Assistant Lecturer:

Sahar Mohammed Shakir

Assistant Lecturer:
Sarah Sattar Jabbar
Structure
Aldehydes are cpd.s of the general formula RCHO ;
Ketones are cpd.s of the general formula RŔCO.
The groups R and Ŕ may be aliphatic or aromatic,
and in one aldehyde, formaldehyde, R is hydrogen.

H H R'
C O C O C O
H R R
Formaldehyde Aldehyde Ketone

Both aldehydes and ketones contain the carbonyl

group, ( C=O ) , and are often referred to collectively
as carbonyl compounds. It is this carbonyl group
that largely determines the chief chemical and
physical properties of aldehydes and ketones.
 O
O O
C
C C H
H H H3C H
Formaldehyde Acetaldehyde Benzaldehyde

O O

O C C
H CH3
C
H3C CH3
OH
Acetone Salicylaldehyde Acetophenone

O C

C
C CH3
H2
Benzyl methyl ketone Benzophenone
● Aldehydes & ketones differ from alcohols in having
two less hydrogen atoms.
● Removal of these two hydrogens from a primary
alcohol as a result of oxidation yields an aldehyde;
where as their removal from a secondary alcohol gives
a ketone.
● The relation between these carbonyl compounds
and alcohols is , therefore , oxidation - reduction
relation.
● Tertiary alcohols can’t undergo this reaction .
Physical properties
● All aldehydes and ketones are liquids except
formaldehyde , which is gas and benzophenone ,
which is solid .
Formaldehyde, b.p. -21 oC , is handled either as an
aqueous solution ( formalin , an aqueous solution of
40% formaldehyde and 15% methanol ) or as one of
it’s solid polymers: paraformaldehyde ( CH2O )n , or
trioxane ( CH2O )3 .

O
H2C CH2
CH2OCH2OCH2O O O
Paraformaldehyde C
H2
Trioxane
● They are colorless except benzaldehyde, which has
a pale yellow color ( due to oxidation ) with a
characteristic odor .
● Aliphatic aldehydes and ketones burn with a blue
flame ( without smoke ) , while aromatic ones burn
with a yellow smoky flame .
● The polar carbonyl group makes aldehydes &
ketones polar cpd.s, & hence they have higher
boiling points than non-polar cpd.s of comparable
molecular weight.
The polarization of carbonyl group can be
represented by various ways,

δ+ δ-
C O or C O
● By themselves, they are not capable of
intermolecular hydrogen bonding since they contain
hydrogen bonded only to carbon; as a result they
have lower boiling points than comparable alcohols
or carboxylic acids.
For example , isopropyl alcohol boils at 82.5˚C while its
oxidation product, acetone, boils at 56˚C.
Another example is ethanol which boils at 78˚C while its
oxidation product, acetaldehyde, boils at 21˚C.

OH
O OH O
H 3C C CH3 C H3C C H C
H 3C CH3 H3C H
H
H
Isopropyl alcohol Acetone Acetaldehyde
Ethyl alcohol
B.p. 82.5 °C B.p. 56 °C B.p. 21 °C
B.p. 78 °C
● The lower aldehydes and ketones are appreciably
soluble in water, presu -
mably because of H -
bonding between solute
and solvent molecules ;
borderline solubility is
reached at about 5 carbons.
Aromatic aldehydes & ketones are insoluble in water
& all of them are soluble in the usual organic solvents

Solubility classification
Aldehydes and ketones that are soluble in water are
soluble in ether too and are classified under class S1
(e.g., formaldehyde and acetone).
Aldehydes and ketones that are insoluble in water are
classified under class N such as benzaldehyde and
benzophenone.
Chemical properties
1- All reactions of aldehydes & ketones are related
to the carbonyl group ( the active group ) .
2- Aldehydes contain a hydrogen atom attached to
it’s carbonyl while ketones don’t, this difference in
the chemical structure affects their chemical
properties in two ways :
a) Aldehydes are easily oxidized to the corresponding
acids and have reducing properties while ketones are
not oxidized under similar conditions & do not show
reducing properties.
b) Aldehydes are usually more reactive than ketones
towards nucleophilic addition , the characteristic
reaction of carbonyl group .
R H

C O H-Y R C OH
H
Y
3- Both aldehydes & ketones are neutral cpd.s that
don’t change the color of litmus paper.

Identification of aldehydes & ketones

1- General test:
2,4-Dinitrophenylhydrazine reagent: reagent)
Both aldehydes and ketones give yellow or orange
precipitate with 2,4-dinitrophenylhydrazine reagent.

