2.

Aldehydes and ketones

2.1 Introduction
sp2
C O

Contain

Also non-bonding
electrons on
oxygen

C O

2.1.1 Nomenclature
Aldehyde:
Delete "e" of alkane - add al

O
R

CH3

CH3

CH3CH2CH2CHCH2CHCHO
2,4-dimethylheptanal C=O position # 1

Ketone: Delete "e" of alkane and add one

O

O
R

CH3

CH2CH3

CH3CCH2CHCH2CHCH3

R'

4,6-dimethyloctan-2-one

Trivial names:

methanal
ethanal

HCHO

formaldehyde

CH3CHO

acetaldehyde

CH3COCH3

acetone

propanone

benzaldehyde

benzaldehyde

CHO

2.2 Preparation of ketones and aldehydes

2.2.1 Ozonolysis of an alkene
A

X
C C

1. O3
2. Zn/H3O+

C O + O C
Y

2.2.2 Friedel-Crafts acylation of

an aromatic ring
CH3
+ CH3COCl

AlCl3

+ HCl

2.2.3 Oxidation of an alcohol

Primary alcohol to an aldehyde
(or carboxylic acid)
CH3CH2OH

PCC

Mild oxidising agent

CH3CHO

whereas
CH3CH2OH

H2CrO4

CH3CO2H

[CH3CHO]

Secondary alcohol to a ketone

OH
CH3CHCH3

H2CrO4

O
CH3CCH3

Ketones do not undergo further oxidation

Summarising
1 alcohol + mild oxidising agent (PCC)
gives aldehydes
(1 alcohol + strong oxidising agent
(H2CrO4) gives carboxylic acid)
2 alcohol + strong oxidising agent
(H2CrO4) gives ketones

Exercises
Give a reaction scheme for the preparation of
pentanal from

i) CH3CH2CH2CH2CH2OH

PCC

pentan-1-ol

CH3CH2CH2CH2CHO

ii) CH3(CH2)3CH CH(CH2)3CH3

dec-5-ene

1. O3
2. Zn / H3O+
2 CH3CH2CH2CH2CHO

iii)

butan-1-ol Only 4Cs so must add 1 more carbon

CH3CH2CH2CH2OH

SOCl2

To make alkyl chloride

1. HCHO
2. H3O+
CH3CH2CH2CH2CH2OH
PCC

CH3CH2CH2CH2Cl
Mg, ether
To get Grignard
reagent
CH3CH2CH2CH2MgCl
To add another
carbon
Mild oxidising
agent

CH3CH2CH2CH2CHO

2.3 Reaction summary

2.3.1 Reduction to an alcohol using NaBH4

CH CH CHO

1. NaBH4

CH CH CH2OH

2. H2O

Aldehydes are reduced to primary alcohols

Ketones are reduced to secondary alcohols

2.3.2 Nucleophilic addition

Nu-

Nu
+

C O

O
C

Nu

OH
C

Or
..

Consider nucleophilic attack at a carbonyl carbon in

aldehydes and ketones. The relative rates of nucleophile
attack decrease down the table as shown;
O
R1

R1

R2

Compound

methanal

aldehyde

alkyl or aryl

alkyl or aryl alkyl or aryl ketone

R2

fastest

slowest

Decreasing ease of attack by a nucleophile

for both electronic and steric reasons

Addition of a Grignard reagent

(R)

carbon nucleophile; 1. RMgX 2. H3O+

Primary alcohol
HCHO
All other aldehydes

ketones

Secondary alcohol
Tertiary alcohols

Addition of cyanide (a carbon nucleophile)

NC-

CH3
+ C O
CH3

CH3 CN H
C
CH3 O

CH3 CN
H
C
CH3 OH

CH3 COOH
C
CH3 OH

Addition of H2O (oxygen nucleophile)

OH Equilibrium
bit more to
C
OH right for
aldehydes

..
Equilibrium
+
H
2O
C O
to left for
ketones
aldehydes or ketones

Addition of an alcohol
Ketones and aldehydes react with two molar
equivalents of an alcohol in the presence of an acid
catalyst to yield an acetal.

OR

..

C O + 2 ROH

+ H2O

OR
acetal

aldehydes or ketones

Addition initially yields a hydroxy ether called a

hemiacetal (both -OH and -OR bonded to the same
carbon atom), which then reacts with a second
equivalent of the alcohol;

C O + ROH
aldehydes or ketones

H+

OR
C

ROH

OH
hemiacetal

H+

OR
C

+ H2O

OR
acetal

Acetals are important as they can be used as protecting

groups during the synthesis of polyfunctional
molecules. Hemiacetals and acetals are also very
important in biological molecules (e.g. carbohydrates).

Addition of compounds with NH2

(a nitrogen nucleophile).
Ammonia and primary amines react with an
aldehyde or ketone by addition followed by
elimination (of water) to yield an imine.
aldehydes or ketones

OH

..

C O + RNH2

C NR + H2O

NHR

imine

R = H or alkyl

Oximes and hydrazones (imine derivatives) are

prepared by treatment of the aldehyde or ketone with
special amine derivatives (hydroxyl amine and
hydrazines respectively).

C O

H2N R

C N R

+ H2O

aldehydes or ketones

Hydroxylamine
NH2-OH
Hydrazine
NH2-NH2

Compound

-OH

oxime

-NH2 hydrazone

C N OH
C N NH2

2.3.3 Summarising:
CH3CH2
C O
NH2OH
CH3
CH3CH2
C NOH
CH3
H2NNH2
CH3CH2
C NNH2
CH3

CN
CH3CH2
O
C
CN
CH3

CH3CH2
OH
C
CO 2H
CH3

2.3.3 Summarising:
CH3CH2
C O
CH3

H+/
ROH

CH3CH2
OH
C
OR
CH3

1. RMgX
2. H3O+
CH3CH2 OH
C
CH3 R

CH3CH2
OR
C
+
OR
H / ROH
CH3
excess