Organic Chemistry

Dr. Omar Mohammed Yahya

 Aldehydes and ketones
These are compounds characterized by the presence of carbonyl group, where
as aldehyde contains a carbonyl group whose carbon is bonded to one
:hydrogen and either an alkyl or aryl group , for example
O
O
C H
CH3 C H
aliphatic aromatic
acetaldehyde benzaldehyde
 :ketones
carbonyl group attached to two alkyl or two aryl groups or one alkyl and one
:aryl group for example
O O O
C CH3 C
H3C C CH3
aliphatic acetophenone aromatic
acetone methyl phenyl ketone benzophenone
mixed

O O

H CCH2CH2C H
butanedial
Naming of carbonyl compound
Common names are almost always used for aldehydes of five carbons or less

O
CH3 CH2 CH2 C H
Propionaldehyde Butyraldehyde
O
δ γ β α
C C C C C H
O O
Br CH2 CH2 CH2 C H CH3 CH C H
Cl
γ- Bromobutyraldehyde α- Chloropropionaldehyde
IUPAC
The IUPAC names of aldehyde are formed by replacing the –e of the
name of the longest carbon chains the aldehyde group with –al. Because
the aldehyde group ,like the carboxyl group ,must always be at the end of
the chian .
CH3 CH3
CH3CHO CH3 CH CHO Cl CH2 CH CH2 CHO
Ethanal 2-Methyl propanal 4-Chloro-3-methyl butanal
The common names of ketones are formed by replacing the names of the
groups attached to the carbonyl group as prefixes to the word ketone .
The names are written as separate words , for example .
O O
CH3 CH2 C CH3 CH3 CH2 C CH2 CH3
Ethyl methyl ketone Diethyl ketone
 Ethyl vinyl ketone

The IUPAC names of ketones are derived from the name of the longest
carbon chain that contains the carbonyl group by replacing the –e with the
suffixe one

butanone-2 methyl-3-penten-2-one-4 cyclohexanone

Physical properties
.Boiling point if carbonyl compound is higher due to the H-bonding-1
.Aldehyde and ketone are polar molecules-2
Many aldehyde have pleasant odors even ketones of lower molecular -3
.weight have rather than pleasant odors

Preparation of carbonyl compound

a- Aldehydes
Oxidation of alcohols-1
:aldehydes can be prepared from the oxidation of primary alcohol for example

aldeyhde

the reaction is called dehydration

Oxidation of methyl benzenes for example -2

p-nitro toluene p-nitro benzaldehyde

 O
O CH3 C
2 CH3 C OH O + H2O
CH3 C
O
Acetic anhydride
b-Ketones
1-Oxidation of Secondary Alcohols , for example
CH3
CH3

H K2Cr2O7 , H2SO4

OH O
CH
CH
H3C CH3
H3C CH3

2-Friedel-Crafts acylation for example

O O
AlCl3
C Cl + C + HCl

benzoyl chloride Diphenyl ketone

benzophenone
The carbonyl group:-
o o
120 120
C O C C

The electronic structure of carbonyl group is similar to

electronic structure of the alkene .The orbital of carbonyl
compound are sp2 .
The different between carbonyl and alkene structure is that
in a carbonyl compound the double bond involves between
two atoms of a wide difference of electronegative .
So carbonyl group is a polar group .
Carbonyl group
 +δ -δ

Resonance structure of carbonyl group

C O the bond length =1.24 Ao

8- -10
1Ao =10 cm = 10 m

the solubility of low carbonyl compound , they are soluble

in water due to the formation of H-bonding
Application to biochemistry
Honey is especially sweet because of the sugar (fructose) .
O

CH2(OH)CCH(OH)CH(OH)CH(OH)CH2OH
f ructose
Test for aldehyde
Most of the reactions of aldehydes and ketones are very
similar , but their ability to be oxidized differs greatly . This
ease of oxidation is the basis of several specific tests for
aldehydes .
One of these is the # Tollens, test # , which consists of
adding the Tollens, reagent , an alkaline solution of
di(ammine) silver(I) ion ,Ag(NH­3)2+ , to the aldehyde . The
aldehyde is oxidized to the carboxylate ion , and the silver ion
is reduced to silver metal :

- -
2 Ag(NH3)2+ + RCHO + 3 OH RCO2 + 2 Ag + 4NH4 + 2 H2O
The silver metal coats the glass surface and forms a silver
mirror , this reaction is commonly the silver mirror test for
aldehyde .