1. CHEMICAL PROPERTIES OF
ALDEHYDES AND KETONES
By:Takeen Khurshid
To: Dr. Geeta Durga

2. Aldehydes:
General formula:
RCHO or RCH=O
Ketones:
General formula:
RCOR’ (R and R’=alkyl or aryl)

3. Naming Of Aldehyde:
•Select the longest continuous carbon chain that contains the C=O group and replace
the ending by the suffix al.
•The CHO group is assigned the number 1 position and takes precedence over other
functional groups that may the present such as –OH, C=C.

4. Common name: listing the alkyl substituents attached to the carbonyl
group, followed by the word ketone.
IUPAC system: replace the ending –e by the suffix –one. The chain is
numbered in such a way as give the lowest number to the C=O group.
Common Dimethyl ketone Methyl phenyl ketone Methyl vinyl ketone Diphenyl ketone
Acetone Acetophenone Benzophenone
IUPAC Propanone Phenyl ethanone 3-Buten-2-one Diphenylmethanone
CH3 C CH3
O
CH3 C C6H5
O
CH3 C CH=CH2
O
H5C6 C
O
C6H5
Naming Of Ketone

5.  Because the polarity of the carbonyl group, aldehydes and ketones are
polar compounds.
 Dipole-dipole attractions, although important, are not as strong as
interactions due to hydrogen bonding. As a result, the boiling points of
aldehydes and ketones are higher than those of nonpolar alkanes, but
lower than those of alcohols.
 The lower aldehydes and ketones are soluble.
C O C
+
O
-
O
C O
C
δ
−
δ
−
δ
+
δ
+
C O H
O
H CO
δ
−
δ
+
δ
+
δ
−

6. C+δ
O-δ
H
H
C+δ
O-δ
H
R
C+δ
O-δ
R'
R
> >
Activity of the carbonyl group
C+δ
O-δNu-
C O-Nu
E+
C OENu

7. alkane alcohol
aldehyde
ketone
carboxylic acid
oxidation
reductionreduction
addition
productnucleophilic
addition
CHEMICAL
PROPERTIES:

8. Aldehydes & ketones, reactions:
1) Oxidation
2) Reduction
3) Addition of cyanide
4) Addition of derivatives of ammonia
5) Addition of alcohols
6) Condensation Reactions
7) Addition of Grignard reagents
8) (Alpha-halogenation of ketones)
9) Cannizzaro reaction

9. Aldehydes
and ketones
Alcohols
Lactones
and esters
Oximes
Amides
CyanohydrinsEnols and
enolate anions
Hydrazones
Alkenes
Alkanes
Ketals and thioketals Carboxyllic acids

10. 1..Hydrate Formation

11. 1- Reduction of carbonyl group
a- Addition of metal hydride
CH3
O
H
2 H2 / Pd
CH3
OH
CH3
OH
1) NaBH4
2) H2O
C O C O-M+H C OHH+ M+
H-
H2O
H+
H2O
H+
O
LiAlH4
OAl
H
OH

12. R C
O
H
R CH OH
R'
R C OH
R'
R''
R C R'
O
+ R'MgX
1) Dry ether
2) H2O
+ R''MgX
1) Dry ether
2) H2O
CH3 C
O
H
CH3 CH
OH
C2H5+ C2H5MgX
1) Dry ether
2) H2O
+ CH3MgX
1) Dry ether
2) H2O
O
CH3
OH
b- Addition of Grignard Reagents: Formation of alcohols

13. c- Clemmenson reduction
d- The Wolf-kishner reduction
O
COOH HCl / Zn(Hg) COOH
H
H
COOH
O
NH2NH2
COOH
N-NH2
COOH
NaOH
∆
H
H

14. e- Wittig reaction
C
O
+ CH2=P(C6H5)3
THF
C
O-
CH2
P(C6H5)3
C
O
CH2
P(C6H5)3
C CH2 + (C6H5)3P=O
H
O
+ (Ph)3P=CH C OC2H5
O
OC2H5
O