NO2 NO2

  
R R
O2N NHNH2 + C O O2N N N C + H2O
R' H R'

2,4-dinitrophenylhydrazine 2,4-dinitrophenylhydrazone
(imine)
yellow-orange ppt.

* An imine is a functional group or chemical cpd.

containing a carbon–nitrogen double bond .
 Procedure:
● To 2 drops of the cpd. add 3 drops of the reagent,
a yellow or orange precipitate will be formed.
● If the cpd. is insoluble in water, dissolve it in 1 mL
of methanol & then add the reagent.

2- Differentiation between aldehydes and ketones:

Differentiation between aldehydes and ketones is
achieved by taking the advantage of the fact that
aldehydes can be easily oxidized while ketones can
not ( they need stronger oxidizing agents ).
Two reagents can be used for this purpose, Tollen’s
reagent or Fehling’s reagent.
Only aldehydes give positive results with these two
reagents.
a- Tollen's test:
( Reduction of ammoniacal silver nitrate )

● Tollen’s reagent is the combination of silver

nitrate solution with ammonium hydroxide in the
presence of sodium hydroxide solution .

● Aldehydes show positive result with this reagent

because the reaction between them involves the
oxidation of the aldehyde to the corresponding
carboxylic acid with an accompanying reduction of
the silver ions from this reagent to silver element in
the form of silver mirror on the inner side of the
test tube.
 2 AgNO3 + 2 NaOH Ag2O + 2 NaNO3 + H2O
Silver nitrate Silver oxide
Brown ppt.

Ag2O + 4 NH4OH 2 Ag(NH3)2OH + 3 H2O

H O
C O + 2 Ag(NH3)2OH C O + 2 Ag° + 4 NH3 + H2O
R R
Aldehyde Carboxylic Silver
acid salt mirror

The oxidation process requires an alkaline medium; therefore

sodium hydroxide solution is used , and in order to overcome
the formation of the brown silver oxide precipitate ( Ag2O),
ammonium hydroxide is used to serve as a complexing agent
for this precipitate making it a water soluble complex.
Note that since the medium is alkaline, salts of the produced
carboxylic acid are formed rather than the acid itself.
 Procedure :
● Preparation of Tollen’s reagent
To 3 mL of silver nitrate solution add 2-3 drops of
10% NaOH solution, & then add drop wise very dilute
ammonia solution with continuous shaking until all
the brown precipitate of silver oxide is dissolved.
This reagent should be freshly prepared prior before
use.
● Add 2-3 drops of the cpd. to 2-3 mL of Tollen’s
reagent, a silver mirror will be formed.
If no reaction occurs , warm the test tube in water
bath for few minutes ( note that excessive heating
will cause the appearance of a false positive test by
decomposition of the reagent).
● The formed silver mirror can be washed using
dilute nitric acid.
Notes:
* If the test tube is not very clean , silver metal
forms merely as a granular gray or black ppt. .
* False - negative tests are common with water
insoluble aldehydes .
* A negative result indicates that the compound
is a ketone .

b- Reduction of Fehling's reagent:

This test , like Tollen’s test , is used to distinguish
aldehydes from ketones.
Only aldehydes can reduce Fehling’s reagent ( a deep
blue solution) to give a red cuprous oxide precipitate.
 H O
2+ Heat
C O + NaOH + 2 Cu C O + Cu2O + H2O
R Copper II R
Copper I
Aldehyde deep blue solution carboxylic
oxide
( Fehling's reagent ) acid salt
( red ppt. )

Excess
Cu2O Cu°
aldehyde
Copper mirror

Procedure :
● Preparation of Fehling's reagent :
Fehling’s reagent is prepared by mixing exactly equal
volumes of Fehling’s A & Fehling’s B solution in a 1:1
ratio immediately before use (usually 1 mL of each).
 Fehling’s A solution is an aqueous solution of copper sulfate
pentahydrate (CuSO4.5H2O) with few drops of concentrated
sulfuric acid.
Fehling’s B solution is an aqueous solution of potassium sodium
tartrate (C4H4K NaO6.4H2O) and sodium hydroxide.

● Add 5 drops of the compound to 1 mL of Fehling’s

solution, and then heat in water bath for 5 minutes
(with shaking for water insoluble compounds).

