ALCOHOLS,PHENOLS AND ETHERS

Reactions of Phenols

ANASWARA SANTHOSH
1.ELECTROPHILIC SUBSTITUTIION REACTION
 +R Effect
 Thus the electron density on benzene ring is increased particularly
on ortho and para positions.
(a)NITRATION
 With dilute HNO3 at low temperature : Mixture of ortho and para
nitrophenols.

 To separate the mixture : steam distillation.

 o-Nitrophenol is steam volatile than p-Nitrophenol
 Intermolecular and intramolecular H-bonding
 With conc. HNO3 : 2,4,6-trinitrophenol (PICRIC ACID)

 Yield is poor.
 Phenol+ Conc.H2SO4  phenol-2,4-disulphonic acid
phenol-2,4-disulphonic acid + conc.HNO3  2,4,6-trinitrophenol
 (b)Halogenation
 Phenol with bromine – solvents of low polarity ( CHCl3,CS2) , low temp. : Monobromophenols.

 Usually halogenation of benzene – presence of Lewis acid (FeBr3) to polarise halogen molecule.
 But in phenol polarisation of Lewis acid takes place without Lewis acid – due to highly Activating prop. of
–OH group.
 Phenol with Br water – 2,4,6-tribromophenol

 White ppt.
 KOLBE’S REACTION
 Phenol on treating with NaOH and
CHCl3 gives Phenoxide ion.
 Phenoxide ion – more reactive towards
electrophilic
Aromatic substitution.
 Phenoxide ion + weak electrophile CO2
in the presence of acid gives o-
hydroxybenzoic acid or SALICYLIC
ACID.
REMER-TIEMANN REACTIION
 On treating phenol with chloroform and
NaOH , a –CHO group is introduced at
the ortho position of
the benzene .
 The intermediate benzalchloride is
hydrolysed in the presence of alkali to
produce ortho hydoxybenzaldehyde or
SALICYLALDEHYDE.
 KOLBE’E REACTION

 REIMER-TIEMANN REACTION
4.REACTION WITH ZINC DUST

 Phenol  Benzene
5.OXIDATION
 Chromic acid Na2Cr2O7 + H2SO4
 Conjugated diketone BENZOQUINONE.
Thankyou!