Phenols

Phenols are aromatic compounds which contain

hydroxyl group directly attached to the aromatic
nucleus.
Classification OH

- Monohydric phenols :

OH OH OH
OH

- Dihydric phenols :
OH

OH
catechol resorcinol hydroquinone

OH OH OH
- Polyhdric phenol HO OH OH

HO OH

OH
phloroglucinol pyrogalol hydroxyquinol
CH3

- Cresols :
OH
Synthesis:
(1) From benzene sulphonic acid :

fusion Na2SO3
SO3 Na + NaOH ONa +
SN H2O
_
OH

(2) By hydrolysis of halobenzene :

Cl + NaOH 300-350o
ONa
pr

chlorobenzene (Cine Substitution)

(3) By hydrolysis of benzenediazonium salts

+ _
N=N OH

H2O
HSO4- + N2 + H2SO4
50-60o
 Mg Br O - O - Mg Br OH
(4) From Grignard Reagents : (Oxidation)
O2 H2O
Mg Br O - O - Mg Br OH +
O2 H2O
+ Mg (OH) Br

Mg (OH) Br
(5) From phenolic acid : (Salicylic acid)

COOH OH
OH
1) Soda lime/
2) Acidification

Salicylic acid Phenol

 (6) Cumene-phenol process : (Commercial preparation)
H 3C CH3 H3C CH3
CH C O O .. H

Cumene
Alk. KMnO4 H+

H Hydroperoxide
CH3
H3C CH3
C O O H H 3C CH3
+ C O+ H 3C C O
+
- H2O
phenyl
shift

Oxonium ion Carbonium ion is much

CH3 more stable than oxonium ion

OH H 3C C O

H3C O + OH-
H
C=O
+
H3C
Acetone Phenol
 Physical Properties of Phenols :

Phenols are generally liquids or solids of low melting point.

They are colorless when pure but usually turn pink or brown -
on exposure to air and light.-

They are more polar than the corresponding saturated Alcohol, -

accordingly they are able to form stronger intermolecular hydrogen bonds-

As a result, they are less volatile and more soluble in water than alcohols -
having the same M Wt.-
 Chemical Reactions
[A] Reactions Involving O – H bond : (Acidity)
(1) Acidity of Phenols
- Phenols are much more acidic than alcohols.
_
O O O O

_ _

etc
_

- Phenols are sufficiently acidic to form salts with strong alkalis.

_ +
OH O Na + H2O

_ +
OH O Na + H2O
+ NaOH

+ NaOH
Effects of Substituents on the aromatic ring on the acid strength
of phenols
•The presence of groups having strong (-R) & (-I) effects
(electron withdrawing group)
_
O O

_ N _ N _
O + O O + O

- o- nitro or p- nitrophenol are soluble in sodium carbonate,

giving off slight effervescence.

- Trinitrophenol (picric acid) is a stronger acid than acetic acid.

-In the meta position, the nitro group will exert only its –I effect, as a result,
m-nitrophenol is a stronger acid than phenol but not as strong as
the o- & p-isomers.
Order of acidity :
OH OH OH
OH OHOH OHOH
OH OH OH
OH
OH
Cl
Cl
N2O NO2N2O NO2 NO2 NO22 N
OH OH OH OH

N2O NO2 Cl 2
NO
Cl N

NO2 NONO NO2 Cl

Cl
2 2
-I & -R -I-I&&-R
-R -I-I-I-R
-I & & -R -I-I-I
&-I-R -I
-I
weak+R
weak +R weak
weak +R
+R
NO2 NO2 H _
p-nitrophenol is more-I acidic
& -R than o-nitrophenol
-I & -R due
-I & -RO O -I
to the hydrogen bond formation.
so it affect the releasing of a proton N
+ O
http://www.adichemistry.com/organic/basics/mesomeric-effect/mesomeric-resonance-effect.html

* Substituents that have +R & -I effects ( OCH3 , halogens & NH2 groups )
OH OH OH

OCH3

OCH3

OCH3
-I +R &-I +R
+R & -I effects weaken each other
OH OH OH OH
Cl

Cl

Cl
-I -I -I
weak +R weak +R

This is due to strong –I & Weak + R effects of halogen.

