1

Jully Tan
School of Engineering
EP101 / EG101 2
Learning Outcome
At the end of this chapter, students are able to:

Provide nomenclature of the ketone and aldehyde
Physical properties of ketone and aldehyde
Synthesis and reaction of ketone and aldehyde

EP101 / EG101 3
Chapter 16
Aldehydes and Ketones I
Nucleophilic Addition to the Carbonyl Group
The general structure of
the carbonyl group is
C=O
H
R
:
:
O
C
The general formula for an aldehyde is
And that for a ketone is
C=O
R'
R
:
:
C=O
H
H
:
:
There is also the unique aldehyde, formaldehyde,
in which there are two hydrogen atoms attached to
the carbonyl group.
The R groups can be either alkyl or aryl.
EP101 / EG101 4
Nomenclature of Aldehydes
Common names are derived from those of the corresponding carboxylic acids
by dropping the "(o)ic acid" and adding "aldehyde."
OH
O
H
O
Acetic acid Acetaldehyde
O
OH
O
H
Benzoic acid Benzaldehyde
IUPAC (systematic) names are based on the following rules when the
aldehyde function has priority and is named by use of a suffix.
(1) Select the longest continuous chain containing the -CHO and use
as the parent the name of the alkane of that chain length.
(2) Replace "e" in the alkane name with "al."
(3) Number from the end where the carbonyl group is located and
follow all the other rules for locating substituent groups.
4-Phenylpentanal 2,2-Dimethylbutanal
H
O
H
O
EXAMPLES:
EP101 / EG101 6
IUPAC systematic names for ketones are based on
these rules:
(1) The name of the longest alkane chain present that contains the
carbonyl group is used as the parent.
(2) Replace the "e" in the alkane name with the suffix "one" and
indicate the carbonyl position by a number. Number from the end
that gives the lower number to the ketone position.
(3) Designate the substituents and their positions in the usual way.
2-Pentanone
2-Methyl-4-phenyl-3-pentanone
O
O
Note use of
alphabetical order.
O
(E)-3-Penten-2-one
Note provision
for C C bond.
EP101 / EG101 7
Physical Properties of Aldehydes and Ketones
Because of the polar carbonyl group ( ~ 2.3-2.8 D), aldehydes and
ketones have higher boiling points than hydrocarbons of comparable size.
However, they have lower boiling points than alcohols of comparable size
because only the latter have intermolecular hydrogen bonds.
CH
3
CH
2
CH
2
CH
3
CH
3
CH
2
CH CH
3
CCH
3
CH
3
CH
2
CH
2
OH
O
= O=
Butane Propanal Acetone 1-Propanol
MW 58 58 58 60
BP -0.5
o
C 49.0
o
C 56.1
o
C 97.2
o
C
Aldehydes and ketones form hydrogen bonds to water molecules and
consequently the lower MW ones are soluble in water up to about C
6.

The smallest ones (formaldehyde and acetone) are miscible with water.
O
H
O
H
H
O H
EP101 / EG101 8
Synthesis of Ketones & Aldehydes
Oxidation of alcohol
Ozonolysis of alkene
Friedel-crafts acylation
Mercuric catalysed hydration of alkynes
Ketone from nitriles

EP101 / EG101 9
Synthetic Methods for Aldehydes
Because aldehydes are between 1
o
alcohols and carboxylic acids in the
oxidation-reduction sequence, they can be synthesized by either selective
oxidation of 1
o
alcohols or by selective reduction of carboxylic acid
derivatives.
RCH
2
OH RCH
O=
RCOOH [O]
[H]
[O]
[H]
or
RCOX
Selective Oxidation with Pyridinium Chlorochromate (PCC)
PCC
CH
2
Cl
2
1-Heptanol Heptanal (78%)
PCC is
It is a unique Cr +6 oxidant. Other oxidants carry oxidation on
to the carboxylic acid stage because aldehydes are more easily
oxidized than alcohols.
OH
H
O
N H Cl CrO
3
Reduction of Carboxylic Acids
Aldehydes can be prepared by controlled reduction of carboxylic acids. Acids
can be reduced with lithium aluminum hydride (LAH), a powerful reducing
agent, but the process goes all the way to 1
o
alcohols.
RCOH
O
=
LiAlH
4
ether solvent
RCH
O
=
LiAlH
4
facile
RCH
2
OH
Lithium aluminum hydride
(lithium tetrahydridoaluminate)
and other metal hydride
reducing agents, transfer
hydride ion (H:
-
) to the
electropositive carbon of the
carbonyl group.
Al
H
H
H
H
-
Li
+
C=O
+ -
EP101 / EG101 10
Ozonolysis of alkenes.
C
H
R
C
R'
R''
1)
2)
O
3
(CH
3
)
2
S
C
H
R
O
+ C O
R'
R''
Friedel-Crafts acylation
Acid chloride/AlCl
3
+ benzene ketone

