Phenols: Preparation and reactions

Phenols are aromatic compounds with a hydroxyl group directly connected to an

aromatic ring. They are hydroxy derivatives of benzene. The general formula of
phenol is C6H6O.
Phenol Structure

Phenol was discovered by Runge (1834) in coal-tar and he named it carbolic acid
(Carbo =  coal, oleum = oil). It is also known as carbolic acid.. it is mildly acidic and
corrosive to the respiratory tract and skin. It can cause chemical burns.

Preparation of phenol
From diazonium salt
Diazonium salts are hydrolyzed to phenols in the presence of dilute acids.

From Grignard reagent

The bubbling of oxygen through the ethereal solution of phenyl magnesium bromide
produces an additional product that hydrolysis in an acidic medium produces phenol.

By Dow’s process (from chlorobenzene)

Chlorobenzene, obtained by the chlorination of benzene, is treated with sodium
hydroxide to form sodium phenoxide. Sodium phenoxide, in reaction with dilute
hydrochloric acid yields phenol.
By sodium salicylate
On distillation with soda lime, sodium salicylate undergoes decarboxylation to form
sodium phenoxide, which on acidification, yields phenol.

From benzene (Raschig process)

Chlorobenzene, obtained from the catalytic oxidation of a benzene and hydrogen
chloride, is hydrolyzed by its mixture with steam over a Si catalyst at 500 °C to
produce phenol.
By direct oxidation of benzene
Benzene with air is passed over vanadium phenoxide at 500-600 oC to get phenol.

Phenol from Cumene

Physical properties of phenol

1. It is a white hygroscopic crystalline solid with a strong phenolic odour.
2. They have higher melting and boiling point than arenes and haloarene of
comparable molecular mass.  The phenol has m.p 43oC b.p. 182 oC.
 3. They are only slightly (sparingly) soluble in water, even though they can
form intermolecular H-bonds with water molecules. The hydrophobic
nature of the benzene ring contributes to the low solubility.
4. On exposure to light and air, it develops slight pink color due the partial
oxidation.
5. It is very poisonous and can cause painful blisters in contact with skin.
Chemical properties of phenol
The reactions of phenol are those of the phenyl and -OH groups. The phenolic -OH
group exhibits the typical replacement reactions of the aliphatic -OH group but differs
from the alcoholic -OH as it has a weakly acidic character.
The acidic nature of phenol is due to the following:
1. The tendency of the oxygen atom to share its lone pair of electrons with the
benzene ring gives rise to resonance.
2. The residual phenolate ion, due to proton removal, shows stability due to
resonance.

Phenol is more acidic than alcohols due to stabilization of phenoxide ion through
resonance. Presence of the electron withdrawing group increases the acidity of phenol by
stabilizing phenoxide ion while the presence of the electron releasing group decreases the
acidity of phenol by destabilizing phenoxide ion. Hence Phenol is more acidic than
Alcohols.

The acidity of phenols could be increased by the attaching of the electron withdrawing
groups (NO2, CN, CHO, COOH). On the other hand, the acidity of the phenol is further
decreased due to the attachment of the electron donating groups (methyl, methoxy,
hydroxy etc.) to the compound.
1. The acidity of the three nitrophenols grows in this order: meta> ortho> para.

2. The most acidic of the three is para nitrophenol.

3. one has to take into account the -R and -I effect.

Now, for the inductive effect, the greatest intensity is observed at the ortho-position, followed
by meta-, and then para-.
For the resonating effect, the intensity is greatest for para and lowest for ortho, while meta has no
such effect. Now keeping in mind, that -R and -I both tend to withdraw electrons away from the
phenol group (and thus increases the acidity), and the R effect has more contribution than
the I effect, we can thus deduce that para-nitrophenol is most acidic, followed by ortho-nitrophenol,
then meta-nitrophenol and since phenol has no ring activating group, it comes out to be least acidic in
the given compounds.
Reaction due to -OH group
Reduction of phenol
Phenol, on heating with the Zn dust, undergoes reduction to form benzene.

Reaction with ammonia

At high temperatures, phenol reacts with ammonia in the presence of anhydrous
ZnCl2 to produce aniline.
Ether formation (Williamson’s synthesis)
Sodium phenoxide reacts with an alkyl halide to form ether.