Substituent have +I effect (electron donating group)

OH OH OH

H3C CH3
+I
CH3

CH3

Cresols are slightly weaker acids than phenol, this indicates that their
destabilizing effect on the phenoxide anion is small.
(2)Formation of esters
Phenols react with acid chlorides or acid anhydrides but not with
free carboxylic
.. acids to form phenyl esters.
OH OCOR

+ RCOCl + HCl

+ RCOOH No reaction

Fries Rearrangement of phenolic esters

Phenolic esters undergo rearrangement to give ortho or para
hydroxy ketones on heating in the presence of aluminium chloride.
OH

COR
OCOR AlCl3 Thermodynamicaly stable
Above 160o

OH 

Below 160o
Unstable by 

COR
Mechanism of Fries rearrangement _
AlCl3
.. +O
O
.. COR COR

AlCl3

Phenyl ester
_
+ _ .. _
O AlCl3 O AlCl3 O AlCl3
COR H

COR +
COR

OH

COR
H2O
+ Al(OH)Cl3
 (3) Formation of Ethers
- Phenols react with alkyl halides or dimethyl sulphates in alkaline medium
_
to give phenolic ethers.
_ +
O Na+ OEt
O Na OEt

OH-- Phenetole
+ Et I OH Phenetole
+ Et I

OCH3
OCH3

+ (CH ) SO OH--
+ (CH33)22SO44 OH Anisole
Anisole
- Phenols react with diazomethane to give phenyl methyl ether.
..
OH
.. OCH3

_ +
OH- + N2
+ CH2 N2

diazomethane Phenyl methyl ether

(Anisole)
Reaction of phenyl alkyl ethers :

-Phenyl alkyl ethers are decomposed by strong acid such as conc. HI & HBr
into phenol and alkyl iodide or bromide.
.. + _
OR H O R I OH

+_
HI + RI

- Diaryl ethers are unaffected by hydrogen iodide even at 200oC.

O + HI No reaction
- High stability of C–O bond is mainly due to the overlap of the unshared pair
electrons of the oxygen atom with the delocalized orbital of the ring which
imparts some double bond characters to aromatic C-O bond,
and accordingly increase its strength.

..
..... O-H

- Phenols or their derivatives don't react with neither conc. halogen acids
nor phosphorus pentachloride to give aryl halides, unless the hydroxyl group
is activated by the presence of strong electron-withdrawing groups in the
o- or p- position.
- Reaction of phenoxide with Allyl halides

Allyl halides react with phenoxide salts to give rise to either the
C- substituted or the O-substituted product
__
OO_ Na+
Na++ Polar solvent
Polarsolvent
solvent
O Na Polar OCH
OCH -- CHCH == CH
CH
oo OCH2 -22CH = CH2 22
low ToC
low T CC
low T
Phenyl
Phenyl
Phenyl allyl
allyl
allyl ether
ether
ether

200
+++ CH
CH222 ==
CH = CH
CH---CH
CH CH222 Br
CH Br
Br 200
200oo
o C
CC
Claisen rearrangement.
Sod.
Sod.phenoxide
Sod. phenoxide
phenoxide non-polar solvent
non-polarsolvent
non-polar solvent
OH
OH
OH
&&high
highTTToooC
CC

CH
CH
CH
22 -- CH
-2CH ==
CH = CH
CHCH
2 22
Mechanism of Claisen rearrangement o-allyl
o-allylphenol
o-allyl phenol
phenol

CHCH
CH
22 2 HC2C
HH
2 C
2
OO O CH CH
CH O
OO CH
CH OH
OH
OH
CH
CHCH
22 2
CH CH CH
CH - CH ==CH
CH22
CH 22 -2 CH
CH =
- CH CH2
CH
2 2
2
H
HH

Simultaneous rearrangement
Simultaneous
Simultaneousrearrangement
rearrangement
[B] Reactions at the nucleus

(1) Halogenation of Phenol

- Phenol reacts with chlorine or bromine water to give precipitate
of the 2,4,6-trihalogen derivative.

