Chapter 3.

Derivatives of hydrocarbons
Aldehydes and Ketones
Prepared by:

Arbanah Muhammad
arbanah@micet.unikl.edu.my

TOPICS COVERED
Aldehydes and Ketones
Structure and Properties
Sources
Reactions
Important of Aldehydes and Ketones

Introduction
o carbonyl compounds : compounds with
C
carbonyl group
O

o examples of carbonyl compounds :

O

O
R

aldehyde

R'

ketone

o general formula : CnH2nO

Carbonyl Group
Both aldehydes and ketones contain the
carbonyl group which has a double
bond between carbon and oxygen.
Remember, oxygen forms only two bonds, so
in the carbonyl group nothing else bonds to
the oxygen.

O
R

Carbonyl Containing Compound

Formula

Family
Aldehyde

Ketone

Carboxylic Acid

Formula

Family
Ester

Amide

Aldehydes and Ketones

Only differ by location of carbonyl

Aldehydes

Ketones

RCHO

RC(=O)R

Results in different properties and reactions

Structure
The functional group of an aldehyde is a
carbonyl group bonded to a hydrogen atom
in methanal, the simplest aldehyde, the carbonyl
group is bonded to two hydrogens
in other aldehydes, it is bonded to one hydrogen and
one carbon

The functional group of a ketone is a

carbonyl group bonded to two carbons

O
O
O
HCH
CH3 CH
CH3CCH3
Methanal
Ethanal
Propanone
(Formaldehyde) (Acetaldehyde) (Acetone)

Example

IUPAC nomenclature and common names for aldehyde and ketone compounds.
Compound

Structure formula

IUPAC

Common name

nomenclature
Aldehyde

Ketone

HCHO

Methanal

Formaldehyde

CH3CHO

Ethanal

Asetaldehyde

CH3CH2CHO

Propanal

Propionaldehyde

CH3CH2CH2CHO

Butanal

Butyraldehyde

CH3COCH3

Propanone

Acetone

CH3CH2COCH3

2-butanone

Methyl ethyl ketone

CH3CH2CH2COCH3

2-penthanone

npropyl methyl
ketone

CH3CH2COCH2CH3

3-penthanone
Diethyl ketone

Synthesis of Aldehydes and

ketones

Preparation of Aldehydes
Oxidation of primary
alcohol
Hydration of
alkynes
Ozonolysis of
alkenes
Hydrolysis of gem
halides

ALDEHYDES

i) Oxidation of 10 Alcohol
General equation :
H
R

PCC

OH

[O]

aldehyde

10 alcohol
Oxidation of primary alcohols to aldehyde using pyridium
chlorochromate (PCC) in anhydrous media such as
dichloromethane.

Example :

H
H 3C

C
H
ethanol

PCC

OH

[O]

H3 C

ethanal

ii) Hydration of Alkynes

General equation :
H2SO4

alkyne

R' + H2O

OH

enol
R'

HgSO4

tautomerism
O
R

CH2

C R'

aldehyde

ii) Hydration of Alkynes

Example :
H

H + H2 O

H2SO4
HgSO4

OH

enol
H

ethyne
tautomerism

ethanal

Keto- Enol Tautomerism

The name enol is derived from the IUPAC designation of it as both

an alkene (-en-) and alcohol (-ol).

Keto and enol forms are examples of tautomers, constitutional

isomers in equilibrium with each other that differ in the location of
hydrogen atom and a double relative to a heteroatom, most often
O, S, or N.

This type of isomerism is called tautomerism.

O
||
CH3-C-CH3
acetone
(keto form)

OH
|
CH3-C = CH2
acetone
(enol form)

iii) Ozonolysis of Alkenes

General equation :
R

R'

alkene

i) O3

ii) Zn/H3O+

O +

R'

aldehyde

Example 1 :
H3 C

CH2 CH3

2-pentene

i) O3
ii) Zn/
H3O+

H
H3 C

ethanal
O

H propanal
C

CH2 CH3

iii) Ozonolysis of Alkenes

Example 2 :
CH3

i) O3

ii) Zn/
H3O+

4-methylcyclopentene

O
C

CH2

CH

CH2

CH3
3-methylpentandial

iv) Hydrolysis of Gem Halides

To produce aromatic aldehyde
Example :
X

CH3
+ 2X2
Toulene

hv or

H
C

H2O

Gem halides

Benzaldehyde

iv) Hydrolysis of Gem Halides

Example :
Cl

CH3
+ 2Cl2
Br
4-bromotoulene

H
C

hv or

Gem halides

Cl

H2O

Br

Br
4bromobenzaldehyd
e

Preparation of Ketones
Oxidation of secondary
alcohol
Hydration of
alkynes
Ozonolysis of
alkenes
Friedel-Crafts
acylation

KETONES

i) Oxidation of 20 Alcohol

General
equation
OH :
R

R' [O]

K2Cr2O7
H

R'

ketone

20 alcohol
Secondary alcohols are oxidised to ketones using oxidation agent such as
PCC, chromic acid or potassium dichromate and sulfuric acid.

Example :
OH
H3 C

CH3 [O]

H
propanol

K2Cr2O7
H+

O
H 3C

CH3

propanone

ii) Hydration of Alkynes

Example :
H3 C

H + H2 O

H2SO4
HgSO4

OH H
H3 C

H enol

propyne
tautomerism

H3 C

H
propanone

iii) Ozonolysis of Alkenes

Example :
CH2 CH3
H 3C

CH2 CH3

i) O3
ii) Zn/
H3O+

O
H3 C

CH2 CH3

2-butanone

3-methyl-3-hexene

+
O

CH2 CH3

H
propanal

iv) Friedel-Crafts Acylation

To produce aromatic ketone

Example :

O
H3 C

O
+

H3 C

Cl

AlCl3

Chloroethane
Benzene

Aromatic
Ketone

Reaction of Aldehydes and Ketones

K2Cr2O7
H2SO4, H2O

Oxidation
Aldehydes are much more easily oxidized than
ketones.
Strong oxidizing agents such as potassium
permanganate, potassium dichromate, readily
oxidize aldehydes and they are also oxidized by
such mild oxidizing agents as silver oxide.
Example
O
||
CH3(CH2)4 - C-H + K2Cr2O7
hexanal

H+

O
||
CH3(CH2)4 C -OH
hexanoic acid

Reduction

Aldehydes are reduced to primary alcohols and ketones to

secondary alcohols by a variety of reducing agents.
Catalytic hydrogenation over a metal catalyst and
reduction with sodium borohydride or litium aluminium
hydride are common.

H
|
R- C=O
aldehyde

H
H+

|
R- C-OH
alcohol 1 0

R
|
R- C=O
ketone

R
H+

R-C-OH
alcohol 20

Example
H
|

LiAlH 4

CH3- C=O
CH3CH2OH
ethanal
ethanol

H+

(alcohol 1o)

CH3
|
CH3-C=O
CH3-CH(CH3)OH
propanone
propanol
(alcohol 2)

NaBH4 /H+
or
H 2/pt

Important of Aldehydes and Ketones