Phenols
Introduction: Phenols are a class of compounds containing the hydroxyl group
(-OH) which is attached to an aromatic benzene ring. Phenols are toxic and have
a powerful sweetly smell to them. They are not the same as alcohols because the
hydroxyl group (-OH) present in phenols is bound to an aromatic benzene ring,
which determines the chemical properties of the compounds within this class.
Phenols beings attached to a benzene ring end up becoming more acidic and in
turn more reactive than alcohols. Most common of the phenols is
hydroxybenzene (C6H5OH) which is also known as Phenol. There are some
compounds in the phenol class which have additional groups attached to the
benzene ring i.e: Cresol (C7H8O), Catechol (C6H4(OH)2) etc.
Properties: The properties of Phenols are classified by two main categories.
The physical properties and the chemical properties. These properties are
determined by their structure and the compounds or functional groups bound to
the benzene ring of the phenol.
Some of the physical and chemical properties of phenols are discussed below:
Physical Properties:
1. Phenols are generally colorless and have a very sweetly odor. They’re
generally toxic.
2. Phenols upon oxidation give pink, red or dark brown colors. When phenol is
oxidized using chromic acid it’s product is para-benzoquinone which
usually has a dark brown color along with an irritating pungent odor.
3. Phenols have a higher boiling point compared to alcohols of similar
molecular weight. For example, phenol (C₆H₅OH) has a boiling point of
181.7°C. The -OH bonds in phenol results in the creation of hydrogen bonds
among the molecules, which increases the intermolecular force which is the
reason behind such a high boiling point.
4. Phenols, in room temperature, are either crystalline solids or viscous liquids.
No phenols are gases.
5. The formation of hydrogen bonds by the hydroxyl groups makes these
compounds polar, this partial polarity enable phenols to be partially soluble
in water. The solubility decreases as the number of carbon atoms and
increases.
6. Phenols compared to water denser. The greater density means that phenols
sink in water.
Chemical Properties:
1. Phenols are weak acids, they have a pKa of around 10. The pKa of Phenol
is around 9.95. Phenols do not react with NaHCO 3 , but they do react with
NaOH and produce phenoxide salts.
C6H5OH + NaOH → C6H5ONa + H2O
2. Benzene is relatively non-reactive but in phenols the presence of hydroxyl
group makes them chemically active, so phenols give halogenation,
sulfonation, nitration etc. reactions.
3. Phenols form quinones when oxidized typically benzoquinone, the most
common benzoquinone is 1,4-benzoquinone.
C₆H₅OH + O2 + (KSO₃)₂NO → C₆H₄O₂ + H₂O
In the reaction above, Phenol when oxidized in the presence of Fremy’s salt
(potassium nitrosodisulfonate) yields 1,4-benzoquinone and water.
4. Reimer-Tiemann Reaction: Reimer-Tiemann reaction is a substitution
reaction where the phenols react to chloroform in the presence of a strong
base (e.g. NaOH/KOH) and produce ortho-hydroxy benzaldehyde.
5. Phenols give a variety of coupling reactions such as: Azo Coupling,
Oxidative Coupling, Carbonyl Coupling and Enzymatic Coupling. These
reactions are especially important in biochemistry since these reactions
serve critical roles in biological systems (i.e. Pigment Synthesis (melanin),
Lignin Formation (plant cell walls), Neurotransmitter Metabolism,
Antioxidant Defense etc.
6. Esterification: Phenols upon reacting with acyl chlorides or acid anhydrides
creates ester.
C6H5OH + (CH3CO)2O → C6H5OCOCH3 + CH3COOH
In the reaction above phenol reacted with acetic anhydride and produced
phenyl acetate and acetic acid as products.
Preparation:
1. Dow’s Process: In Dow’s method of phenol synthesis Chlorobenzene
(C6H5Cl) first reacts with aqueous sodium hydroxide (NaOH(aq)) at 350o C
(623K) and a pressure of 4000psi (300atm). The product Sodium phenoxide
is the acidified to produce Phenol. This method is simple but not the most
common one since it requires harsh conditions for production.
2. Cumene Process: The most common method of phenol production would
be the Cumene hydroperoxide process also known as Cumene process. It is
famous because in this way we can prepare both phenol and acetone thus
it’s cost effective. Which is why this method is applied at the industrial
scale.
Firstly, benzene and propylene create cumene or isopropylbenzene (C9H12),
in the next step the cumene is oxidized to form cumene hydroperoxide. The
cumene hydroperoxide is then cleaved using acid cleavage to produce
phenol and acetone.
3. Hydrolysis of Diazonium salts: A diazonium salt like benzene diazonium
chloride is hydrolyzed resulting in the replacement of the N 2+ (diazo group)
with a hydroxyl group forming phenol.
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