This method is used for the quantitative estimation of phenols

OH OH

Br Br
Br2/H2O

no water Br2,4,6-tribromophenol
- Halogenation in anhydrous medium at low temperature -
gives monohalogenated phenol- OH OH

Br2/CS2
OoC

Br
 - Iodophenols are prepared by indirect methods.
I I I I

Reduction Na NO2
H2SO4/OoC

Iodobenzene _
NO2 NH2 OH N = N HSO
_ 4
+

H2O

- The o- isomers may be prepared by first blocking-

the p- position and one o- position by sulphonation. - I
OH OH OH
HSO3 Br HSO3
H2SO4
Br2/H+ desulphonate

SO3H SO3H
OH

Br

o-bromophenol
 OH
(2) Sulphonation HSO3
o
OH 20 C
(RT)

+ H2SO4 OH heat

110oC

SO3H
thermodynamically
stable
The m- isomer can be prepared by controlled fusion-
of m- benzenedisulphonic acid with KOH. -
SO3H SO3H SO3H

KOH/fusion
Acidify
SO3H OH

m-benzenedisulphonic m-hydroxy benzene

acid sulphonic acid
(3) Coupling : (p- Diazocoupling)

_ _
O O O

+
+ Ar - N = N
_
H
N = N - Ar
p-hydroxyazobenzene
(4) Nitration of Phenol : dil HNO3/R.T.
OH OH

20%
25oC
+ dil. HNO3
R.T.

NO2
Mechanism

- The mechanism of this reaction differs from that of ordinary nitration

because the nitrating agent in case of phenol is nitrosonium ion,
and not the nitronium ion. NO2

- Phenols are first nitrosated and the nitroso-phenols produced are -

then rapidly oxidized to the corresponding nitro compounds. -

- Nitrous acid (HNO2) that is present initially in the mixture is produced

through the reduction of some nitric acid by phenol.
H+ + _
HNO2 + 2HNO3 NO + H3O + 2NO3
Nitrosonium ion
H
 Nitrosonium ion can not nitrate the unactivated ring, such as benzene ring,
but can nitrate the activated one as phenol, since nitrosonium ion is a weaker
electrophile than the nitronium ion.

Mechanism
H+H+ H ++
H +
_ _ _ _
HNO
HNO + 2HNO
HNO
3 2 ++ 2HNO NO + H O +
3 3 NO + 3H3ONO
2NO +3 +H33H
+NO2NO O3O+ +2NO
2NO
2
2 + 2HNO
HNO
3 2 2HNO 3 3

H HH
.. .. +.. H ++ +
H H..+ HH + + +
H O-N=O H
H O - N = O HH OO- -NN==OO -N=O - N-HN
=2O + NO H2H O O+ +NONO
H+O O - N = O H HO
++O O
H
= O
2 O + NO 2
+ Nitrosonium ionNitrosonium ionion
..
Nitrosonium
Nitrosonium ion
..
OH
OH +O +O+O OH OHOH OH OHOH
+O OH OH
+
- H++ + -H
- H+ HNO 3 HNOHNO3
+ - H+ HNO 3
+ ++ oxidation 3 oxidation
oxidation
+ +
NO oxidation
NO NO
NO H NO H
H
NO
NO
H NO NO NO NO2 NO2
NO NO2
NO p-nitrosophenol NO p-nitrophenol
p-nitrophenol
p-nitrosophenol p-nitrosophenol 2
p-nitrophenol
p-nitrosophenol p-nitrophenol
o- Nitrophenols are also produced in this reaction in smaller
amounts than the p- isomers, and they are usually separated from each other
by steam distillation where o- isomer, will be more volatile than
the corresponding p- isomer.

The increased volatility of the o- isomers is due to intramolecular-

hydrogen bonding (chelation) which causes them to behave as monomers, -
whereas in the p- isomers intermolecular hydrogen bonding (association) -
results in their steam involatility.-

H _
_ _
O O
O H O H
+ +
N N O N O
+ O
O O
(Association)
(Chelation)
More volatile
 (5) Nitrosation

