Aldehyde & Ketone

Reactions

Formation of an Aldehyde
Oxidation of Primary Alcohols
General equation:
Primary alcohol
RCH2CH=O
EXAMPLE:
1-propanol

aldehyde

Formation of a Ketone
Oxidation of Secondary Alcohols
General equation:
Secondary alcohol
R
O
[ OO]
C
H
R-C-R
R

EXAMPLE:
2-propanol

ketone

Review from Chapter 13!!

Oxidation of Tertiary Alcohols
General equation:
Tertiary alcohol
REACTION!!!

NO

YOU TRY THESE!

Write an equation showing the
oxidation of the following alcohols.
Be sure to name the product formed.
(a) 1-pentanol
(b) 2-butanol

Oxidation of Aldehydes
Aldehydes are easily oxidized further
to form carboxylic acids.
Oxidation process:
Primary alcohol Aldehyde
]
[O ]
Carboxylic [ Oacid
1-butanol
[O ]

2-methyl-1-propanol

[O ]

Reduction Reactions

O
H
O+H
C
a
t
a
l
y
s
t
R
R
1
2
H
H
R
1R
2

Both aldehydes and ketones are

easily reduced back to the
corresponding alcohol. This process
is called hydrogenation.

Lab Tests for

Aldehydes and Ketones
Tollens Test
Tests for ALDEHYDES (not ketones)
Silver ion is reduced to silver metal
The aldehyde is oxidized to a
carboxylic acid anion
AKA the Silver Mirror Test

Tollens Test
O
O
R-CH
+
Ag(NH ) +
O+ Ag0
3

R-C-

Aldehyde
silver ammonia
carboxylic
silver
complex
acid anion
metal

Write equations for the following

reactions
1. ethanal + Tollens reagent

2. 2- pentanone + Tollens reagent

3. propanal + Tollens reagent

Benedicts Test
Indicates the presence of an
aldehyde
A buffered aqueous solution of
copper (II) hydroxide and sodium
citrate
Reacts to oxidize aldehydes
Forms a red solid Cu2O

Benedicts Test
All sugars are aldehydes or ketones
Benedicts solution can be used to
test urine for glucose (an aldehyde),
which is common in uncontrolled
diabetes
The amount of red precipitate formed
is directly proportional to the amount
of glucose in the urine.

Benedicts Test
O OH OH H
H
HC C - C - C - C - CH2OH + 2Cu+2
H H OH
OH
(from
Benedicts Solution)

O OH OH H H
O - C - C - C - C - C -CH2OH
H
H OH OH
precipitate

+ Cu2O
red

Addition Reactions
I. Addition of an Alcohol to an Aldehyde Acetal
formation
O H
H+
OH
H
R1-C-H
+
O-R2
R1-C-OR2
+
O-R2
H
Aldehyde

H+

alcohol

OR2
R1-C-OR2
H

Acetal

Hemiacetal (quite reactive)

Addition Reactions
-OR group is an alkoxyl group
Hemiacetals are very reactive, so in
the presence of acid and excess
alcohol, will continue to react to form
an acetal

Addition Reactions
2. Addition of an alcohol to a ketone KETAL
formation
O
H
OH
H
R1-C-R2 +
O-R3 H+
R1-C-OR3
+
OR3
R2
Ketone

alcohol

Hemiketal

OR3
H+

R2
Ketal

R1-C-OR3

Practice Problems
Propanal + Methanol

3-hexanone + ethanol

Keto-Enol Tautomers
Many aldehydes & ketones exist in a
mixture of two constitutional
isomers, informally referred to as
1
1
tautomers.
R
O
R
OH

R
Keto form

R
Enol form

Practice
Draw the enol form of the aldehydes
and ketones listed below.
Ethanal
2-pentanone
Butanal

Aldol Condensation
Reaction in which aldehydes &
ketones react to form larger
molecules. A new carbon-carbon
bond isO formed in the Oprocess.
O H -or
1
R

Aldehyde

OH

enzym e
Aldehyde

R
Aldol

Actually occurs between an aldehyde

in the keto form and one in the enol
form.

Example
Write an equation for the aldol
condensation of two molecules of
butanal.
O

Butanal

HO

OH

Butanal (enol form)

- -

3 hydroxy 2 ethylhexanal