Board Questions

Topic : Haloalkanes and haloarens

MOHMMED.ILIAS

1. Write the IUPAC names

2. Write the IUPAC names

3. Write structures of the following compounds:

a) 2-Chloro-3-methylpentane
b) 1-Chloro-4-ethylcyclohexane
c) 4-tert. Butyl-3-iodoheptane
d) 1,4-Dibromobut-2-ene
e) 1-Bromo-4-sec. butyl-2-methylbenzene
4. Among the isomeric alkanes of molecular formula C5H12, identify the one that on
photochemical chlorination yields
a) A single monochloride.
b) Three isomeric monochlorides.
c) Four isomeric monochlorides
5. A hydrocarbon C5H10 does not react with chlorine in dark but gives a single monochloro
compound C5H9Cl in bright sunlight. Identify the hydrocarbon.
6. Account for the following :
a) Thionyl chloride is preferred because the other two products are escapable gases.
Hence the reaction gives pure alkyl halides
b) Why is sulphuric acid not used during the reaction of alcohols with KI?
HI formed will oxidized into I2 by sulphuric acid
c) Electrophilic substitution reactions in haloarenes occur slowly.
Due to -I effect of halogen atom, it withdraws electrons from the benzene ring and thus
ring gets deactivated
d) Haloalkanes, though polar, are insoluble in water
they fail to form hydrogen bonds with water. More energy is required to break hydrogen
bonds in water and less energy is released when new attractions are set up.
e) C—Cl bond length in chlorobenzene is shorter than C—Cl bond length in CH3—Cl.
C-Cl bond in chlorobenzene acquires some double-bond character due to reasonance
f) The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride.
g) SN1 reactions are accompanied by racemization in optically active alkyl halides.
Racemic mixture formed is optically inactive.
Rotation due to one enantiomer is cancelled by another enantiomer
h) n-Butyl bromide has higher boiling point than t-butyl bromide.
n-Butyl bromide has higher boiling point than t-butyl bromide because it has larger
surface area hence have more Van der Waals’ forces.
i) Racemic mixture is optically inactive.
Rotation due to one enantiomer is cancelled by another enantiomer
j) The presence of nitro group (-NO2) at o/p positions increases the reactivity of
haloarenes towards nucleophilic substitution reactions
The presence of nitro group (-NO2) at ortho and para positions withdraws the electron
density’ from benzene ring and by stabilising carbanion intermediate thus facilitating
the attack of nucleophile.
k) Ethyl iodide undergoes SN2 reaction faster than ethyl bromide.
I is better leaving group/C—I bond is weaker than C—Br bond.
l) (±) 2-Butanol is optically inactive.
(±)-Butan-2-ol is optically inactive because in racemic mix one type of rotation is
cancelled by other
m) Although chlorine is an electron withdrawing group, yet it is ortho-, para-directing in
electrophilic aromatic substitution reactions. Explain why it is so?
Chlorine withdraws electrons through inductive effect and releases electrons through
resonance. Through inductive effect, chlorine destabilises the intermediate carbocation
formed during the electrophilic substitution. Through resonance, halogen tends to
stabilise the carbocation and the effect is more pronounced at ortho- and para- positions.
The resonance effect tends to oppose the inductive effect for the attack at ortho- and
para positions and hence makes the deactivation less for ortho- and para attack. Reactivity
is thus controlled by the stronger inductive effect and orientation is controlled by
resonance effect
n) Haloalkanes undergo nucleophilic substitution whereas haloarenes undergo electrophilic
substitution. Explain.
o) Haloalkanes easily dissolve in organic solvents, why?
Because the new forces of attraction set up between haloalkanes and solvent molecules
are of the same strength as the forces of attraction being broken.
p) Why does p-dichlorobenzene have a higher m.p. than its o- and m-isomers?
 p-isomers are comparetively more symmetrical and fit closely in the crystal lattice, thus