Treatment of phenol with nitrous acid produces mainly p-nitrosophenol. -

This compound is proved to be tautomeric with p-benzoquinone monoxime -

OH O-H O

HNO2

N=O N - OH

p-nitrosophenol p-benzoquinone
monoxime
Liebermann's Nitroso Reaction :
-This is used as test for phenols.
- If nitrosation is carried out in the presence of conc. H2SO4,
the p-nitrosophenol formed condenses with a molecule of phenol to give
indophenol acid sulphate.
On dilution with water, indophenol (red) is liberated which forms blue
sodium salt on addition of excess sodium hydroxide.
..
OH OH

H2SO4
- H2O HSO4-

+
N=O .. OH
OH N

indophenol acid sulphate

H2O
_ +
O Na+ O-H

NaOH

N O N OH

sod. salt of indophenol (blue) indophenol (Red)

(6) Kolbe-Schmidt Reaction
OH

_ COO- Na+
o
O Na+ 120-150 C
sodium salicylate

CO2 OH
pr

240-300oC thermodynamically
stable
Mechanism _
COO Na+
_
O Na+
O OH
_
O H COO
C _
COO
O
(7) Reimer-Tiemann reaction : (CHCl3/NaOH)

Phenols react with chloroform in the presence of strong bases

to gives o-phenolic aldehydes in addition to small amounts
of the corresponding p-isomers.

_ _
O Na + O Na+ OH

CHO CHO
NaOH H+
+ CHCl3
H2O
Salicyladehyde
Salicylaldehyde
Mechanism

Involves the formation of the electron-deficient dichlorocarbene intermediate

by the partial hydrolysis of chloroform in alkaline medium.

Cl Cl
H C Cl :C + NaCl + H2O
Cl Cl
_
OH Dichlorocarbene
electro defficient center
_
_
O O O
H
CHCl2
..
CCl2 CCl
_ 2

_
OH O _
OH
CHO CHO
H+
(8) Gattermann reaction : (HCN/HCl/AlCl3)

__ HH- -CC==NH
NH
HCl ++ HH- -CC == NN
HCl
Cl
Cl
.... Imidoformylchloride
Imidoformyl chloride
OH
OH
OH
++OH OH
++OH

Cl
Cl
++ CH
CH == NH - -Cl
Cl
..NH
..

__
HH CH- -NN- -HH
CH HH CH==NH
CH NH
Cl
Cl AlCl33
AlCl
OH
OH OH
OH
- -HH++

NH33 ++
NH HH22OO
HH++

CHO
CHO CH==NH
CH NH
(9) Lederer-Manasse reaction (p-Hydroxy methylation of Phenol)

OH OH

H+ or OH-
+ HCHO
(6 days)

CH2OH
p-hydroxybenzyl alc.
 Mechanism

In alkaline medium
_ _
O O O OH

+ CH2 = O H+

_
H CH2O
CH2OH CH2OH
In acidic medium
+ +
+ CH2 = OH CH2 - OH
CH2 = O + H

: OH + OH
OH

+ - H+
+ CH2 - OH

H CH2OH CH2OH
(10) Mannich reaction : (Aminomethylation)
-Phenols, react with formaldehyde and a secondary amine
in slightly acid mediumto give the corresponding
dialkylaminomethyl derivative.
_
O
..
H2C = O + R2NH +
H2 C NR2
H+

H
OH
+ .. - H2O +
+
CH2 - NR2 H2C = NR2 H2C NR2

H
: OH
OH

R R2N H2C CH2 NR

+
+ H2CN

R
CH2

NR
 (11) Chloromethylation (HCHO/HCl.)
OH OH
OH
CH2Cl

HCHO/HCl +

ZnCl2
CH2Cl
H

H O-H
H
H H OH +
-H2O C - Cl
C=O C H+ C
+ HCl +
H Cl H
H H Cl
This reaction is vigorous that usually polymers are obtained to obtain
.the monochloromethylated product we have to decrease the electron-donating
power of the OH group by blocking it with AlCl3 or adding an electron-withdrawing group.
OH OH

CH2Cl
HCHO/HCl

NO2 NO2
2-hydroxy-5-nitrobenzyl
chloride
 acylation :
OH
(12) Oxidation of Phenols is the process of adding an
acyl group to a compound
K2S2O8/OH- Hydroquinone
(Quinol)
OH K. persulphate
OH
+
KMnO4/H
Ring Rupture
O

CrO3 or
Benzoquinone
air oxidation

For the oxidation of the phenolic derivatives, the hydroxyl group is protected-
by acylation or tosylation.-

CH3 CH3
COOH COOH

+ C6H5 - SO2Cl OH KMnO4 HOH

benzene sulphonyl
chloride
OH
tosyl OSO2 - C6H5 OSO2 - C6H5
OH
(13) Reduction of Phenols

- Distillation of phenol with zinc dust converts in into benzene.

