Chapter 9

Ketones and
Aldehydes

Carbonyl Compounds

Carbonyl Structure
Carbon is sp2 hybridized.
C=O bond is shorter, stronger, and
more polar than C=C bond in alkenes.

IUPAC Names for

Ketones
Replace -e with -one. Indicate the
position of the carbonyl with a
number.
Number the chain so that carbonyl
carbon has the lowest number.
For cyclic ketones the carbonyl
carbon is assigned the number 1.

Chapter 9

Examples
O

O
CH3

C CH CH3
CH3

Br

3-methyl-2-butanone
3-methylbutan-2-one

3-bromocyclohexanone

O
CH3

C CH CH2OH
CH3

4-hydroxy-3-methyl-2-butanone
4-hydroxy-3-methylbutan-2-one

Chapter 9

Naming Aldehydes
IUPAC: Replace -e with -al.
The aldehyde carbon is number 1.
If -CHO is attached to a ring, use the
suffix -carbaldehyde.

Chapter 9

Examples
CH3

CH2

CH3

CH CH2

C H

3-methylpentanal

CHO
2-cyclopentenecarbaldehyde
cyclopent-2-en-1-carbaldehyde

Chapter 9

Name as Substituent
On a molecule with a higher priority
functional group, C=O is oxo- and -CHO
is formyl.
Aldehyde priority is higher than ketone.
COOH

CH3

CH3

CH CH2

C H

3-methyl-4-oxopentanal

CHO
3-formylbenzoic acid
Chapter 9

Common Names for

Ketones
Named as alkyl attachments to -C=O.
Use Greek letters instead of numbers.
O

O
CH3

CH3CH C CH CH3

C CH CH3

Br

CH3
methyl isopropyl ketone

CH3

bromoethyl isopropyl ketone

Chapter 9

Historical Common
Names
O
C

O
CH3

CH3

C CH3
acetophenone

acetone

O
C

benzophenone

Chapter 9

10

Aldehyde Common
Names

Use the common name of the acid.

Drop -ic acid and add -aldehyde.

1
2
3
4
5

C: formic acid, formaldehyde

Cs: acetic acid, acetaldehyde
Cs: propionic acid, propionaldehyde
Cs: butyric acid, butyraldehyde.
Cs: valeric acid, valeraldehyde
Br

CH3

CH CH2

C H

-bromobutyraldehyde
3-bromobutanal

Chapter 9

11

Boiling Points
More polar, so higher boiling point
than comparable alkane or ether.
Cannot H-bond to each other, so lower
boiling point than comparable alcohol.

Chapter 9

12

Solubility
Good solvent for alcohols.
Lone pair of electrons on oxygen of
carbonyl can accept a hydrogen
bond from O-H or N-H.
Acetone and acetaldehyde are
miscible in water.

Chapter 9

13

Formaldehyde
Gas at room temperature.
Formalin is a 40% aqueous solution.
H
H
H

O
C

H
C

C H
O
H

heat

O
H C H
formaldehyde,
b.p. -21C

H2O

HO
OH
H C
H
formalin

trioxane, m.p. 62C

Chapter 9

14

Industrial Importance
Acetone and methyl ethyl ketone
are important solvents.
Formaldehyde used in polymers
like Bakelite .
Flavorings and additives like
vanilla, cinnamon, artificial butter.

Chapter 9

15

Synthesis Review
Oxidation
2 alcohol + Na2Cr2O7 ketone
1 alcohol + PCC aldehyde

Ozonolysis of alkenes.

Chapter 9

16

Synthesis Review (2)

Friedel-Crafts acylation
Acid chloride/AlCl3 + benzene
ketone

Hydration of terminal alkyne

Use HgSO4, H2SO4, H2O for methyl
ketone

Chapter 9

17

Aldehydes from Acid

Chlorides
Use a mild reducing agent to prevent
reduction to primary alcohol.
O
CH3CH2CH2C

Cl

LiAlH(O-t-Bu)3

Chapter 9

O
CH3CH2CH2C

18

Ketones from Acid

Chlorides
Use lithium dialkylcuprate (R 2CuLi),
formed by the reaction of 2 moles of
R-Li with cuprous iodide.
2 CH3CH2CH2Li

CuI

(CH3CH2CH2)2CuLi

O
(CH3CH2CH2)2CuLi +

CH3CH2C Cl

Chapter 9

CH3CH2C

CH2CH2CH3

19

Nucleophilic Addition
A strong nucleophile attacks the
carbonyl carbon, forming an
alkoxide ion that is then
protonated.
A weak nucleophile will attack a
carbonyl if it has been protonated,
thus increasing its reactivity.
Aldehydes are more reactive than
ketones.

Chapter 18

20

Addition of Water
In acid, water is the nucleophile.
In base, hydroxide is the nucleophile.
Aldehydes are more electrophilic since
they have fewer e--donating alkyl groups.
O
H

+ H2O

HO

OH
C

K = 2000

a gemdiol

O
CH3

+ H2O

CH3

HO
CH3

OH
C
CH3

a
Chapter gemdiol
9

K = 0.002
21

Addition of Alcohol

Chapter 9

22

Mechanism
Must be acid-catalyzed.
Adding H+ to carbonyl makes it more
reactive with weak nucleophile, ROH.
Hemiacetal forms first, then acidcatalyzed loss of water, then addition of
second molecule of ROH forms acetal.
All steps are reversible.

