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.

OH OH CH3 OH
OH COOH

Br

phenol m-bromophenol o-cresol salicylic acid

OH OH COOH
OH
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
H
O
N
O NO2

o-nitrophenol p-nitrophenol
bp 100oC at 100 mm bp decomposes
0.2 g / 100 mL water 1.69 g / 100 mL water
volatile with steam non-volatile with steam
phenols, syntheses:
1. From diazonium salts

N2 OH
H2O,H+

2. Alkali fusion of sulfonates

SO3 Na NaOH,H2O ONa OH

H+

300o
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 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF

OH ONa

+ NaOH + H2O

SA SB WB WA
CH4 < NH3 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF

OH ONa

+ NaOH + H2O

SA SB WB WA
water insoluble water soluble

OH

+ NaHCO3 NR phenol < H2CO3

CH4 < NH3 < HCCH < 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?

 ROH + H2O H3O+ + RO-

ArOH + H2O H3O+ + ArO-

OH OH O O O O O

Resonance stabilization of the phenoxide

ion, lowers the PE of the products of the
ionization, decreases the ΔH, shifts the equil
farther to the right, makes phenol more
acidic than an alcohol
effect of substituent groups on acid strength?

OH O

G + H2O G + H3O

Electron withdrawing groups will decrease the negative

charge in the phenoxide, lowering the PE, decreasing the
ΔH, 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 ΔH,
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

3 5 1 4 2
SO3H COOH OH CH2OH

1 2 3 4
2. ester formation (similar to alcohols)

OH
CH3 O H+ O
+ CH3CH2C CH3CH2C + H2O
OH O

H3C

O
OH H3C C
COOH O
+ (CH3CO)2O COOH

salicyclic acid aspirin

 O
analgesic
H3C C anti-inflamatory
O
antipyrretic
COOH anticoagulant

Reye's syndrome
aspirin not to be used by children
with high fevers!

OH

aspirin substitute
Tylenol

H3C C NH Kidney damage!

O

acetaminophen
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.

OH OCH2CH3

+ 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

Br
polyhalogenation!
OH OH OH
Br2, CCl4 Br
+
non-polar solvent
Br
c) sulfonation
OH OH
H2SO4, 15-20oC SO3H

OH

H2SO4, 100oC

SO3H

At low temperature the reaction is non-reversible and the lower Eact ortho-
product is formed (rate control).
At high temperature the reaction is reversible and the more stable para-
product is formed (kinetic control).
d) Friedel-Crafts alkylation.

OH OH
CH3 AlCl3
+ H3C C CH3
Cl
H3C C CH3
CH3
e) Friedel-Crafts acylation

OH OH
O AlCl3
+ CH3CH2CH2C
Cl

Do not confuse FC acylation with esterification:

OH
O
O
+ CH3CH2CH2C O
Cl
Fries rearrangement of phenolic esters.

OH
O
O
+ CH3CH2CH2C O
Cl

AlCl3

OH

O
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)

OH N2 Cl OH
CH3 CH3
+

benzenediazonium N
chloride N

an azo dye
h) Kolbe reaction (carbonation)

ONa OH
COONa
125oC, 4-7 atm.
+ CO2

sodium salicylate

EAS by the weakly H+

electrophilic CO2

O C O OH
COOH

salicylic acid
i) Reimer-Tiemann reaction

OH OH
CHO
CHCl3, aq. NaOH H+
70oC

salicylaldehyde

The salicylaldehyde can be easily oxidized to salicylic acid

Spectroscopy of phenols:

Infrared:
O—H stretching, strong, broad 3200-3600 cm-1
C—O stretch, strong, broad ~1230 cm-1
(alcohols ~ 1050 – 1200)

nmr: O—H 4-7 ppm (6-12 ppm if intramolecular

hydrogen bonding)