OH H

Zn dust
distillation

- Catalytical hydrogenation to give the corresponding cyclohexanols.

OH OH

Ni/H2
160oC
 Quinones
O

O
o-benzoquinone p-benzoquinone
usually red in colour usually yellow
(they are chromophores)

an atom or group whose presence is

responsible for the colour of a compound.
 O
p-Benzoquinone O

Preparation
(1) p-Benzoquinone is repared by the oxidation of hydroquinone O
with ferric chloride,MnO2/H2SO4 or by dichromate;
O
the best oxidizing agent is sod. chlorate/H2SO4o-benzoquinone
and vanadium pentoxide p-benzoquinone
OH
as catalyst. OH usually red in colour O
(they are chromophores)
usually yellow

K2S2O8/OH- NaClO3/H2SO4
V2O5

OH O
(2) In laboratory from Aniline, p-diaminobenzene, p-aminohydroxy compounds
by oxidation using dichromate in sulphuric acid.

NH2 N-OH O O OH

[o] [o]
[o] [o]

NH2 N-OH O N-OH NH2

1,4-Diaminobenzene Dioxime p-Benzoquinone P-benzoquinone p-Aminophenol
monoxime
 Reactions of p-benzoquinones :
1) Addition reactions :
(1) With HCl :(1,4-addition reaction)
O
O OH OH

HNO3
+ H+Cl- H
Cl
Cl Cl
O
O O
OH
Chloroquinol
Chloro-p-benzoquinone

-By repeating the process of adding HCl and then oxidation

the final product obtained is tetrachloro-p-benzoquinone
(chloranil) which is used as a fungicide
and as an oxidizing agent.
O O O

Cl Cl Cl
1) HCl 1) HCl
2)HNO3 2)HNO3
Cl Cl Cl Cl

O O O
2,5-Dichloro-1,4-benzoquinone Chloranil
(2) With primary or secondary amines : (1,4-addition )
O OH

O O

+ C6H5 NH
.. 2
(oxidation)
NHC6H5

O OH
O OH

C6H5HN
C6H5NH2 O

NHC6H5 NHC6H5

O OH
O

C6H5HN
O
[o]

NHC6H5

O
Final product (2,5-dianilino-p-benzoquinone)
(3) Acetylation of quinone : (Thiele acetylation)

O OH OH

ACETIC ANHYDRIDE
H+ H
+ Ac2O
1,4-addition
OCOCH3 OCOCH3

O OCOCH3 O OH

Ac2O
hydroxyquinol triacetate
OCOCH3

OCOCH3
II] Reduction of p-benzoquinone
O
OH

H2SO3
Sulphurous acid

O
OH

Reduction of p-benzoquinone to hydroquinone involves the formation

of a colored intermediate known as Quinhydrone. This intermediate
is believed to be a charge-transfer complex formed from the quinone
(acting as electron acceptor) and hydroquinone (electron donor) and
is stabilized by hydrogen bonding.

O H O

poor with acid electron rich with electron

(electron acceptor) (electron donor)

O H O
p-Benzoquinone is so easily reduced that it is used as an oxidizing agent -
specially in reactions where inorganic oxidizing agents are not required.-

The presence of electron-withdrawing substituents to increase the oxidizing -

power of the quinone, thus chloranil is more efficient oxidizing agent than-
p-benzoquinone itself-

Cl Cl

Cl Cl

O
Chloranil
 Polyhydric phenols
OH OH OH

OH

OH

OH
Catechol Resorcinol Quinol or hydroquinone
1,2-Dihydroxybenzene 1,3-Dihydroxybenzene 1,4-Dihydroxybenzene