require more heat to break these strong forces of attraction. Therefore higher melting
point than o- and m-isomers
q) The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride
Since dipole moment is a product of charge and distance, therefore, chlorobenzene has a
lower dipole moment than cyclohexyl chloride due to the lower magnitude of charge (δ-)
on Cl atom and small C-Cl distance.
▪ C-Cl bond in chlorobenzene acquires some double-bond character due to
reasonance -Cl bond in chlorobenzene is less polar than in cyclohexyl chloride due
to Cl atached to sp2-hybridised carbon
r) Haloalkanes undergo nucleophilic substitution whereas haloarenes undergo electrophilic
substitution. Explain. (Comptt. Delhi 2012)
7. Account for the following
a) why the boiling points of chlorides, bromides and iodides are considerably higher than
those of the hydrocarbons of comparable molecular mass?
Due to greater polarity as well as higher molecular mass as compared to the parent
hydrocarbon, the intermolecular forces of attraction (dipole-dipole and van der Waals)
are stronger in the halogen derivatives
b) For the same alkyl group, the boiling points of alkyl halides decrease in the order:
RI> RBr> RCl> RF
This is because with the increase in size and mass of halogen atom, the magnitude of
van der Waal forces increases.
c) The boiling points of isomeric haloalkanes decrease with increase in branching due to
decrease in surface area and the magnitude of van der Waal forces decreases
d) the para-dichlorobenzene isomers are high melting as compared to their ortho and
meta-isomers.
It is due to symmetry of para-isomers that fits in crystal lattice better as compared to
ortho- and meta-isomers
e) haloalkanes tend to dissolve in organic solvents because the new intermolecular
attractions between haloalkanes and solvent molecules have much the same strength as
the ones being broken in the separate haloalkane and solvent molecule
f) Groups like cyanides and nitrites possess two nucleophilic centres and are called
ambident nucleophiles
g) Haloalkanes react with KCN to form alkyl cyanides as main product while AgCN forms
isocyanides as the chief product. Explain.
KCN is predominantly ionic and provides cyanide ions in solution. Although both carbon
and nitrogen atoms are in a position to donate electron pairs, the attack takes place
mainly through carbon atom and not through nitrogen atom since C—C bond is more
stable than C—N bond. However, AgCN is mainly covalent in nature and nitrogen is free
to donate electron pair forming isocyanide as the main product
h) Neopentyl chloride shows SN1 reaction .why?
i) Arrange each set of compounds in order of increasing boiling points.
(i) Bromomethane, Bromoform, Chloromethane, Dibromomethane.
(ii) 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane
8. Arrange the following compounds in increasing order of reactivity towards SN2 displacement:
2-Bromo-2-Methylbutane, 1-Bromopentane, 2-Bromopentane.
9. Illustrate Sandmeyer’s reaction with the help of a suitable example
Sandmeyer’s reaction: The substitution of diazo group of benzene diazonium chloride by Chloro,
Bromo with the help of solution of CuCl dissolved in HC1, CuBr/HBr respectively is known as
Sandmeyer’s reaction
10. Chirality : The objects which are non-superimposable on their mirror image are said to be chiral
and this property is known as chirality
11. Racemic mixture : A mixture which contains the equal proportions of two enantiomers of a
compound in equal proportions is called racemic mixture
12. Which one of the following compounds is more easily hydrolyzed by KOH and why?
CH3CHClCH2CH3 or CH3CH2CH2Cl
13. Of the two bromoderivatives, C6H5CH (CH3)Br and C6H5CH(C6H5)Br, which one is more reactive in
SN1 substitution reaction and why
14. How would you differentiate between S<subN1 and SN2 mechanisms of substitution reactions?
Give one example of each
15. Write the structure of the alkene formed by dehydrohalogenation of 1-Bromo-1-
methylcyclohexane with alcoholic KOH.
16. Which is chiral

