Derivatives of hydrocarbons

Aldehydes and Ketones

Aldehydes and Ketones

structure and properties
Sources
Reactions
Important of aldehydes and ketones
 Introduction
o carbonyl compounds : compounds with carbonyl
C
group
O

o examples of carbonyl compounds :

O O
R C H R C R'

aldehyde 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 O

H R R
R
Carbonyl Containing Compound
Formula Family Formula Family

Ester
Aldehyde

Ketone Amide

Carboxylic Acid
 Aldehydes and Ketones
Only differ by location of carbonyl

Aldehydes RCHO

Ketones 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 CH3 CCH3
Meth anal Ethanal Prop anone
(Formaldehyde) (Acetaldeh yd e) (Aceton e)
Example
Table 8.1: IUPAC nomenclature and common names for aldehyde and ketone compounds.

Compound Common name

Structure formula IUPAC

nomenclature
Aldehyde HCHO Methanal Formaldehyde

CH3CHO Ethanal Asetaldehyde

CH3CH2CHO Propanal Propionaldehyde

CH3CH2CH2CHO Butanal Butyraldehyde

Ketone 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

ALDEHYDES

Ozonolysis of alkenes

Hydrolysis of gem halides

i) Oxidation of 10 Alcohol
General equation :
H H
PCC
R C OH [O] R C O
H aldehyde
10 alcohol

Oxidation of primary alcohols to aldehyde using pyridium chlorochromate

(PCC) in anhydrous media such as dichloromethane.

Example : H
H
PCC H3 C C O
H3 C C OH [O]
H ethanal
ethanol
ii) Hydration of Alkynes

General equation :
H2SO4 H OH enol
R C C R' + H2O R C C R'
HgSO4
alkyne
tautomerism

O
R CH2 C R'

aldehyde
ii) Hydration of Alkynes
Example :
H OH enol
H2SO4
H C C H + H2O H C C H
HgSO4
ethyne
tautomerism

H O
H C C H
H
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 OH
|| |
CH3-C-CH3 CH3-C = CH2
acetone acetone
(keto form) (enol form)
 iii) Ozonolysis of Alkenes
General equation :
H H H H
i) O3
R C C R' R C O + O C R'
ii) Zn/H3O+
alkene aldehyde

Example 1 :
H H H
i) O3
H3 C C C CH2 CH3 H3 C C O +
ii) Zn/
2-pentene H 3 O+ ethanal H propanal
O C CH2 CH3
iii) Ozonolysis of Alkenes
Example 2 :
CH3
i) O3 O O
C CH2 CH CH2 C
ii) Zn/ H
H 3O+ CH3 H

4-methylcyclopentene 3-methylpentandial
iv) Hydrolysis of Gem Halides
To produce aromatic aldehyde

Example :
H
X X H O
CH3 C C

hv or H 2O
+ 2X2

Toulene Gem halides Benzaldehyde

iv) Hydrolysis of Gem Halides
Example :
H
Cl Cl H O
CH3 C
C

hv or H 2O
+ 2Cl2

Br Gem halides
Br Br
4-bromotoulene
4-bromobenzaldehyde
 Preparation of Ketones
Oxidation of secondary alcohol

Hydration of alkynes
KETONES

Ozonolysis of alkenes

Friedel-Crafts acylation
i) Oxidation of 20 Alcohol
General equation :
OH O
K2Cr2O7
R C R' [O] R C R'
H+
H 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 O
K2Cr2O7
H3C C CH3 [O] H3 C C CH3
H+
H propanone
propanol
 ii) Hydration of Alkynes
Example :
OH H
H2SO4
H3 C C C H + H2O H3 C C C H enol
HgSO4
propyne
tautomerism

O H
H3 C C C H
H
propanone
iii) Ozonolysis of Alkenes
Example :

CH2 CH3 O
i) O3
H3 C C C CH2 CH3 H3 C C CH2 CH3
ii) Zn/
H H 3 O+ 2-butanone

3-methyl-3-hexene
+
O C CH2 CH3
H

propanal
iv) Friedel-Crafts Acylation
To produce aromatic ketone

Example :
O
H3C C
O
AlCl3
+ H3C C Cl

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 O
|| ||
CH3(CH2)4 - C-H + K2Cr2O7 H+ CH3(CH2)4 C - OH
hexanal hexanoic acid
Reduction

Aldehydes are reduced to primary alcohols and ketons 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 H
| H+ |
R- C=O R- C-OH
a1dehyde alcohol 10

R R
| H+ |

R- C=O R-C-OH
ketone a1cohol 20
 Example

H
| LiAlH4
CH3- C=O CH3CH2OH
ethanal H+ ethanol
(alcohol 1o)

CH3 NaBH4 /H+

| or
CH3-C=O CH3-CH(CH3)OH
propanone H2/pt propanol
(alcohol 2)
Important of Aldehydes and
Ketones