General

Organic Chemistry
Two credits
Second Semester 2009

King Saud bin Abdulaziz University for Health Science

Reference Book: Organic Chemistry: A Brief Course,

by Robert C. Atkins and Francis A. Carey
Third Edition

Instructor: Rabih O. Al-Kaysi, PhD.

 Lecture 18

Chapter 11

Aldehydes and
Ketones
Nucleophilic Addition
to the
Carbonyl Group
Nomenclature
IUPAC Nomenclature of Aldehydes

O O

H H

Base the name on the

O O chain that contains
the carbonyl group
HCCHCH and replace the -e
ending of the
hydrocarbon by -al.
 IUPAC Nomenclature of Aldehydes

O O

H H

4,4-dimethylpentanal 5-hexenal

O O

HCCHCH 2-phenylpropanedial
(keep the -e ending
before -dial)
 IUPAC Nomenclature of Aldehydes

when named as C H when named

a substituent as a suffix

formyl group carbaldehyde or

carboxaldehyde
 Substitutive IUPAC Nomenclature of Ketones

O O
CH3CH2CCH2CH2CH3 CH3CHCH2CCH3

CH3

Base the name on the chain

that contains the carbonyl
H3C O group and replace -e by -one.
Number the chain in the
direction that gives the lowest
number to the carbonyl
carbon.
 Substitutive IUPAC Nomenclature of Ketones

O O
CH3CH2CCH2CH2CH3 CH3CHCH2CCH3

3-hexanone CH3

4-methyl-2-pentanone

H3C O

4-methylcyclohexanone
Functional Class IUPAC Nomenclature of Ketones

O O
CH3CH2CCH2CH2CH3 CH2CCH2CH3

List the groups

attached to the
carbonyl separately in
O alphabetical order, and
add the word ketone.
H2C CHC CH CH2
Functional Class IUPAC Nomenclature of Ketones

O O
CH3CH2CCH2CH2CH3 CH2CCH2CH3

ethyl propyl ketone benzyl ethyl ketone

O
divinyl ketone
H2C CHC CH CH2
Structure and Bonding:
The Carbonyl Group
 Structure of Formaldehyde

planar
bond angles: close to 120°
C=O bond distance: 122 pm
 The Carbonyl Group

very polar double bond

1-butene propanal

dipole moment = 0.3D dipole moment = 2.5D

Resonance Description of
Carbonyl Group

•• • •• –
O• • •
• O•
C C
+

nucleophiles attack carbon;

electrophiles attack oxygen
 Bonding in Formaldehyde

Carbon and oxygen are sp2 hybridized

Bonding in Formaldehyde

The half-filled
p orbitals on
carbon and
oxygen
overlap
to form a π
bond
Physical Properties
 Aldehydes and ketones have higher boiling
than alkenes, but lower boiling points than alcohols.

boiling point

–6°C
More polar than
O alkenes, but cannot
49°C form intermolecular
hydrogen bonds to
other carbonyl groups
OH 97°C
Sources of Aldehydes and Ketones
Many aldehydes and ketones occur naturally

2-heptanone
(component of alarm pheromone of bees)
Many aldehydes and ketones occur naturally

trans-2-hexenal
(alarm pheromone of myrmicine ant)
Many aldehydes and ketones occur naturally

citral (from lemon grass oil)

 Synthesis of Aldehydes and Ketones

from alkenes
A number of ozonolysis
reactions already from alkynes
studied provide
efficient synthetic hydration (via enol)
routes to from arenes
aldehydes and
ketones. Friedel-Crafts acylation

from alcohols
oxidation
 What about..?

aldehydes from carboxylic acids

O O
C C
R OH R H

1. LiAlH4 PDC, CH2Cl2

2. H2O
RCH2OH
 Example

benzaldehyde from benzoic acid

O O
COH CH

1. LiAlH4 PDC
2. H2O CH2Cl2
CH2OH
(81%) (83%)
 What about..?

ketones from aldehydes

O O
C C
R H R R'

1. R'MgX OH PDC, CH2Cl2

2. H3O+
RCHR'
 Example

3-heptanone from propanal

O O
C CH3CH2C(CH2)3 CH3
CH3CH2 H
(57%)
1. CH3(CH2)3MgX
H2CrO4
2. H3O + OH
CH3CH2CH(CH2)3 CH3
Reactions of Aldehydes and
Ketones:
A Review and a Preview
 Reactions of Aldehydes and Ketones

Already covered in earlier chapters:

reduction of C=O to CH2

Clemmensen reduction
Wolff-Kishner reduction
reduction of C=O to CHOH
addition of Grignard and organolithium
reagents
 Principles of Nucleophilic
Addition to Carbonyl Groups:
Hydration of Aldehydes and
Ketones
Hydration of Aldehydes and Ketones

C O ••
••

H2O

•• ••
HO C O H
•• ••
 Substituent Effects on Hydration Equilibria

O OH

C + H2O R C R'
R R'
OH
compared to H
electronic: alkyl groups stabilize
reactants
steric: alkyl groups crowd
product
 Equilibrium Constants and Relative Rates
of Hydration

C=O hydrate K % Relative

rate

CH2=O CH2(OH)2 2300 >99.9 2200

CH3CH=O CH3CH(OH)2 1.0 50 1.0

(CH3)3CCH=O (CH3)3CCH(OH)2 0.2 17 0.09

(CH3)2C=O (CH3)2C(OH)2 0.0014 0.14 0.0018

 When does equilibrium favor hydrate?

when carbonyl group is destabilized

alkyl groups stabilize C=O
electron-withdrawing groups destabilize C=O
 Substituent Effects on Hydration Equilibria

O OH

C + H2O R C R
R R
OH
R = CH3: K = 0.000025
R = CF3: K = 22,000
 Mechanism of Hydration (base)

Step 1:

H
– •• •• •–
•O•
• • + C O •• HO C O•
•• •• •• ••
 Mechanism of Hydration (base)

Step 2:

•• •• •–
HO C O•
•• ••

H
H
•• •• –• • H O ••
HO C OH + • O• ••
•• •• ••
 Mechanism of Hydration (acid)

Step 1:
H
C O •• + H O ••
•• +
H

H
+
•O•
C OH + • •
••
H
 Mechanism of Hydration (acid)

Step 2:

H H
+ ••
•O• + C OH •O C OH
• • •
•• + ••
H H
 Mechanism of Hydration (acid)

Step 3:
H •• H
+O H •• H
O
H ••

+ H
•O ••
•• • C OH
•O •• + ••
• C OH
•• H
H
Cyanohydrin Formation
 Cyanohydrin Formation

• ••
C O •• + HCN •N C C O H
•• ••
 Cyanohydrin Formation

•
–
•N C •• C O ••
••
 Cyanohydrin Formation

H
•• •–
•
•N C C O• H O ••
•• +
H

• •• • O ••
•N C C O H •
••
H
 Example

Cl Cl
O OH
NaCN, water
Cl CH Cl CHCN
then H2SO4

2,4-Dichlorobenzaldehyde
cyanohydrin (100%)
Example

O OH
NaCN, water
CH3CCH3 CH3CCH3
then H2SO4
CN
(77-78%)

Acetone cyanohydrin is used in the

synthesis of methacrylonitrile