HALOALKANES & HALOARENES-3

1. Aryl chlorides and bromides can be easily prepared by electrophilic substitution of arenes
with chlorine and bromine respectively in the presence of Lewis acid catalysts. But why
does preparation of aryl iodides requires presence of an oxidizing agent?

ANS:

Iodination reactions are reversible in nature. To carry out the reaction in the forward
direction, HI formed during iodination is removed by oxidation. HIO 4 is used as an
oxidizing agent.

2. Out of o-and p-dibromobenzene which one has higher melting point and why?

ANS:

p-dibromobenzene has higher melting point than its o-isomer. It is due to symmetry of p-
isomer which fits in crystal lattice better than the o-isomer.

3. Why can aryl halides not be prepared by reaction of phenol with HCl in the presence of
ZnCl2?

ANS:

C—O bond in phenols is more stable due to resonance effect and it has double bond
character, hence breaking of this bond is difficult.

4. Allyl chloride is hydrolysed more readily than n-propyl chloride. Why?

ANS:

Allyl chloride shows high reactivity as the carbocation formed by hydrolysis is stabilised by
resonance while no such stabilisation of carbocation exists in the case of n-propyl chloride.
5. Why is it necessary to avoid even traces of moisture during the use of a Grignard
reagent?

[OR]

Grignard reagent should be prepared under anhydrous conditions. Why?

ANS:

Grignard reagents are highly reactive and react with water to give corresponding
hydrocarbons.

RMgX + H2O → R-H + Mg(OH)X

6. What are ambident nucleophiles? Explain with an example.

ANS:

Ambident nucleophiles are nucleophiles having two nucleophilic sites. Thus, ambident
nucleophiles have two sites through which they can attack.

E.g Nitrite ion

Nitrite ion can attack through oxygen resulting in the formation of alkyl nitrites. Also, it can
attack through nitrogen resulting in the formation of nitroalkanes.

7. Which compound in each of the following pairs will react faster in SN2 reaction?

(i) CH3Br or CH3I (ii) (CH3)3CCl or CH3Cl

ANS:

(i) CH3I

In the SN2 mechanism, the reactivity of halides for the same alkyl group increases in the
order. This happens because as the size increases, the halide ion becomes a better leaving
group.

R−F << R−Cl < R−Br < R−I

Therefore, CH3I will react faster than CH3Br in SN2 reactions with OH−.
(ii) CH3Cl

The SN2 mechanism involves the attack of the nucleophile at the atom bearing the leaving
group. But, in case of (CH3)3CCl, the attack of the nucleophile at the carbon atom is
hindered because of the presence of bulky substituents on that carbon atom bearing the
leaving group. On the other hand, there are no bulky substituents on the carbon atom
bearing the leaving group in CH 3Cl. Hence, CH3Cl reacts faster than (CH 3)3CCl in SN2
reaction with OH−.

8. Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolysed by aqueous KOH?

ANS:

Hydrolysis by aqueous KOH proceeds through the formation of carbocation. If carbocation

is stable, then the compound is easily hydrolyzed by aqueous KOH.

C6H5CH2Cl forms primary carbocation where as C6H5CHClC6H5 forms secondary

carbocation, which is relatively more stable. Hence, C 6H5CHClC6H5 more easily hydrolysed
by aq.KOH than C6H5CH2Cl.