Chapter 9

23

Mechanism for
Hemiacetal
Oxygen is protonated.
Alcohol is the nucleophile.
H+ is removed.
=>

Chapter 9

24

Hemiacetal to Acetal
HO

OCH3

+
HO

OCH3

OCH3
+

H+

+ HOH

HOCH3
OCH3
HOCH3

+
CH3O

H
OCH3

CH3O

OCH3

Chapter 9

25

Oxidation of
Aldehydes

Easily oxidized to carboxylic acids.

Chapter 18

26

Cyclic Acetals
Addition of a diol produces a cyclic acetal.
Sugars commonly exist as acetals or
hemiacetals.
CH2 CH2
O
O

O
+

CH2
HO

CH2
OH

Chapter 9

27

Tollens Test
Add ammonia solution to AgNO3
solution until precipitate dissolves.
Aldehyde reaction forms a silver mirror.
O
+

R C H + 2 Ag(NH3)2 +
+

NH3)2 +

3 OH

H2O

3 OH

H2O

O
2 Ag + R C O

2 Ag + R C O

4 NH3 + 2 H2O
=>

Chapter 18

28

SILVER MIRROR

Reduction Reagents
Sodium borohydride, NaBH4,
reduces C=O, but not C=C.
Lithium aluminum hydride, LiAlH4,
much stronger, difficult to handle.
Hydrogen gas with catalyst also
reduces the C=C bond.

Chapter 18

30

Catalytic Hydrogenation
Widely used in industry.
Raney nickel, finely divided Ni
powder saturated with hydrogen gas.
Pt and Rh also used as catalysts.
O

OH
Raney Ni

Chapter 18

H
31

Tautormers

Constitutional isomers in equilibrium with each other that

differ in the location of a hydrogen atom and a double
bond are called tautomers.
A case of tautomerization occurs with ketones
(aldehydes) that are in equilibrium with their enol form,
which are called keto enol tautomers
O

OH

Keto Form

Enol Form

ALDEHYDE AND KETONE

REVIEW

Name

H3C

a.
b.
c.
d.

CH
CH

Cis-2-pentenal
Cis-2-pentanal
Trans-2-pentenal
Trans-2-pentanal

C
CH2

Answer
a.
b.
c.
d.

Cis-2-pentenal
Cis-2-pentanal
Trans-2-pentenal
Trans-2-pentanal

The aldehyde is in position one. The

double bond is trans.

Name

H3C

a.
b.
c.
d.

CH2

C
CH2

OH

2-Oxobutanoic acid
2-Butanone-1-carbaldehyde
2-Oxopentanoic acid
3-Oxopentanoic acid

Answer
a.
b.
c.
d.

2-Oxobutanoic acid
2-Butanone-1-carbaldehyde
2-Oxopentanoic acid
3-Oxopentanoic acid

The carbon in the carboxylic acid is

position one.

Identify the chemical

name for acetone.
a.
b.
c.
d.

Methanal
Ethanal
Propanone
Butanone

Answer
a.
b.
c.
d.

Methanal
Ethanal
Propanone
Butanone

Acetone is called propanone or

dimethyl ketone.

1. CH3CH2MgCl
+
2. H3O

O
C
H3C

a.
b.
c.
d.

2-Propanone
2-Butanone
2-Pentanone
3-Pentanone

3. Na2Cr2O7, H2SO4

Answer
a.
b.
c.
d.

2-Propanone
2-Butanone
2-Pentanone
3-Pentanone

2-Butanone is formed in the Grignard

reaction. The secondary alcohol is oxidized to
a ketone with sodium dichromate.

O
1. CH3CH2Li

C
H3C

a.
b.
c.
d.

2-Propanone
2-Butanone
2-Pentanone
3-Pentanone

OH

2. H3O+

Answer
a.
b.
c.
d.

2-Propanone
2-Butanone
2-Pentanone
3-Pentanone

The ethyl group adds to the carbonyl carbon.

O
2 CH3CH2OH

C
H3C

a.
b.
c.
d.

CH3

H+

2,2-Diethoxypropane
2-Ethoxy-2-propanol
Propane-2,2-diol
2-Ethoxypropane

Answer
a.
b.
c.
d.

2,2-Diethoxypropane
2-Ethoxy-2-propanol
Propane-2,2-diol
2-Ethoxypropane

Two molecules of ethanol are added to

the carbonyl, with loss of water.

O
H3C

a.
b.
c.
d.

1. Ag(NH3)2, OH

C
CH2

2. H+

1-Propanol
Propanoic acid
Propane-1,1-diol
1-Hydroxypropanoic acid

Answer
a.
b.
c.
d.

1-Propanol
Propanoic acid
Propane-1,1-diol
1-Hydroxypropanoic acid

The Tollens reagent reduces an

aldehyde to a carboxylic acid.

O
H3C

a.
b.
c.
d.

NaBH4

C
CH2

CH3

2-Butanone
2-Butanol
2-Hexanone
Butane

CH3CH2OH

Answer
a.
b.
c.
d.

2-Butanone
2-Butanol
2-Hexanone
Butane

Butanone is reduced to 2-butanol.

End of
Chapter 9
Chapter 9

50