Aldol condensation of Aldehydes, Ketone and Mechanism
Aldol condensation is occurred only in
carbonyl compounds which have
alpha hydrogen atoms and alpha carbon atoms. Both aldehyde and ketone compounds are defined as carbonyl compounds.
Aldol condensation can be used to extend the carbon chain.
The alpha hydrogen in carbonyl compounds has acidic characteristics which is an important fact in this reaction mechanism.
Therefore, those Hydrogen are easily removed with
bases (alkalis) and give carbanion. Then this carbanion reacts with another carbonyl molecule to give the final product, aldol product.
Content
In this tutorial, we study about followings of aldol condensation.
Reagents used and products of the reaction
Alpha Carbon atoms
Alpha hydrogen atoms
Aldol condensation between same aldehyde or ketone
Ethanal aldol condensation
Aldol condensation of propanal
Propanone aldol condensation
Aldol condensation of mixture of different types of aldehydes or ketones
Examples of Aldol condensation of mixture different types of aldehydes or ketones
Aldol condensation of ethanal and propanone
Mechanism of Aldol condensation of aldehyde and ketone
β-hydroxyketone or β-hydroxyaldehyde is given as the product. These compounds contains a hydroxyl group and a carbonyl group.
If these products are heated alone or with Iodine (I2), hydroxyl group is eliminated and form a double bond between carbon
atoms (alkene group).
Alpha Carbon atoms
The carbon atoms where they are existing next to the carbonyl carbon. As example acetaldehyde has one alpha carbon. Propanone has two
alpha carbons. But formaldehyde does not have alpha carbon.
Alpha hydrogen atoms
All Hydrogen atoms existing on alpha carbon (α carbon) atoms are defined as α Hydrogen atoms.
Alpha hydrogen and alpha carbon are required for aldol condensation.
Aldol condensation with same aldehyde or ketone
Aldehyde or ketone which has alpha hydrogen reacts with any strong bases such as NaOH, KOH and
Ba(OH)2 and give aldol as the product. This reaction doubles the number of carbon atoms of initial aldehyde or ketone.
To dehydrate the aldol compound, it is heated alone or with I2.
Ethanal aldol condensation
Ethanal is an aldehyde. Ethanal reacts with dilute NaOH or KOH in
aldol condensation. There are two carbon atoms in ethanal molecule. But in the product,
there are four carbon. After aldol condensation, aldol product is heated with I2 or heated alone. The -OH group is
eliminated (dehydration) and give double bond.
Aldol condensation of propanal
Aldol condensation of propanal also gives an aldol product.
Propanone aldol condensation
Propanone is a ketone. Propanone contains three carbon atoms. After aldol condensation of propanone , there are six carbon
atoms in the carbon chain. First gives the aldol product with dilute NaOH or KOH. Then aldol product is heated alone or heated with
I2. Alcohol group in the aldol product is eliminated (dehydration) by forming a double bond.
Aldol condensation of mixture of different types of aldehydes or ketones
If two or more aldehydes or ketones
are mixed together with strong alkali, it gives a product mixture, not a single product as earlier discussed.
Examples of Aldol condensation of mixture different types of aldehydes or ketones
Mixture of ethanal and propanal with NaOH(aq) gives mixture of four products.
Propanone and propanl also react with KOH(aq) and give four products in the mixture.
Aldol condensation of ethanal and propanone
Both Ethanal and propanone are aldehydes. This ethanal and propanone mixture with NaOH(aq) give four different products
as below.
Steps of formation of four different products
Two carboanions can be given in the initial step (from ethanal and propanone).
One carboanion can attack ethanal or propanone to give two products.
Also other carboanion can attack with ethanal or propanone to give two products.
Four products can be given as a product mixture.
Mechanism of Aldol condensation of aldehyde and ketone
Aldol condensation with dilute strong alkali
Dilue NaOH, KOH, Ba(OH)2 can be used as reagents for aldol condensation. Reaction is stared by OH- ions provided
from strong alkali. At the end of reaction, OH- ions are regenerated again.
Therefore OH- ions are behaved as a catalyst.
Also OH- ions are behaved as nucleophiles.
They can attack at positively charged parts such as carbonyl carbon atom.
Mechanism is very hard and complex to understand in mixture of aldehyde and ketone compounds. So try to understand the first mechanism when
only one aldehyde compound or one ketone compound is in the reaction.
Aldol condensation mechanism steps
Hydroxyl ions attack alpha hydrogen atom in the carbonyl compound. Then bond between alpha hydrogen and alpha carbon is broken and electrons
of that bond are concentrated to alpha carbon. That forms a carbanion. Now that alpha hydrogen atom connects with hydroxyl ion and forms a
water molecule.
