Aromatic 

Aldehydes and Ketones

Aromatic aldehydes are aromatic compounds that contain
a CHO (formyl) group. The simplest of aromatic aldehydes
is benzaldehyde, C6H5CHO.
CHO CHO
CH3

benzaldehyde o-tolualdehyde

O
C CH2CH=O
H H

formaldehyde phenylacetaldehyde
Aromatic Aldehydes and Ketones
All aromatic ketones have at least one aryl or phenyl
groups attached to the carbonyl C.
O O
C C
H3C

benzophenone acetophenone
 Methods of preparation of aromatic aldehyde 

Rosenmund reduction: The Rosenmund reduction is a

chemical reaction that reduces benzoyl chloride to
benzaldehyde using hydrogen gas over palladium with barium
sulfate.
The reaction was named after Karl Wilhelm Rosenmund.
 Methods of preparation of aromatic aldehyde

By oxidation of benzyl alcohol: This involves the treatment of

benzyl alcohol with dil. HNO3 or acidic potassium dichromate or
chromic anhydride in acetic anhydride or with copper catalyst at
350o C.
This process is used for commercial production of benzaldehyde.
 Methods of preparation of aromatic aldehyde

Etard’s reaction: Toluene is treated with chromium dichloride dioxide

(chromyl chloride) in carbon tetrachloride solution and the complex,
which is precipitated, is decomposed with water to benzaldehyde.

Gattermann-koch aldehyde synthesis: Benzene is converted into

benzaldehyde by passing a mixture of carbon monoxide and HCl gas
under high pressure into the ether solution of benzene in presence of
anhydrous aluminium chloride and cuprous chloride.
Methods of preparation of aromatic ketone

Friedel-Crafts Acylation: This electrophilic aromatic

substitution allows the synthesis of monoacylated products
in presence of Lewis acid as catalyst from the reaction
between arenes and acyl chlorides or anhydrides. The
products are deactivated, and do not undergo a second
substitution.
Methods of preparation of aromatic ketone
Friedel-Crafts Acylation: Acetophenone (methyl phenyl
ketone) may be prepared from the reaction of benzene
with ethanoyl chlorides in presence of AlCl3 catalyst.
AlCl3
C6H6 + CH3COCl C6H5COCH3 + HCl

Benzophenone (diphenyl ketone) may be prepared by

Friedel-Craft condensation between benzoyl chloride and
benzene.
AlCl3
C6H6 + C6H5COCl C6H5COC6H5 + HCl
Mechanism
Mechanism for for
Friedel-Crafts acylation
Friedel-Crafts EAS
Acylation
Step 1: The acyl
O halide reacts with the
C + AlCl3 RC=O + AlCl4 Lewis acid to form a
R Cl more electrophilic C,
an acylium ion.
O Step 2: The p electrons of the
RDS CR aromatic C=C act as a
+ RC=O nucleophile, attacking the
H electrophilic C+. This step
destroys the aromaticity giving
the cyclohexadienyl cation
O O intermediate.
CR C R + HCl + AlCl3
+ AlCl4
H
Step 3: Removal of the proton from the sp3 C bearing the acyl- group reforms the
C=C and the aromatic system, generating HCl and regenerating the active catalyst.

The addition of the electrophile is the rate determining step (RDS), the reactivities of the
arenes are in the order: Toluene > Benzene > Nitrobenzene
 Reactions of Aldehydes and Ketones

Cannizaro Reaction: The adduct of an aldehyde

and OH (KOH) can transfer hydride ion to another
aldehyde -CHO resulting in a simultaneous
oxidation and reduction (disproportionation)
2 C6H5CHO + KOH → C6H5CH2OH + C6H5COOK
 Reactions of Aldehydes and Ketones

Clemmensen reduction: Acetophenone can be reduced to

ethylbenzene by heating the ketone with amalgamated zinc
(a mixture of zinc and mercury) and concentrated
hydrochloric acid for a long time.
 Reactions of Aldehydes and Ketones
Oxidation of acetophenone: Oxidation with cold
potassium permanganate gives phenylglyoxylic acid
(benzoylformic acid) which, on firther oxidation, is
converted into benzoic acid.

