Phenols

Ar-OH

Phenols are compounds with an OH group

attached to an aromatic carbon. Although they
share the same functional group with alcohols,
where the OH group is attached to an aliphatic
carbon, the chemistry of phenols is very different
from that of alcohols.

Nomenclature.
Phenols are usually named as substituted phenols. The
methylphenols are given the special name, cresols. Some other
phenols are named as hydroxy compounds.
CH3

OH

OH

OH
OH

COOH

Br
phenol

m-bromophenol
OH

OH

o-cresol

salicylic acid

OH

COOH

OH

OH

OH
OH
catechol

resorcinol

hydroquinone

p-hydroxybenzoic acid

physical properties
phenols are polar and can hydrogen bond
phenols are water insoluble
phenols are stronger acids than water and
will dissolve in 5% NaOH
phenols are weaker acids than carbonic acid and
do not dissolve in 5% NaHCO3

Intramolecular hydrogen bonding is possible in some

ortho-substituted phenols. This intramolecular hydrogen
bonding reduces water solubility and increases volatility.
Thus, o-nitrophenol is steam distillable while the
isomeric p-nitrophenol is not.
OH
O
N
O

H
O

o-nitrophenol
bp 100oC at 100 mm
0.2 g / 100 mL water
volatile with steam

NO2
p-nitrophenol
bp decomposes
1.69 g / 100 mL water
non-volatile with steam

phenols, syntheses:
1. From diazonium salts
N2

OH
H2O,H+

2. Alkali fusion of sulfonates

SO3 Na

NaOH,H2O
300o

ONa

H+

OH

Reactions:
alcohols

phenols

1. HX

NR

2. PX3

NR

3. dehydration

NR

4. as acids

phenols are more acidic

5. ester formation

similar

6. oxidation

NR

Phenols, reactions:
1. as acids
2. ester formation
3. ether formation
4. EAS
a) nitration

f) nitrosation

b) sulfonation

g) coupling with diaz. salts

c) halogenation

h) Kolbe

d) Friedel-Crafts alkylation

i) Reimer-Tiemann

e) Friedel-Crafts acylation

as acids:
with active metals:
OH

ONa
Na

+ H2(g)
sodium phenoxide

with bases:
CH4 < NH3 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF
ONa

OH
+ NaOH
SA

SB

+ H2O
WB

WA

CH4 < NH3 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF
ONa

OH
+ NaOH
SB

SA
water insoluble

+ H2O
WB

WA

water soluble

OH
+ NaHCO3

NR

phenol < H2CO3

CH4 < NH3 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF

water

5% NaOH

5% NaHCO3

phenols

insoluble

soluble

insoluble

carboxylic
acids

insoluble

soluble

soluble

We use the ionization of acids in water to measure acid

strength (Ka):
HBase + H2O

H3O+ + Base-

Ka = [H3O+ ][ Base ] / [ HBase]

ROH Ka ~ 10-16 - 10-18

ArOH Ka ~ 10-10

Why are phenols more acidic than alcohols?

OH

ROH + H2O

H3O+ + RO-

ArOH + H2O

H3O+ + ArO-

OH

Resonance stabilization of the phenoxide

ion, lowers the PE of the products of the
ionization, decreases the H, shifts the equil
farther to the right, makes phenol more
acidic than an alcohol

effect of substituent groups on acid strength?

O

OH
G

+ H2O

+ H3O

Electron withdrawing groups will decrease the negative

charge in the phenoxide, lowering the PE, decreasing the H,
shifting the equil farther to the right, stronger acid.
Electron donating groups will increase the negative charge
in the phenoxide, increasing the PE, increasing the H,
shifting the equilibrium to the left, weaker acid.

Number the following acids in decreasing order of acid

strength (let # 1 = most acidic, etc.)

OH

OH

OH

OH

OH

NO2

CH3

Br

SO3H

COOH

OH

CH2OH

2. ester formation (similar to alcohols)

OH
CH3

+ CH3CH2C

O
OH

H+

CH3CH2C

O
O

H3C
O
H3C C

OH
COOH

O
COOH

+ (CH3CO)2O
salicyclic acid

aspirin

+ H2O

O
H3C C

O
COOH

aspirin

analgesic
anti-inflamatory
antipyrretic
anticoagulant
Reye's syndrome
not to be used by children
with high fevers!

OH
aspirin substitute
Tylenol
H3C C NH
O
acetaminophen

Kidney damage!

3. ether formation (Williamson Synthesis)

Ar-O-Na+ + R-X Ar-O-R + NaX
note: R-X must be 1o or CH3
Because phenols are more acidic than water, it is possible
to generate the phenoxide in situ using NaOH.
OCH2CH3

OH
+ CH3CH2Br, NaOH
CH3

CH3

4. Electrophilic Aromatic Substitution

The OH group is a powerful activating group in EAS
and an ortho/para director.
a) nitration
OH

OH
HNO3

O2N

NO2

polynitration!

NO2
OH

OH

OH
dilute HNO3

NO2
+
NO2

b) halogenation

OH

OH
Br2 (aq.)

Br

Br

no catalyst required
use polar solvent

polyhalogenation!

Br

OH

OH

OH
Br2, CCl4
non-polar solvent

Br
+
Br

c) sulfonation
OH

OH

SO3H

H2SO4, 15-20oC

OH
H2SO4, 100oC
SO3H

At low temperature the reaction is non-reversible and the lower Eact orthoproduct is formed (rate control).
At high temperature the reaction is reversible and the more stable paraproduct is formed (kinetic control).

d) Friedel-Crafts alkylation.

OH

OH
+

CH3
H3C C CH3
Cl

AlCl3

H3C C CH3
CH3

e) Friedel-Crafts acylation
OH

OH
+

CH3CH2CH2C

AlCl3

Cl
O

Do not confuse FC acylation with esterification:

OH
+

CH3CH2CH2C

O
Cl

O
O

Fries rearrangement of phenolic esters.

OH
+

CH3CH2CH2C

O
O

Cl

AlCl3
OH

f) nitrosation
OH

OH
HONO

p-nitrosophenol
NO
EAS with very weak electrophile NO+
OH

OH
CH3

CH3

NaNO2, HCl

NO

g) coupling with diazonium salts

(EAS with the weak electrophile diazonium)
N2 Cl

OH

OH
CH3

CH3
+
benzenediazonium
chloride
an azo dye

N
N

h) Kolbe reaction (carbonation)

OH

ONa
+ CO2

COONa

125oC, 4-7 atm.

sodium salicylate
H+

EAS by the weakly

electrophilic CO2

O C O

OH
COOH

salicylic acid

i) Reimer-Tiemann reaction

OH

OH
CHCl3, aq. NaOH

H+

CHO

70oC
salicylaldehyde

The salicylaldehyde can be easily oxidized to salicylic acid

Spectroscopy of phenols:

Infrared:
OH stretching, strong, broad 3200-3600 cm-1
CO stretch, strong, broad ~1230 cm-1
(alcohols ~ 1050 1200)

nmr: OH 4-7 ppm (6-12 ppm if intramolecular

hydrogen bonding)

o-cresol

C--O

O--H

o-cresol
OH

b
CH3

ethyl salicylate (intramolecular hydrogen bonding)

d
OH O
C

O CH2CH3