Ester formation
Phenol reacts with an acyl halide, aryl halide, or acid anhydride in an alkali solution to
form phenyl esters.

Reaction with PCl5

Phosphorous pentachloride reacts with phenol to give chlorobenzene.

Reaction with benzoyl chloride

Benzoyl chloride reacts with phenol in the presence of aqueous NaOH to form phenyl
benzoate.

Reaction due to benzene ring

Electrophilic substitution reaction
a. Halogenation: When bromine water is added to phenol, a white precipitate of
2,4,6- tribromophenol is formed.

b. Nitration: Phenol reacts with conc. nitric acid in the presence of sulphuric acid to
form 2,4,6-trinitrophenol (picric acid). But in the presence of dilute nitric acid, it gives
a mixture of ortho and para nitrophenol.

Catalytic hydrogenation
Phenol reacts with hydrogen in the presence of a nickel catalyst at 150°C to from
cyclohexanol.
Oxidation
Exposure to air and light, phenol turns pink due to partial oxidation. It forms a
complex mixture of products on oxidation. Quinone is one of the oxidation products
of phenol which form phenoquinone on reaction with phenol. Phenoquinone has
brilliant red color.

Kolbe’s reaction
Sodium phenoxide, on heating with CO 2 at 135°C under 4 – 7 atm pressure, produces
sodium salicylate, which on acidification with dilute HCl, gives salicylic acid.
Salicylic acid acts starting material for the preparation of aspirin (an analgesic).
Reimer-Tiemann reaction
When phenol is heated in the presence of chloroform and alkali, salicylaldehyde is
formed. This is known as the Reimer-Tiemann reaction.

Friedel-Craft’s reaction
In the presence of anhydrous aluminium chloride, phenol reacts with an alkyl halide to
form p-Cresol.

Coupling reaction
At low temperatures, benzene couples with benzene diazonium chloride in a slightly
alkaline medium to form p-hydroxyazobenzene which is a red dye.
Condensation reactions
a. In the presence of concentrated sulfuric acid, phenol undergoes a condensation
reaction with an acid anhydride to form phenolphthalein.

b. Condensation of phenol and formaldehyde in the presence of a basic catalyst form

phenyl-formaldehyde resin. Methylene bridges are formed in ortho, para, or both
positions during this reaction. Depending on the reaction conditions, both linear and
cross-linked polymers are formed.
Bakelite makes phonograph records, combs, wire insulation, switches, and automobile
distribution caps. In contrast, soft bakelite is used for binding glue for laminated
wooden planks and in varnishes and lacquers. Sulphonate bakelites are used as ion
exchange resin.
Uses of phenol
1. It is used for the manufacture of Bakelite.
2. It acts as row material for making salicylic acid and drugs like salol and
aspirin.
3. In low concentrations, phenol is used as a disinfectant in household
cleaners and mouthwash.
4. Cough drops and other antiseptics contain less toxic phenols like n-
hexylresorcinol.
5. Butylated hydroxytoluene is a common antioxidant in foods.
6. Phenol is commonly used in ingrown toenail surgeries.
7. It makes photographic developers, detergents, wood preservatives, and
selective weed killers.
8. Muscle spasticity can be treated with phenol injections.

Differences between aliphatic alcohol and phenol

S.N. Phenol Alcohol

1. It has characteristic phenolic order. Alcohols have a wine-like odour.

2. Acidic in nature. They are neutral.

On reaction with FeCl3 it gives violet

3. They don’t react with FeCl3.
coloration.

4. It forms dyes with the diazonium salt. No action with a diazonium salt.

Alcohols don’t undergo a hydrogenation

5. Phenol undergoes hydrogenation reaction.
reaction.

Alcohols undergo a dehydrogenation reaction to

6. It does not dehydrogenate.
give aldehyde.

Similarly between aliphatic alcohol and phenol

S.N. Phenol Alcohol

Phenol on reaction with acetyl chloride or acid Alcohol also forms ester on reaction with
1.
anhydride forms ester. acetyl chloride or acid anhydride.

The reaction of sodium phenoxide with alkyl The reaction of sodium alkoxide with alkyl
2.
halide produces ethers halide also produces ethers
 Alcohols on reduction produce aliphatic
3. Phenols on reduction form aromatic hydrocarbon
hydrocarbon.