● Aldehydes change the color of Fehling’s solution

from blue to green, orange precipitate, and then red
precipitate or copper mirror.
Ketones don’t change the color of this reagent.
On the other hand , this test does not give a sharp
result with aromatic aldehydes.
3- Special tests for aldehydes and ketones containing
a terminal methyl group:
O
These compounds include,
acetaldehyde, acetone, acetophenone, C CH3
and benzyl methyl ketone. All of them
have a methyl group attached to the carbonyl group.

a- Iodoform (Haloform) test:

Follow the same procedure of iodoform test
mentioned earlier (identification of alcohols).

b- Sodium nitroprusside test:

To few drops of the compound add 1 mL of sodium
nitroprusside ( Na2[Fe(CN)5NO].2H2O ) solution and
excess of 30% sodium hydroxide solution, a red color
complex is a positive test.
4- Polymerization reaction:
To 0.5 mL of formaldehyde or salicylaldehyde add
0.2 gm of resorcinol and drop-by-drop concentrated
sulfuric acid to get a red or reddish violet color , or a
white ring that changes to a reddish violet ring.
Acid catalysis reaction by protonating formaldehyde
and increasing the electron deficiency of the carbonyl
carbon.

So, the first stage can be viewed as both electrophilic

substitution on the ring by the electron – deficient
carbon of formaldehyde , and nucleophilic addition
of the aromatic ring to the carbonyl group.
5- Cannizzaro reaction:
In the presence of concentrated alkali, aldehydes
containing no - hydrogens undergo self oxidation –
reduction to yield a mixture of the corresponding
alcohol & a salt of the corresponding carboxylic acid.
This reaction is known as Cannizzaro reaction.
Therefore , one molecule of the aldehyde serves as the
oxidizing agent while the other serves as the
reducing agent.
Benzaldehyde , salicylaldehyde , and formaldehyde
can undergo Cannizzaro reaction because they do
not have an alpha hydrogen atom .
O H O
C C C
H OH O Na
NaOH
2 H
Heat
Benzaldehyde Benzyl alcohol Sodium benzoate
 Procedure:
● To few drops of benzaldehyde (or other aldehydes)
add 0.5 mL of 30% NaOH solution & heat gently on a
water bath with shaking for 5 minutes.
A precipitate of sodium benzoate is produced.
● Dissolve this precipitate by adding few drops of
distilled water, & then add drops of concentrated HCl
to liberate benzoic acid as a white precipitate.

Note :
As mentioned earlier, formaldehyde can undergo this
reaction; however, this reaction can't be relied on for
testing formaldehyde since the acid produced, formic
acid, is liquid that can't be observed separately as
compared to the solid benzoic acid resulted from
benzaldehyde.
1- Sketch the hydrogen bonding between benzaldehyde
and water.

2- Aldehydes and ketones have higher boiling points

than hydrocarbons , but have lower boiling points
than alcohols, explain why?

3- What is paraformaldehyde, and from which aldehyde

is formed? Write down it's molecular formula.

4- Aldehydes are usually more reactive than ketones

towards nucleophilic addition, explain why?
5- Write the imine product formed in the reaction
of each of the following :
a- Acetaldehyde and benzylamine, C6H5CH2NH2.
b- Benzaldehyde and butylamine, CH3CH2CH2CH2NH2.

6- Using chemical tests how would you distinguish

among 1-pentanol , 2-pentanone , 3-pentanone ,
and pentanal ?

7- Which of the following compounds give positive

Cannizzaro test ? Why ?
Benzaldehyde , Acetaldehyde , Salicylaldehyde .

8- Cannizzaro reaction can't be relied on for testing

formaldehyde, explain why and write the equation
of the reaction .
* Robert T. Morrison , Robert N. Boyd : “ Alcohols and
Ethers” . Organic Chemistry, (6th) edition, Prentice-Hall
Inc.
* Shriner R.L. , Hermann C.K.F. , Morrill T.C., Curtin D.Y.
and Fuson R.C. : “ Chemical tests for functional groups ” .
The Systemic Identification of Organic Compounds ,
(8th) edition, John Wiley and Sons Inc., New York. 2004;
247-350.
* Carey, Francis A.: “ Aldehydes and Ketones: Nucleophilic
Addition to the Carbonyl Group ” . Organic Chemistry ,
(6th) edition, McGraw-Hill companies, Inc.
* Azhar M. Jasim , Duraid H. Mohammad, A Laboratory
Manual on Practical Organic Chemistry for 2nd year
students, University of Baghdad , College of Pharmacy,
Department of Pharmaceutical Chemistry, 2012.