10. Haloalkanes and haloarenes.

Named reactions
Distingish tests
1.Write the products of the following reactions

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Arrange each set of compounds in order of increasing boiling points.
(i) Bromomethane, Bromoform, Chloromethane, Dibromomethane.
Chloromethane Bromomethane Dibromomethane Bromoform
(ii) 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane.

17

Isopropyl chloride < 1-Chloropropane < 1-Chlorobutane

Identify chiral and achiral molecules in each of the following pair of compounds.

18

Which would undergo SN2 reaction faster?

19

Which compound undergoes faster SN1 reaction?

20

Which would you expect to react more rapidly by an SN2 mechanism? Explain.

21

Which compound in each of the following pairs will react faster in SN 2 reaction with OH?
(i) CH3Br or CH3I
(ii) (CH3)3CCl or CH3Cl

22
Arrange the compounds of each set in order of reactivity towards S N2 displacement:
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 3-Bromo-2-methylbutane

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(iii) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2-methylbutane, 1-Bromo-3methylbutane.

Identify the process

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If (A) is the only compound obtained, the process is called retention of configuration.
If (B) is the only compound obtained, the process is called inversion of configuration.
If a 50:50 mixture of the above two is obtained then the process is called racemisation and the
product is optically inactive, as one isomer will rotate light in the direction opposite to another.
2.Write the IUPAC name of the following.

25
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,

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(vi) methyl chloride is treated with KCN?

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

1. 1.Why is sulphuric acid not used

during the reaction of alcohols
with KI?

H2SO4 is an oxidizing agent, oxidizes iodide

to I2.

2. 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.

Aq. KOH produces OH-, which is stronger

nucleophile favours substitution, hence form
alcohol. In alcoholic KOH, alkoxide ion
formed is stronger base favours elimination,
hence form alkene.

3. Out of C6H5CH2Cl and

C6H5CHClC6H5, which is more
easily hydrolysed by aqueous
KOH, Why?

SN1 depends on stability of carbocation.

Hence under SN1, C6H5CHClC6H5 (20) is more
reactive, since C6H5CH+C6H5 (20) carbocation
is more stable than 10 carbocation.
SN2 depends on steric hindrance, therefore
under SN2, C6H5CH2Cl (10) is more reactive
due to less steric hindrance.

4. p-Dichlorobenzene has higher

Due to its symmetry; it fit better in crystal

m.p. and solubility than those of

o- and m-isomers. Discuss.

lattice than o- and m-isomers

5. The dipole moment of

chlorobenzene is lower than that
of cyclohexyl chloride, why?

In chlorobenzene, (i) C-Cl bond has partial

double bond character due to resonance,
hence shorter bond length, less
dipolemoment. (ii)Carbon is sp2 hybridised,
more electronegative than sp3 hybridised,
shorter bondlength and less polarity , hence
less dipolemoment,

6. Haloarenes are less reactive

towards nucleophilic substitution
reactions than haloalkanes.
Explain.

In haloarenes (chlorobenzene), (i)C-X bond

has partial double bond character due to
resonance, hence shorter bond length,
difficult to break (ii)Carbon is sp 2 hybridised,
more electronegative than sp3 hybridised,
makes the C-X bond shorter and stronger
bond.
In vinylchloride, resonance gives rise to
partial double bond character in C-X bond ,

7. Vinylchloride is unreactive in
nucleophilic substitution
reactions. Why?
8. Alkyl halides, though polar,
are immiscible with water, why ?

9. Alkyl halide is soluble in

organic solvents. Why?

difficult to break.
[It cannot form H- bond with water.] (or)
Alkyl halides are polar molecules, held by
dipole-dipole attraction. Water molecules are
held by H-bonds. Since the new forces of
attraction between water and alkyl halide
molecules are weaker than the forces of
attraction already existing between alkyl
halide - alkyl halide molecules and waterwater molecules, therefore, alkyl halides are
immiscible (not soluble) in water.
The new force of attraction between alkyl
halide - organic solvent molecules have the
same bond strength as those between alkyl
halide - alkyl halide molecules and organic
solvent-organic solvent molecules

10. Grignard reagents should be

prepared under anhydrous
conditions, why? (or)
Why is
it necessary to avoid even traces
of moisture during the use of a
Grignard reagent?

Grignard reagents are highly reactive and

react with water to give corresponding
hydrocarbons.
RMgX + H2O RH + Mg(OH)X

11. What are ambident

nucleophiles? Explain with an

Nucleophile with two nucleophilic centres.

Eg: CN-and NCNO2- and ONO-

example
12. Haloalkanes react with KCN
to form alkyl cyanides as main
product while AgCN forms
isocyanides as the chief product.
Explain.

13. Why can aryl halides not be

prepared by reaction of phenol
with HCl in the presence of
ZnCl2?
14. Allyl chloride and benzyl
chloride is hydrolysed more
readily than n-propyl chloride.
Why?
15. Although chlorine is an
electron withdrawing group, yet
it is ortho-, para- directing in
electrophilic aromatic
substitution reactions. Why?

16. The electrophilic substitution

reactions in haloarenes occur
slowly and require more drastic
conditions as compared to those
in benzene. Why?
17. The boiling points of alkyl
halides decrease in the order: RI
> RBr > RCl > RF
18. Presence of a nitro group at
ortho or para position increases
the reactivity of haloarenes
towards nucleophilic
substitution.

KCN is predominantly ionic and provides

cyanide ions in solution. The attack takes
place mainly through carbon atom since C
C bond is more stable than CN bond hence
form alkyl cyanide. AgCN is covalent in
nature and nitrogen donate electron pair
forming isocyanide as the main product.

In phenol, C-O bond has partial double

bond character due to resonance, hence
shorter bond length, difficult to break
In allyl and benzyl chloride, the
carbocation formed is stabilised by
resonance.
Chlorine withdraws electrons through
inductive effect and releases electrons
through resonance. Inductive effect
destabilises the carbocation formed.
Resonance effect stabilise the carbocation.
Resonance effect opposes the inductive
effect, hence makes the deactivation less at
ortho- and para- position. . [Reactivity is
controlled by the stronger inductive effect
and orientation is controlled by resonance
effect].

Due to electronwithdrawing inductive

effect
(-I effect) of halogen.
Size of halogen atom increases,
vanderwaals force increases, boiling
point increases
Nitro group, being an electron
withdrawing group, decreases the
electron density over the benzene ring
and stabilises the carbanion formed
through resonance.

19. Electrophilic substitution

reaction with iodine takes place
in the presence of an oxidising
agent (HNO3, HIO4).
20.Why is thionyl chloride
preferred for the preparation of
haloalkanes from alcohols ?

21.Chloroform is stored in dark

coloured bottles completely filled so
that air is kept out.

It is a reversible reaction. Oxidising agent

oxidises HI to I2.

Because the two by-products (SO2 &HCl)

are escapable gases. Hence gives pure alkyl
halide.

ROH + SOCl2

RCl + SO2

+HCl
Chloroform is slowly oxidized by air in the
presence of light to form poisonous gas
phosgene.