Aldehyde & Ketone

Reactions
 Formation of an Aldehyde
Oxidation of Primary Alcohols
General equation:
Primary alcohol aldehyde

RCH2CH=O

EXAMPLE:
1-propanol
 Formation of a Ketone
Oxidation of Secondary Alcohols
General equation:
Secondary alcohol ketone
R
O [O] O
C H
R-C-R
R
H

EXAMPLE:
2-propanol
 Review from Chapter 13!!
Oxidation of Tertiary Alcohols
General equation:
Tertiary alcohol NO REACTION!!!
 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 Carboxylic acid
[O] [O]
1-butanol

[O] [O]
2-methyl-1-propanol
 Reduction Reactions
Both aldehydes and ketones are easily
reduced back to the corresponding alcohol.
This process is called hydrogenation.
OH
O H Catalyst
+ R1 R2
H
R1 R2 H
 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 ) +
3 2 R-C-O- + Ag0

Aldehyde silver ammonia carboxylic

silver
complex acid anion metal
Tollens Reagent mirror
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 -CH OH + Cu2O
2
H H OH OH red precipitate
 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 alcohol Hemiacetal (quite reactive)

OR2
H+ R1-C-OR2
H
Acetal
 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+ R1-C-OR3
R2
Ketal
 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 tautomers.
1 1
R O R OH

2 3 2 3
R R R R

Keto form 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 is formed in the process.
OH O
-
O O OH or 1

R
1 + R
2 R
enzyme 2
R
Aldehyde Aldehyde 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 OH HO O
+

Butanal Butanal (enol form) - - -

3 hydroxy 2 ethylhexanal