Next, carbanion attacks the carbonyl carbon of another molecule of aldehyde or ketone. A new carbon-carbon bond is formed. Due to form of new carbon
- carbon bond, electrons of pi bond (C=O) are transferred towards the oxygen atom to ensure the octal rule for carbon atom and oxygen atom.
Then, oxygen atom will gets a -1 charge.
Finally, -O- attacks a water molecule and get a hydrogen atom to form alcohol group. It forms OH- ion.
Mechanism of Acetaldehyde aldol condensation
Mechanism of Propanone aldol condensation
Summary of aldol condensation
Have Questions?
What aldehydes are unable to do aldol condensation?
Formaldehyde (HCHO) molecule does not have
alpha carbon because it has only one carbon atom. Therefore we cannot do aldol condensation with formaldehyde.
Benzaldehyde has an alpha carbon atom. But that alpha carbon
does not have alpha hydrogen atom. So benzaldehyde also cannot show aldol condensation.
Self condensation of acetaldehyde in acidic medium
In a acidic medium too, self condensation of acetaldehyde is occurred through a different mechanism. Acid behaves as the catalyst.
But, as the product, aldol is not given always. As the reason we can think, in the presence of acidic medium, aldol is dehydrated and
give crotanaldehyde as the product.
What are the all of the aldol products formed between propanal and acetaldehyde in NaOH
Propanal - CH3CHCHO - Aldehyde
Acetaldehyde - CH3CHO - aldehyde
Two carboanions are formed from propanal and acetaldehyde. So, those two carboanions can react with both propanal and acetaldehyde to give
four different products.
Formaldehyde and 4-pentanone aldol condensation
Two carbonyl compounds exist to show the aldol condensation. You know formaldehyde cannot show aldol condensation itself. Therefore,
4-pentanone is the compound which has the capability of producing the nucleophile to start the reaction. Reaction happens as below.
Reaction between 4-pentanone molecules and formed nucleophiles by 4-pentanone molecules
Reaction between formaldehyde molecules and formed nucleophiles by 4-pentanone molecules
What aldehyde does not work in a aldol condensation?
Aldehydes without alpha carbon and alpha hydrogen does not have the ability to do aldol condensation. As examples, formaldehyde and benzaldehyde can be given. Formaldehyde does not have alpha carbon and benzaldehyde does not have alpha hydrogen.
Is aldol condensation is an oxidation - reduction ( redox) reaction?
Yes. In aldol condensation two molecules of carbonyl compound are participated. Alpha carbon of one molecule is oxidized and carbonyl
carbon of other molecule is reduced during the reaction.
Why formaldehyde does not give aldol condensation ?
Formaldehyde does not have an alpha carbon atom. Therefore, there is no alpha hydrogen. Without alpha hydrogen aldol condensation is not occurred.
Is aldol condensation a nucleophilic addition reaction?
Yes. Carbonyl carbon is positively charged and it is attacked by carbanion. And a new carbon group is attached to the aldehyde or ketone.
What will be given when ketone is attacked by NaOH and H2O
A ketone molecule become a carboanion due to attack of OH-. Carboanion attacks the carbonyl carbon atom of another ketone molecule. Water also contribute to the mechanism to form the alcohol group. As the product, a compound which has more carbon atoms than previous ketone is given.
Why benzaldehyde do not react with NaOH to produce aldol product.
To occur the aldol condensation, there should be both alpha hydrogen and alpha carbon atom in the aldehyde or ketone. In the benzaldehyde,
there is an alpha carbon atom. But there is no alpha hydrogen atoms. So benzaldehyde does not have chance to react with dilute NaOH to show aldol condensation reaction.
What about methanal in aldol condensation
Methanal does not have both alpha hydrogen and alpha carbon atom. So there is no possibility for aldol condensation of methanal.
Aldehyde + NaOH products
When only one aldehyde compound is with dilute NaOH, one product is given. If there are two different aldehyde compounds, four different
products are given.
What are the aldol reagents?
Dilute strong alkalis such as NaOH or KOH or Ba(OH)2 are used as aldol reagents.
Reaction of aldehyde and ketone with sodium hydroxide
Mixture of products are given as the result when aldehyde and ketone are together and react with sodium hydroxide.
For aldol condensation, why need H on alpha carbon?
Due to acidity of those hydrogen atoms, these type of reactions are occurred. A base can react with these alpha hydrogen atoms.
methyl ketone and formaldehyde aldol reaction?
Formaldehyde do not have an alpha carbon or alpha hydrogen atoms. Therefore, carbanion cannot be made by formaldehyde. But, formaldehyde can be attached by the carbanion made by methyl ketone compound.
