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Aldehydes, Ketones and Carboxylic Acids

Aldol Condensation Mechanism & Alpha Hydrogen

Reactions
Aldol Condensation, in organic chemistry, is a condensation reaction of enol aka enolate and
carbonyl compound. When enol ions react with carbonyl compound it forms a β-hydroxyketone
or β-hydroxyaldehyde. This process is followed by dehydration which results in conjugated
enone. And Alpha-hydrogen atom is an atom in which the hydrogen atom is reacted with the
alpha-carbon atom. Similarly, the beta-hydrogen atom is an atom in which the hydrogen atom is
reacted with the beta-carbon atom. Let us learn about different reactions of the alpha-hydrogen
atom.

Table of content

1 Suggested Videos
2 What is Alpha-Hydrogen?
2.1 Browse more Topics under Aldehydes Ketones And Carboxylic Acids
2.2 Acidity of Alpha-Hydrogen Present in Aldehydes and Ketones

3 Aldol Condensation
4 Mechanism of Aldol Condensation
4.1 Aldol Condensation in Aldehydes with Base as a Catalyst
4.2 Mechanism of Aldol Condensation in Ketonic Compounds
5 Cross Aldol Condensation Reaction
6 Other Types of Reactions with α-Hydrogen

6.1 Cannizzaro Reaction

6.2 Electrophilic Substitution Reaction
6.3 Halogenation of Ketones
7 Solved Examples for You

Suggested Videos
 Physical Properties of Carboxylic Acids | Chemistry JEE

Preparation
Preparation of
of Electrophilic
Electrophilic
Physical
Physical Introduction
Introduction and
and Aldehyde
Aldehyde and
and Substitution
Substitution
Properties
Properties of
of structure
structure of
of Ketone
Ketone from
from Reactions
Reactions of
of
Carboxylic
Carboxylic Acids
Acids carboxylic
carboxylic acid
acid Alkynes
Alkynes Carboxylic
Carboxylic Acids
Acids

What is Alpha-Hydrogen?
To understand alpha hydrogen we first need to understand alpha carbon. An alpha carbon is the
first carbon that is joined to the functional group. In the case of aldehydes and ketones, a
functional group is a carbonyl group. The functional group is responsible for the formation of
alpha hydrogen.

Learn more about Carbonyl group here in detail.

The hydrogen present on the alpha-carbon is the alpha-hydrogen and it is slightly acidic in nature
due to the carbonyl group and its resonance stabilization mechanism. Thus, alpha-hydrogen and
its acidic nature are responsible for several different reactions which we will study in this topic.

Browse more Topics under Aldehydes Ketones And Carboxylic Acids

 Chemical Reactions and Uses of Carboxylic Acids

Methods of Preparation of Carboxylic Acids

Nomenclature and Structure of Carbonyl Group

Nomenclature and Structure of Carboxyl Group

Nucleophilic Addition Reaction

Oxidation

Physical properties of Aldehydes, Ketones and Carboxylic Acids

Preparation of Aldehydes

Preparation of Aldehydes and Ketones

Preparation of Ketones

Reactions due to Alpha-Hydrogen

Reduction

Uses of Aldehydes and Ketones

Acidity of Alpha-Hydrogen Present in Aldehydes and Ketones

Due to the acidic property of α-hydrogen in aldehydes and ketones, the compounds undergo
different types of reactions. The acidic property of α-hydrogen in aldehydes and ketones is
because of the high electron-withdrawing capacity of the carbonyl group and resonance
stabilization of the conjugate base.
Aldol Condensation
Aldol reaction happens in aldehydes and ketones if the compounds contain no less than one α-
hydrogen. Therefore, the reaction occurs in the presence of alkali (dilute). The dilute alkali acts
as a catalyst in the reaction and helps in the formation of β-hydroxy aldehydes or aldol and β-
hydroxy ketones or ketol.

This reaction is known as aldol condensation. The reaction derives its name from two different
functional groups namely aldehyde and alcohol because these two products are present in the
reaction. The β-hydroxy aldehydes or aldol and β-hydroxy ketones or ketol lose water molecules
easily to produce α, β-unsaturated carbonyl compounds.