[O] [O]
C6H5COCH3 → C6H5COCOOH → C6H5COOH
 Test of Aldehydes and Ketones
The common laboratory test for aldehydes is the Tollens’ test or Tollens’
silver mirror test.
When exposed to the Tollens’ reagent, a basic solution of
ammoniacal silver, Ag(NH3)2+, an aldehyde undergoes oxidation.
The silver ion (Ag) is reduced to silver metal (Ag) as the
aldehyde is oxidized to a carboxylic acid anion. Silver metal
precipitates from solution and coats the flask, producing a
smooth silver mirror.
Ketones cannot be oxidized to carboxylic acids and do not
react with the Tollens’ reagent.
 Phenols
 Phenol, also known as carbolic acid, is an aromatic
organic compound with the formula C6H5OH.
 It is a white crystalline solid that is volatile.
 The molecule consists of a phenyl group (C6H5‒)
bonded to a hydroxyl group (‒OH).
 Phenol is derived from the old name for benzene
(phene), to include the suffix that indicates it possesses
a hydroxyl group (‒ol). 

OH
 Physical Properties of Phenols

 The OH group of phenols allows hydrogen

bonding to other phenol molecules and to
water.
 Compared to compounds of similar size and
molecular weight, hydrogen bonding in
phenol raises its melting point, boiling point,
and solubility in water.
Hydrogen Bonding of Phenols

O H O
Hydrogen Bonding with Water
 Acidity of Phenols
Most characteristic property of phenols is their
acidity.
Phenols are more acidic than alcohols but less
acidic than Carboxylic acids.
To explain why, let’s compare the
ionization of Ethanol and Phenols
Acidity of Phenols
 Acidity of Phenols
Phenol is a very weak acid. Phenol can lose a hydrogen ion
because the phenoxide ion formed is stabilized to some extent. The
negative charge on the oxygen atom is delocalized around the ring.
The more stable the ion is, the more likely it is to form. One of the
lone pairs on the oxygen atom overlaps with the delocalized
electrons on the benzene ring.
This overlap leads to a delocalization which extends from the ring
out over the oxygen atom. As a result, the negative charge is no
longer entirely localized on the oxygen, but is spread out around the
whole ion.
Spreading the charge around makes the ion more stable than it
would be if all the charge remained on the oxygen. However,
oxygen is the most electronegative element in the ion and the
delocalized electrons will be drawn towards it. That means that
there will still be a lot of charge around the oxygen which will tend to
attract the hydrogen ion back again. That is why phenol is only a
very weak acid.
 Sources & Uses of Phenols
 Phenols was first isolated from coal tar.

 Phenol is an important industrial chemical.

 Major use is in phenolic resins for adhesives

and plastics.
Preparation of Phenols
 Reactions of Phenols
A hydroxyl group is very powerful activating
substituent, and electrophilic aromatic substitution in
phenol occurs far faster, and under milder condition,
than in benzene.
Halogenation
 Acylation of Phenols
Phenols are examples of bidentate nucleophiles, meaning that they can react
at two positions:
on the aromatic ring giving an aryl ketone via C-acylation, a Friedel-Crafts
reaction with acyl chloride or anhydride and AlCl3 or,
on the phenolic oxygen giving an ester via O-acylation, an esterification
with acyl chloride or anhydride.
 Preparation of Salicylic Acid
Heating phenol with alkali and carbon dioxide under high
pressure (100 atm) / temperature (125˚C) results in
regioselective ortho-substitution. This process is also known
as the Kolbe-Schmitt synthesis. o-hydroxybenzoic acid is
more commonly known as salicyclic acid.
 Aspirin Synthesis
Aspirin (acetylsalicylic acid) can be synthesized from the
reaction of salicylic acid and acetic anhydride in presence
of a catalyst, sulfuric acid (H2SO4).
 Uses of Aspirin
Aspirin often used to treat pain, fever, & inflammation.
 