17. Out of and which one is optically active and why?)

18. Which molecule is chiral ?

19. Answer

20. The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in
the presence of alcoholic KOH, alkenes are major products. Explain
21. 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) l-Bromo-3-methylbutane, 2-Bromo-2-methyl-butane, 3-Bromo-2-methylbutane
(iii) 1-Bromobutane, l-Bromo-2,2-dimethyl-propane, l-Bromo-2-methylbutane
22. Write the structure of the product formed when chlorobenzene is treated with methyl chloride
in the presence of sodium metal and dry ether
23. Which of the following two reactions is SN2 and why?

24. Write the structural formula of A, B, C and D in the following sequence of reaction
25. The 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 beta-elimination reaction
26. What happens when
(i) CH3—Cl is treated with aqueous KOH?
(ii) CH3—Cl is treated with KCN?
(iii) CH3—Br is treated with Mg in the presence of dry ether?
Chlorobenzene is treated with Cl2/FeCl3,
(ii) Ethyl chloride is treated with AgNO2,
(iii) 2-bromopentane is treated with alcoholic KOH?
27. Which compound sn2 faster
In the following pairs of the halogen compounds which compound undergoes
a. faster SN1 reaction

(b) Which compound in each of the following pairs will react faster in SN2 reaction with
-OH group?
(i) CH3Br or CH3I
(ii) (CH3)3CCl or CH3Cl
(c) which one undergoes SN2 substitution reaction faster and why?

d Which compound in the following couples will react faster in SN2 displacement and
why?
(a) 1-bromopentane or 2-bromopentane
(b) l-bromo-2-methylbutane or 2-bromo-2-methylbutane.
e Which alkyl halide from the following pair is (i) Chiral and (ii) undergoes SN1
reaction faster?
(a) (CH3)2CBr
(b) CH3CH2CHBrCH3
f
Which alkyl halide from the following pair is (i) Chiral and (ii) undergoes SN2
reaction faster?

g hich one in the following pairs undergoes SN1 substitution reaction faster and why?
(All India 2009)
 h hich one in the following pairs of substances undergoes SN2 substitution reaction
faster and why? (Delhi 2009)

i ut of

which is an example of vinylic halide?

j n the following pair of halogen compounds, which compound will react faster
by SN1 mechanism? (Comptt. Delhi 2013)

k Arrange the following in increasing order of boiling point:

(i) CH3CH2CH2CH2Br
(ii) (CH3)3.Br
(iii) (CH3)2C.Br
28. Write the major product(s) in the following:

a.

c
29. How do you convert

a) Chlorobenzene to biphenyl
b) Propene to 1-iodopropane
c) 2-bromobutane to but-2-ene
d) Aniline to bromobenzene
e) Chlorobenzene to 2-chloroacetophenone
f) Chloroethane to butane
g) 2-Bromopropane to 1-bromopropane
h) Benzene to p-chloronitrobenzene
i) Propene to propan-1-ol
j) Ethanol to but-1-yne
k) 1-Bromopropane to 2-bromopropane
l) Toluene to benzyl alcohol
m) Benzene to 4-bromonitrobenzene
n) Benzyl alcohol to 2-phenylethanoic acid
o) Ethanol to propanenitrile
p) Aniline to chlorobenzene
q) 2-Chlorobutane to 3, 4-dimethylhexane
r) 2-Methyl-1-propene to 2-chloro-2-methylpropane
s) Ethyl chloride to propanoic acid
t) But-1-ene to n-butyliodide (
u) Chlorobenzene to p-nitrophenol
v) 2-Bromopropane to 1-bromopropane
w) Chloroethane to butane
x) Benzene to diphenyl
y) tert-Butyl bromide to isobutyl bromide
z) Propene to 1-nitropropane
aa) Ethanol to ethyl fluoride
bb) But-1-ene to but-2-ene
cc) Prop-1-ene to 1-fluoropropane
30. Write the equations for the preparation of 1-bromobutane from :
(i) 1-butanol (ii) but-l-ene

31. Out of SN1 and SN2, which reaction occurs with

(a) Inversion of configuration
(b) Racemisation
32. Give chemical tests to distinguish between the following pairs of compounds :
(a) Benzyl chloride and Chlorobenzene
33. Complete the following
a

c
d

A B
 k

A B

34. Primary alkyl halide C4H9Br (a) 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 compound (d), C8H18 which is different from the compound formed when n-
butyl bromide is reacted with sodium. Give the structural formula of (a) and write the
equations for all the reactions
35. Write the short note

• Alkyl iodides are often prepared by the reaction of alkyl chlorides/ bromides with NaI
in dry acetone. This reaction is known as Finkelstein reaction.

• The synthesis of alkyl fluorides is best accomplished by heating an alkyl

chloride/bromide in the presence of a metallic fluoride such as AgF, Hg2F2 , CoF2 or
SbF3 . The reaction is termed as Swarts reaction

• Wurtz-Fittig reaction
A mixture of an alkyl halide and aryl halide gives an alkylarene when treated with sodium
in dry ether and is called Wurtz-Fittig reaction

• Fittig reaction
Aryl halides also give analogous compounds when treated with sodium in dry ether, in
which two aryl groups are joined together. It is called Fittig reaction

• Wurtz reaction
Alkyl halides react with sodium in dry ether to give hydrocarbons containing double the
number of carbon atoms present in the halide. This reaction is known as Wurtz reaction

36

Retention : inversion : racemic mixture

37