These compounds are aldol condensation products. The products due to ketones in this reaction
are called ketol. However, the general name of the reaction is aldol condensation because they
are fairly similar in their properties with aldehydes.
On mixing with dilute acid or base (aqueous), aldehydes containing α-hydrogen can react with
themselves thereby resulting in the formation of β-hydroxy aldehyde compounds or aldol
compounds. This is because the resulting compound will have a functional group, aldehyde, and
alcohol. Refer to the example below.

Mechanism of Aldol Condensation

The mechanism of aldol condensation initiates with the formation of carbanion intermediate.
Refer to the steps below to observe the mechanism of aldol condensation in the presence of a
base as a catalyst.
Aldol Condensation in Aldehydes with Base as a Catalyst

Step 1: Removal of α-hydrogen from the base

Step 2: The first step results in the formation of carbanion which undergoes a nucleophilic
addition reaction with the carbonyl group present in the second molecule of the aldehyde
(in this case ethanal). The second step results in the formation of the condensation
product.

Step 3: Protonation of alkoxide ion will occur due to reaction with water.

Step 4: Heating of the aldol compound in the basic solution will help in dehydrating the
product to form α β-unsaturated aldehyde compound.
Mechanism of Aldol Condensation in Ketonic Compounds

The reactivity of ketones towards aldol condensation is less in comparison to aldehydes.

However, a small quantity of aldol product formation is possible with the use of acid catalysts in
the reaction. The aldol compound formed will soon dehydrate to form a resonance stabilized
compound. Hence, the dehydration step of aldol condensation in ketonic compounds brings the
reaction to completion.

Aldol condensation by acid catalysis includes two major steps. In the first step conversion of the
ketonic compound to its corresponding enolic form will occur. In the second step, enol will attack
the protonated carbonyl group.

Step 1: Protonation of the oxygen of the carbonyl group occur.

Step 2: The water molecule behaving as a base will remove the acidic α hydrogen leading
to the formation of Enol.

Step 3: The enol attacks a protonated carbonyl group of a second ketone molecule.
Cross Aldol Condensation Reaction
Cross aldol condensation refers to the aldol condensation reaction that occurs in between two
different organic compounds, in this case, two different aldehydes and ketones. Therefore, the
reaction leads to the formation of a series of product. If the α-hydrogen atoms are present in both
aldehyde and ketone, the reaction will produce a mixture of four compounds.

The optimum result of cross aldol condensation reaction is possible if an aldehyde compound
contains α-hydrogen and another aldehyde compound does not contain α-hydrogen. Refer to the
example below to see the reaction with the mixture of ethanal and propanal.
Moreover, cross aldol condensation reaction is also possible if one of the components in the
reaction mixture is a ketone.

Other Types of Reactions with α-Hydrogen

Cannizzaro Reaction

Aldehydes or ketones lacking α-hydrogen atoms can possibly undergo self-oxidation and
reduction reactions on heating with alkali (concentrated). The reaction will result in the reduction
of one aldehyde molecule to alcohol and at the same time oxidation of another aldehyde
molecule to carboxylic acid salt.

Electrophilic Substitution Reaction

This reaction is possible in aromatic aldehydes and ketones at the ring in which the carbonyl
group will behave as the meta-directing and deactivating group.

Halogenation of Ketones

Ketones having the α-hydrogen atom in the presence of a base react to form α-haloketones. For
instance, methyl ketones and iodine reacts in the presence of a base to undergo complete
halogenation reaction.
When sodium hydroxide reacts with iodine, it leads to the generation of sodium hypoiodite in
solution. The reaction will result in the formation of sodium benzoate and iodoform.
Additionally, the iodoform is a pale yellow color solid. Hence, this reaction refers to as iodoform
test in order to detect methyl ketones. Refer to the example below.

Solved Examples for You

Question 1: Select the reaction which will not form a new carbon-carbon bond.

1. Cannizzaro Reaction

2. Wurth Reaction

3. Aldol Condensation

4. Friedel-Crafts Reaction

Solution: Option 1 (Cannizzaro Reaction).