Aspirin is also used long-term, at low doses, to help

prevent heart attacks, strokes, and blood clot formation in
people at high risk of developing blood clots. 
Low doses of aspirin may be given immediately after a
heart attack to reduce the risk of another heart attack or of
the death of heart tissue. 
Aspirin may be effective at preventing certain types of
cancer, particularly colorectal cancer.
 Aromatic amines
 Organic compounds that contain nitrogen and are
basic (alkaline) are called amines.
 Aromatic amines are derivatives of ammonia, NH3
contain N attached to one or more aromatic groups.
NH2 NH2 NH2 NH2
CH3

CH3
CH3
aniline o-toluidine m-toluidine
p-toluidine

H3C CH3
N
H
N

N,N-dimethylaniline diphenylamine
 Preparation of Amines
Reduction of Nitrobenzene: Industrial aniline production
involves two steps.
First, benzene is nitrated with a concentrated mixture of
nitric acid and sulfuric acid at 50 to 60 °C to yield
nitrobenzene.
The nitrobenzene is then hydrogenated (typically at 200–
300 °C) in the presence of metal. 
CH3 CH3
HNO3,H2SO4
+ ortho-

NO2

H2,Ni

CH3

NH2

p-toluidine
 Preparation of Amines

Ammonolysis of chlorobenzene: The reaction of ammonia

with chlorobenzene under reduced pressure and at high
temperature in presence of copper salts (catalyst) forms
aniline.
 Preparation of Amines

Reduction of nitriles: Benzyl bromide produce benzyl

cyanide with sodium cyanide. β-phenethylamine (1-amino-
2-phenylethane) can be synthesized by reduction
of benzyl cyanide with hydrogen in liquid ammonia, in the
presence of a Raney-Nickel catalyst, at a temperature of
130 °C and a pressure of 13.8 Mpa

NaCN 2 H2, Ni
CH2Br CH2C N CH2CH2NH2

benzyl bromide 1-amino-2-phenylethane

 Chemical Properties of Amines
Amines resemble ammonia in their reactions. Amines are
bases, and like ammonia, produce OH- ions in water.

34
 Chemical Properties of Amines
Diazotization: The nitrosation of aniline with nitrous acid
(generated in situ from sodium nitrite and a strong acid, such
as hydrochloric acid, sulfuric acid, or HBF4) leads to diazonium
salts. In aqueous solution diazonium salts are unstable at
temperatures above +5 °C; the -N+≡N group tends to be lost as
N2 (nitrogen gas).

Diazonium salts are important intermediates for the

preparation of azo compounds. 
 Chemical Properties of Amines
Azo compound: Liquid aniline is added to a cold solution of
benzene diazonium chloride, and the mixture is shaken
vigorously. A yellow solid is produced. These strongly
coloured azo compounds are frequently used as dyes known
as azo dyes. The one made from aniline is known as "aniline
yellow". Azo compounds account for more than half of modern
dyes.
 Methyl orange indicator: an azo dye
The IUPAC name of methyl orange is
sodium 4-[(4-dimethylamino)phenylazo]benzenesulfonate.
This is an azo dye exists in two forms depending on the pH. 

pH-related color changes result from changes in the way

electrons are confined in a molecule when hydrogen ions are
attached or detached.
 Methyl orange indicator: an azo dye
When methyl orange is added in acidic solution, a hydrogen
ion attaches and the molecule absorbs blue-green light, which
makes its solution appear red. Methyl orange is red in acidic
solutions (in fact solutions of pH less than 3.1).

Methyl orange in acidic solution

 Methyl orange indicator: an azo dye
If an alkali is added a hydrogen ion is removed, then the
yellow form if generated. Methyl orange is yellow at pH
greater than 4.4.
In between pH 3.1 and 4.4, at some point there will be equal
amounts of the red and yellow forms and so methyl orange
looks orange.

Methyl orange in basic solution

Methyl orange indicator: an azo dye
 Methyl orange indicator: an azo dye
Methyl orange (Sodium 4-[(4-dimethylamino)phenylazo]benzenesulfonate) is
an azo dye which exists in two forms depending on the pH. pH-related color
changes result from changes in the way electrons are confined in a molecule
when hydrogen ions are attached or detached.
When methyl orange is added in acidic solution, a hydrogen ion attaches
and the molecule absorbs blue-green light, which makes its solution appear
red. Methyl orange is red in acidic solutions (in fact solutions of pH less than
3.1). If an alkali is added a hydrogen ion is removed, then the yellow form if
generated. Methyl orange is yellow at pH greater than 4.4.
In between pH 3.1 and 4.4, at some point there will be equal amounts of the
red and yellow forms and so methyl orange looks orange.
Methyl orange in acidic solution

Methyl orange in basic solution