15. 2- Oxidation reaction
a-
b- Tollenis test
c- Iodoform reaction
R-CHO or Ar-CHO
KMnO4
or K2Cr2O7
RCOOH or ArCOOH
RCOO-
+ 2 Ag(NH3)+
2 + OH-
+ 2 Ag + 4 NH3 + 3 H2ORCHO
C O
CH3
R
+ 3 I2 + 4 NaOH R
O
O
-
Na
+ + CHI3 + 3 NaI
CH3
CH3
O
I2 / NaOH
CH3
COONa
+ CHI3

16. R C OH
R'
CN
R C R'
O
+ HCN
O
H
+ HCN
OH
CN
Cyanohydrin
Benzaldehyde cyanohydrin
O
+ HCN
OH
CN
H2 / Pt
or LiAlH4 and H3O
+
OH
NH2
H3O
+
Heat
OH
COOH
3- Addition of Hydrogen Cyanide: Formation of cynohydrins

17. R C
O
R
2
R C OH
R'O
R
2
+ R'OH
CH3 C
O
H
CH3 CH
OH
OC2H5
+ C2H5OH
H
+ R''OH
H
+ R C OR''
R'O
R
2
R
2
=H:
R
2
=Alkyl
Aldehyde
Ketone
Hemiacetal
Hemiketal
Acetal
Ketal
H
+
C2H5OH
H
+
CH3 CH
H5C2O
OC2H5
Hemiacetal Acetal
CH3 C
O
CH3
CH3 C
OH
OC2H5
CH3
+ C2H5OH
H
+
C2H5OH
H
+
CH3 C
H5C2O
OC2H5
CH3
Hemiketal Ketal
4- Addition of alcohols:

18. C O
NH3
C NH
Imine
NH2OH
Hydroxylamine
C N OH
C N NH2
C N NH
C N NH
O2N
NO2
C N NH C NH2
O
Oxime
NH2 NH2
Hydrazine
Hydrazone
NH2 NH
Phenylhydrazone
Phenylhydrazine
NH2 NH
O2N NO2
2,4
-
Dinitrophenylhydrazone
NH2 NH C NH2
O
Semicarbazide
Semicarbazone
6- Addition of Ammonia and Ammonia Derivatives

19. 7.ALDOL CONDENSATION
 Condensation between two molecules of an Aldehyde or a
ketone to form a β-hydroxyl aldehyde or a β-hydroxy ketone is
known as a ALDOL CONDENSATION.
 ALDOL CONDENSATION is possible only when the carbonyl
compound contains atleast one α-hydrogen atom.

20. MECHANISM
enolate
ion
An enolate ion is the anion formed when
an alpha hydrogen in the molecule of
an aldehyde or a ketone is removed as a
hydrogen ion.

21. The alkoxide ion is the conjugate
base of alcohols.

22. Alkoxide ion is protonated by water.

23. Crossed aldol condensation
In the presence of a strong base, two
different molecules of aldehyde or ketone
combine to form a β-hydroxyaldehyde or a
β-hydroxyketone.
This reaction is called as the aldol
condensation.

24. The enolate ion (carbanion) is the actual
nucleophilic reagent.
The reaction breaks down to the
following:
The α-carbon of the donor attaches itself to
the carbonyl carbon of the acceptor.

25. Step 1: Deprotonation and formation of
nucleophile.
• Step 2: Attack by nucleophile: Formation of alkoxide
ion.

26.  Step 3: Hydrolysis and formation of Aldol type product
Step 4: Intramolecular dehydration

27. 8- Cannizzaro reaction
Aldehyde which does not contain α hydrogen undergoes Cannizzaro
reaction.
CHO
+ NaOH (30 %)
∆
+
CH2OH
COO-
Na+
CH
+ OH-
C
O-
OH
O
H
C
C CH2O-
+
OH
O
O
H
C CH2OH
+
O-
O
more stable anion