Ketone Syntheses
Oxidation of Secondary Alcohols
H OH
Cyclohexanol
K
2
Cr
2
O
7
or CrO
3
H
2
SO
4
O
=
Cyclohexanone
These oxidations generally
proceed well with few side
reactions.
Aryl Ketones by Friedel-Crafts Acylation
+
Butanoyl chloride
AlCl
3
Phenyl propyl ketone
Cl
O
O
Ozonolysis of Alkenes
1,2-Dimethylcyclopentene
O
3
CH
2
Cl
2
, -78
o
C
Zn
H
2
O
2,6-Heptanedione
O
O
EP101 / EG101 11
Ketones by Hydration of Alkynes
Alkynes, like alkenes, add water in the presence of electrophilic catalysts
such as H
+
or Hg
2+
. Hydration of alkynes is conducted in aqueous
solutions of sulfuric acid with mercuric sulfate as catalyst. It follows
Markovnikov's rule, with the hydrogen attaching to the carbon with the
greater number of hydrogens.
-C C-
Alkyne
+ H
2
O
HgSO
4
H
2
SO
4
-C=C-
H
OH
"Enol"
(or vinylic alcohol)
fast
-C-C-
H
H
O
=
The "enol" rapidly rearranges to the ketone. The enol and ketone
constitutional isomers actually are connected by an equilibrium which
usually lies heavily on the side of the ketone. This process called
tautomerization is catalyzed by acid.
-C=C-
H
:OH
:
O
H
H
+
H
2
O + -C C-
H
H
:OH
=
+
Conjugate acid
of ketone
Enol form
(less stable)
+
H
-C C-
H
H
:O:
=
H
3
O
+
+
Keto form
(more stable)
EP101 / EG101 12
Ketones from Nitriles
Reaction of a nitrile with either a Grignard or organolithium reagent,
followed by hydrolysis, yields a ketone.
R-C N:
Nitrile
(R = alkyl or aryl)
+ R'-M
ether
R-C-R'
N-M =
Imine salt
R-C-R'
O
=
H
3
O
+
H
2
O
The nitrile is a polar function similar to a carbonyl. The carbanionic
center of an organometallic reagent adds to the electropositive carbon of
the nitrile producing the salt of an imine.
-
+
During aqueous workup, the imine is hydrolyzed to a ketone.
R-C=N- M
:
+ H-O-H R-C=N-
R'
H
:
Imine
hydrolysis
R-C=O:
R'
:
R'
- +
- +
EP101 / EG101 13
Examples
Butanenitrile
(1) ether
(2) H
3
O
+
+
O
Butyrophenone
(Phenyl propyl ketone)
MgBr
N
Benzonitrile
+ N:
Li
(1) ether
(2) H
3
O
+
EP101 / EG101 14
Characteristic Reactions of Aldehydes and Ketones
Reduction reactions
Alcohol formation
Alkane formation
Oxidation reactions
Nucleophilic addition reactions
Grignard additions to form alcohols
Addition of water (hydration) to form gem-diols
Addition of alcohols to form acetals/ketals
EP101 / EG101 15
Reduction Reactions of Aldehydes and Ketones
Alcohol formation
Hydrogenation
Hydride reduction
Alkane formation
Clemmensen reduction
Wolff-Kishner reduction

R C
O
H
H
2
/ Pt
R CH
2
OH
R C
O
H
R CH
2
OH
LiAlH
4
ether
H
2
O
H
+
R C
O
H R CH
3
conc. HCl
Zn(Hg)
R C
O
H R CH
3
NH
2
NH
2
OH
-
/ H
2
O
EP101 / EG101 16
Oxidation of Aldehydes and Ketones
Conversion of Aldehydes to Carboxylic acids
Oxidation of Aromatic Aldehydes/Ketones to Benzoic acid derivatives
Haloform reaction of methyl carbonyls
EP101 / EG101 17
Aldehyde / Ketone Oxidations

HIO
4
C
O
C
O
H R RCOOH + HCOOH
+
HIO
3
R C
O
H RCOOH
Ag(NH
3
)
2
+
(Tollens reagent)
C
O
H
or
C
O
R
COOH
KMnO
4
or K
2
Cr
2
O
7

CH
3
C
O
R
X
2
OH
-
/ H
2
O
HCX
3
+ RCOO
-
Ar C
O
H or (ArCOOH)
EP101 / EG101 18
Aldehyde / Ketone Nucleophilic Addition Reactions

R C R'
O
R"MgX
H
+
H
2
O
R C
OH
R'
R"
R C R'
O
R C R'
O
R C R'
O
H
2
O
C
R
R'
OH
OH
dry HCl
R''OH
C
R
R'
OH
OR"
C
R
R'
OR"
OR"
hemiketal ketal
H
+
or OH
-
gem diol
HCN
C
R
R'
OH
CN
cyanohydrin
R C R'
O
H
2
N G ( H
2
O) -
C N G
R
R'
EP101 / EG101 19
Ketals: Acetals of Ketones
Acetal (ketal) formation with ketones is generally not a favorable process:
C
R'
R
OR''
OR''
+ H
2
O
H
+
C=O
R'
R
+ 2 R''OH
Ketal
Ketone
H
+
As in the hydration reaction, the equilibrium heavily
favors the ketone.
Cyclic ketals, formed from 1,2- or 1,3-diols, are an exception:
C=O
R'
R
+ HOCH
2
CH
2
OH
1,2-Ethanediol
(ethylene glycol)
H
+
H
+
C
R'
R
O-CH
2
O-CH
2
+ H
2
O
Cyclic ketal (stable)
Cyclic acetals or ketals hydrolyze easily in aqueous acid solution:
C=O
R'
R
+ HOCH
2
CH
2
OH
H
+
C
R'
R
O-CH
2
O-CH
2
+ H
2
O
excess