rich arenes.
 Study the graph showing the boiling points of bromoalkanes and
identify the compounds.

a. 1 = Bromomethane, 2= 2-Bromobutane, 3= 1-Bromobutane, 4=

2-Bromo-2-methylpropane
b. 1 =1-Bromobutane, 2= 2-Bromo-2-methylpropane, 3=
2-Bromobutane, 4= Bromomethane
c. 1 = Bromomethane, 2=1-Bromobutane, 3=
2-Bromo-2-methylpropane, 4= 2-Bromobutane,
d. 1 =Bromomethane, 2= 2-Bromo-2-methylpropane, 3=2-
Bromobutane, 4= 1-Bromobutane
 Various isomeric haloalkanes with the general formula C4H9Cl
undergo hydrolysis reaction. Among them, compound “A” is the most
reactive through SN 1 mechanism. Identify “A” citing the reason for
your choice. Write the mechanism for the reaction.
Ans: “A” is (CH3)3CCl, the carbocation intermediate obtained in tertiary
alkyl halide is most stable, making A most reactive of all possible
isomers.
 (a) Arrange the isomeric dichlorobenzene in the increasing order of
their boiling point and melting points. (b) Explain why the electrophilic
substitution reactions in haloarenes occur slowly and require more
drastic conditions as compared to those in benzene
ANS: (a) m-dicholrobenzene < o-dicholrobenzene < p-dicholrobenze
symmetrical structure and close packing in para isomer ortho has a
stronger dipole dipole interaction as compared to meta
(b) the halogen atom because of its –I effect has some tendency to
withdraw electrons from the benzene ring. As a result, the ring gets
somewhat deactivated as compared to benzene and hence the
electrophilic substitution reactions in haloarenes occur slowly and
require more drastic conditions as compared to those in benzene
 An organic compound A with the molecular formula (+)C 4H9Br
undergoes hydrolysis to form (+/-) C4H9OH. Give the structure of A
and write the mechanism of the reaction.
ANS:
 Give reason for the following: a. During the electrophilic substitution
reaction of haloarenes, para substituted derivative is the major
product.
b. The product formed during SN 1 reaction is a racemic mixture.
ANS: a. At the ortho position, higher steric hindrance is there, hence
para isomer is usually predominate and is obtained in the major
amount. b.During the SN 1 mechanism, intermediate carbocation
formed is sp2 hybridized and planar in nature. This allows the attack of
nucleophile from either side of the plane resulting in a racemic
mixture.
 a. Name the suitable alcohol and reagent, from which
2-Chloro-2-methyl propane can be prepared.
b. Out of the Chloromethane and Fluoromethane , which one is has
higher dipole moment and why?
ANS: a. Tert butyl alcohol or 2-methyl propan-2-ol using Lucas reagent
mixture of Conc.HCl and ZnCl2 the reaction will follow the SN 1
pathway. b.Chloromethane is having higher dipole moment . Due to
smaller size of fluorine the dipole moment of flouromethane is
comparatively lesser.
 Give a chemical test to distinguish between C2H5Br and C6H5Br.
ANS: 1-bromoethane will form a yellow precipitate of AgBr when treated
with dil: HCl and AgNO3 and bromobenzene will not produce yellow
precipitate.

 Identify the compound which is most reactive toward SN2 reaction from the
following.

2-Bromopentane, 2-Bromo-2-methyl butane, 1-Bromopentane,

Which alkyl halide from the following pair is chiral?

(CH3)2CHBr and CH3CH2CHBrCH3

ANS:

1-Bromopentane > 2-Bromopentane>2-Bromo-2-methylbutane lesssterichindrance

CH3 CH2CHBrCH3 3rd carbon lacks symmetry it is anasymmetriccentre

1 2 3 4

 Ethylene dibromide and ethylidene bromide are isomers. Identify the

incorrect statement about these isomers given below.
a) Both undergo elimination reaction to give same alkene.
b) Both are hydrolyzed to give the same product.
c) Both have the same percentage of bromine.
d) These are position isomers.