OH OH OH

HO OH OH

HO OH

OH
Phloroglucinol Pyrogallol Hydroxyquinol
1,3,5- 1,2,3-Trihydroxybenzene 1,2,4-Trihydroxybenzene
Trihydroxybenzene
1) Preparation of catechol : by the action of alkaline
hydrogen peroxide on salicylaldehyde.
CHO _
O Na+
NaOH
+ H2O2 + HCOO Na
OH _
O Na+
Mechanism
_
CH = O CH - O

- O - OH O - OH
_ _
O O
CHO
_
O CH - O
H2O
O+
_ _
O O
_
O
_
+ HCOO
_
O
2)Preparation of resorcinol

• Resorcinol is prepared by fusion of benzene m-

disulphonic acid with alkalis.
SO3H OH


+ KOH
SO3H OH
3) Preparation of hydroquinone : (quinol)

O
OH OH

Fe / H2O K2S2O8/KOH
or H2SO3/H2O
sulphurous acid
O
OH
(4) Preparation of Phloroglucinol

By fusion of resorcinol with NaOH. •

OH OH

fusion
+ NaOH
OH HO OH
(5) Preparation of pyrogallol

OH OH

HO OH HO OH


with a steam of CO2

COOH
Gallic acid
 Chemical reactions

• Polyhydric phenols are more easily oxidized than the

monohydric phenols especially when the hydroxyl
groups are ortho or para to each other, for example
catechol and hydroquinone are readily oxidized, even by
air, to o- & p- benzoquinones respectively.

OH O

Na2Cr2O7 / H+
p-Benzoquinone

OH O
• In polyhydric phenols, the aromatic ring is very much
activated towards electrophilic substitution especially
when the hydroxyl groups are meta to each other,
because in these cases their activating effects will
reinforce each other.
HO OH

OH
 Houben-Hoesch Reaction
(Modified Gattermann's reaction)

R O
C

HO OH HO OH
_
RC = N/ZnCl2/HCl

OH OH
PhloroglucinolPhoroglucinol
OH OH

CH3CN / ZnCl2 / HCl

OH OH
Resorcinol C
O CH3

2,4-Dihydroxyacetophenone
Mechanism
_ _
+
R C = N + HCl R C=N - H

Cl R
_
HO OH C N-H
R Cl
ZnCl2 HO OH
C N-H

Cl
OH

R R OH

C O C NH

HO OH HO OH

H2O
H+

OH OH
• Phloroglucinol reacts with certain reagents as if it is
triketocyclohexane, it has been suggested that
phloroglucinol exists in two tautomeric forms. (comment)

OH O N - OH

NH2OH

HO OH O O HO - N N - OH

Phloroglucinol
Triketocyclohexane Phloroglucinol
1,3,5- trioxime
Cyclohexanetrione
 Naturally occurring Phenols
OH OH CH3
OCH3 CH

CH3

H3C

CHO
Vanillin Thymol
Oil of vanilla podes Oil of thyme and mint
‫زعتر‬
OCH3 OCH3 OH

OCH3 OCH3

/alc.KOH

CH = CH - CH3 CH2CH = CH2 CH = CH - CH3

Anethole Eugenol Isoeugenol

Oil of anise ‫يانسون‬ Oil of cloves ‫قرنفل‬ Oil of nutmeg ‫جوزة الطيب‬
seeds
 - Important derivatives of catechol :
Guaiacol
OCH3
•
OH

• It can be prepared from o-anisidine

OCH3 OCH3

NH2 OH
(1) Na/NO2/H2SO4
(2) H2O/Boil

o- anisidine guaiacol
 Industrial uses of Phenols

• The food preservative BHT & BHA

OH
H3C CH3
C C
H3C CH3
BHT
H3C CH3
(butylated hydrxytoluene)

CH3 OH
CH3
C
CH3
CH3
BHA
(butylated hydroxyanisole)
OCH3
Preparation

OH OH

(H3C)3C C(CH3)3

H+
+ (CH3)2 - C = CH2
2-Methylpropene
Isoprene
CH3 CH3
p-Methylphenol BHT
(p-cresol)

OH OH
OH

C(CH3)3
H+ +
+ (CH3)2 - C = CH2
2-Methylpropene C(CH3)3

OCH3 OCH3
BHA OCH3
p-Methoxyphenol