CHAPTER – 31

HALOGEN COMPOUNDS
*** Recall the reactions by which halogenoarenes can be produced.

Reactivity of Halogenoarenes - Difference in Reactivity of

Halogenoalkanes & Halogenoarenes

 Halogenoarenes are very unreactive compared to halogenoalkanes

 The difference in reactivity between the two compounds is because of the carbon-halogen bond
strengths.

Halogenoalkanes

 The halogenoalkane (chloroethane) can take part in nucleophilic substitution reactions

 A nucleophile, such as a hydroxide (OH-) ion, will attack the slightly positive carbon atom
 A covalent bond is formed between that carbon atom and the nucleophile which causes the
carbon-halogen bond to break
 Overall, the halogen is replaced by the nucleophile.

Halogenoarenes

 Halogenoarenes, such as chlorobenzene, do not readily undergo nucleophilic

substitution reactions.

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 Only under extremely harsh conditions, such as temperatures of 200 oC and a pressure of 200
atmospheres, will the chlorine in chlorobenzene get replaced by a nucleophile such as a hydroxide
(OH-) ion.
 This is because the carbon-chlorine bond is very strong and cannot be easily broken
o One of the lone pairs of electrons on the chlorine will interact with the π system of the
ring.
o This causes the carbon-chlorine bond to have a partial double-bond
character, which strengthens the bond.

 The unreactivity of halogenoarenes can therefore be explained by the delocalisation of a

lone pair on the halogen over the benzene.
 This causes additional stabilisation of the system and strengthens the carbon-halogen bond,
which affects the reactions that halogenoarenes will undergo.
 It gets harder to break the carbon-halogen bond in halogenoarenes, which decreases
reactivity.

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 CHAPTER – 31
INTRODUCTION TO PHENOLS
Phenols are benzene compounds which have an -OH group attached directly to it.

 In a phenol molecule, one of the lone pairs on the oxygen overlaps with the delocalised
electron system.
 This increases the electron density of the delocalised electron system.
 It makes phenols much more reactive than benzene itself.
 Also, it increases the acidity of phenol as well.

Physical properties of phenols

 Phenol has a higher melting and boiling points than methylbenzene. This is because phenols
can form hydrogen bonds between them in addition of van der Waals' forces and permanent
dipole-dipole forces.
 However, the large non-polar benzene ring makes phenol only slightly soluble in water, as it
disrupts hydrogen bonding with water molecules.
 Phenol is weakly acidic, losing an H+ ion from its hydroxyl group

Comparing the strength of organic acids

The strength of organic acids depends on,
 The strength of the O-H bond which is to be broken.
 The stability of the anion formed.

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Comparing acidity of phenol, water and ethanol

 Phenol’s conjugate base (the phenoxide ion) has its negative charge spread over the whole
ion as one of the oxygen’s lone pairs overlaps with the delocalised π bonding system, hence
reducing the charge density of the C6H5O-(aq) compared with OH-(aq) in water or C2H5O-(aq) in
ethanol.
 Therefore H+(aq) ions are less attracted to the phenoxide than hydroxide or
ethoxide ions, making phenoxide less likely to re-form the undissociated
molecules.
 Phenol ionises to form a stable negative ion, so the position of equilibrium
lies further to the right-hand side.

 Ethanol is the weakest acid due to the electron-donating alkyl group

attached to the oxygen atom in the ethoxide ion, concentrating more
negative charge on the oxygen atom, which more readily accepts H+ ions
(equilibrium lies further to the left-hand side).

On the other hand, water is a stronger acid than ethanol but weaker than phenol. This is because
in ethoxide ion, the presence of an alkyl group intensifies the negative charge on the oxygen
atom. In a hydroxide ion, no such thing happens.

*** Ethanoic acid is the strongest because of the stability of ethanoate ion formed. In an ethanoate

ion, the negative charge is spread throughout the -COO group. This delocalisation of electron and
negative charge stabilises it to a greater extent. However, since oxygen atoms are the most
electronegative, more negative charge will still be concentrated here.

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Production of phenol
 Phenols can be prepared from phenylamines under the following reaction conditions:
o NaNO3 with dilute acid (to form HNO2)
o Ice to keep the temperature below 10 oC (step 1)
o Heat (step 3)
 This reaction involves three steps:

Step 1 - The HNO2 is so unstable that it needs to be prepared in a test-tube by reacting sodium
nitrate (NaNO3) and dilute hydrochloric acid (HCl) while keeping the temperature below 10 oC
using ice.

Step 2 - Phenyl amine is then reacted with the HNO2 to form an unstable diazonium salt.

Step 3 - The diazonium salt is so unstable that it will thermally decompose when heated to form
a phenol

Reactions of Phenols

1. Reaction with sodium metal

Reagent: Sodium metal, Na

Condition: Room temperature

This reaction is more vigorous than the one with alcohol because phenol is more acidic.
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2. Reaction with sodium hydroxide

Reagent: Sodium hydroxide

Condition: Room temperature

Phenol is a strong enough acid to react with sodium hydroxide solution to give sodium phenoxide
and water.

***Since alcohols will not react with sodium hydroxide, this can be used as a test to distinguish
alcohols from phenols.

3. Halogenation
Reagent: Chlorine gas/bromine water
Condition: Room temperature
Product: 2, 4, 6-trihalophenol

Phenol will react with halogens even without the presence of halogen carriers. This proves that
phenol is more reactive than benzene itself.

Observations:
 The reddish-brown of bromine decolourises.
 A white precipitate is formed, this is 2, 4, 6-tribromophenol.
 Steamy fumes of hydrogen bromide is observed.

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4. Nitration

Reagent: Nitric acid

Condition: Room temperature
Product: Nitrophenols

Unlike benzenes, concentrated sulfuric acid is not needed for nitration to occur. This proves that
phenol is more reactive than benzene itself.
 With dilute nitric acid, mono-substitution occurs. 2-nitrophenol and 4-nitrophenol is
produced.

 With concentrated nitric acid, tri-substitution occurs. 2, 4, 6-trinitrophenol is produced.

5. Reaction with diazonium ions

 Diazonium ions are very reactive compounds containing an -N2+ group.

 When phenols are dissolved in sodium hydroxide (NaOH), a solution of sodium phenoxide is
obtained.
 This solution is cooled in ice and cold diazonium ion is added to the sodium phenoxide.
 After the reaction has occurred, a yellow-orange solution or precipitate of an azo
compound is formed.
 These are compounds in which two benzene rings are linked by a nitrogen bridge.

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Reactions of Other Phenolic Compounds

Phenolic compounds are those that contain a phenol functional group. An example of a phenolic
compound is 1-naphthol.

 1-Naphthol contains a phenol group attached to another benzene ring

 Just like with phenol, the -OH group in 1-naphthol is also electron-donating and activates the
benzene ring to electrophilic substitution reactions.
 The electrophiles are directed to the 2 and/or 4 positions
 Substitution at the 6 position is not possible as there is no hydrogen atom on this carbon
o This carbon is bonded to a carbon atom of the second benzene ring.
 1-Naphthol and other phenolic compounds react in a similar way as phenol.