CHEMISTRY

ACTIVITY
Atharva Kale
Class XII
 ALDOL
CONDENSATION
ATHARVA KALE
CLASS 12 CHEMISTRY
 Index

1. What is aldol condensation

2. Discovery of aldol condensation and discovery
3. Types of Aldol condensation
4. Reaction mechanism
5. Reactions Associated with aldol condensation
6. Advantages of Aldol Condensation
7. Practical Application
What is Aldol condensation
 The Aldol condensation is a fundamental
organic reaction in which an enol or
enolate reacts with a carbonyl compound
(aldehyde or ketone) to form a β-
hydroxyaldehyde or β-hydroxyketone,
respectively. The reaction is named after
two compounds involved in the process:
aldehyde (Ald-) and alcohol (-ol).
The reaction can be represented as follows:
:-For aldehydes: RCHO + R'CHOH →
RCH(OH)CHRR' + H2O
:-For ketones: R2C=O + R'CHOH →
R2C(OH)CHRR' + H2O
 In this reaction, the enol or enolate acts
as a nucleophile attacking the carbonyl
carbon of the aldehyde or ketone,
resulting in the formation of a new
carbon-carbon bond and a hydroxy group
(-OH) at the β-position (the carbon
adjacent to the carbonyl carbon). The
reaction generally occurs under basic or
acidic conditions, and the type of
catalyst used can influence the reaction
rate and selectivity.
Discovery of aldol
condensation and how was it
discovered
 The Aldol condensation is a valuable
reaction in organic synthesis as it
provides a way to form carbon-
carbon bonds and introduce
functional groups in a single step. It
has applications in the preparation of
complex molecules, such as natural
products, pharmaceuticals, and
various other organic compounds.
However, it is important to consider
side reactions like the formation of
enolates, dehydration, and self-
condensation, which may affect the
selectivity and yield of the desired
product.
 The discovery of the Aldol
condensation is attributed to the
French chemist Charles-Adolphe
Wurtz. He first reported this reaction
in 1872. Wurtz was a prominent
chemist known for his significant
contributions to the field of organic chemistry. The
reaction was named "Aldol" by combining the names of
aldehyde and alcohol, which are involved in the process.
Yes, Charles-Adolphe Wurtz, the same chemist credited
with the discovery of Aldol condensation, is also
associated with the development of the Wurtz reaction.
The Wurtz reaction is named after him and was first
described by Wurtz in 1855.

About the thought of discovery

The discovery of the Aldol condensation happened during

Wurtz's research on the reactions of aldehydes and
ketones. He observed that when aldehydes or ketones
were treated with bases, such as hydroxides, they
underwent a condensation reaction to form new
compounds that contained both aldehyde and alcohol
functional groups. The original experimental setup for
the Aldol condensation involved the use of aldehyde or
ketone, a base, and an appropriate solvent. Wurtz's
findings provided new insights into the chemistry of
carbonyl compounds and expanded the possibilities for
the synthesis of complex organic molecules.
Types of Aldol condensation
 There are three main types of Aldol
condensation reactions:
1) Crossed Aldol condensation: Involves the
reaction between two different carbonyl
compounds, usually an aldehyde and a ketone, to
yield a β-hydroxy carbonyl compound.
2) Intramolecular Aldol condensation: Occurs
when a molecule contains two carbonyl groups
that can react with each other to form a cyclic
compound.
3) Claisen-Schmidt condensation: A special type
of crossed Aldol condensation involving the
reaction between an aldehyde or ketone and an
aromatic compound containing an α-hydrogen,
often in the presence of a base.
 The Aldol condensation is a valuable reaction
in organic synthesis as it provides a way to
form carbon-carbon bonds and introduce
functional groups in a single step. It has
applications in the preparation of complex
molecules, such as natural products,
pharmaceuticals, and various other organic
compounds. However, it is important to
consider side reactions like the formation of
enolates, dehydration, and self-condensation,
which may affect the selectivity and yield of
the desired product.
Reaction mechanism
 The Aldol condensation reaction involves
several steps in its mechanism. The
reaction can proceed via either an
enolate mechanism or an enol
mechanism, depending on the reaction
conditions and the nature of the starting
materials. Here, I'll describe the enolate
mechanism, which is the most common
pathway for Aldol condensation under
basic conditions:
 Formation of the enolate: The first step
is the deprotonation of one of the α-
hydrogen atoms adjacent to the carbonyl
group of the carbonyl compound
(aldehyde or ketone) by a base (e.g.,
hydroxide ion, alkoxide ion, or ammonia).
This results in the formation of an
enolate ion, which is a resonance-
stabilized carbanion.
 For an aldehyde (RCHO): RCHO + Base (B)
→ RCH(O^-) + B-H
 For a ketone (R2C=O): R2C=O + Base (B)
→ R2C(O^-) + B-H
 Nucleophilic attack: The enolate ion acts as a
nucleophile and attacks the electrophilic carbon of
another carbonyl compound (aldehyde or ketone).
This step leads to the formation of a new carbon-
carbon bond.
RCH(O^-) + R'CHO → RCH(OH)CHRR' (enolate
intermediate)
 Proton transfer: The enolate intermediate formed
in the previous step is protonated by the base (or a
solvent molecule) to yield the β-hydroxy carbonyl
compound (aldol) and regenerate the base.
RCH(OH)CHRR' + B-H → RCH(OH)CHRR' + Base (B)
 Tautomerization (optional): The aldol product can
undergo tautomerization to convert from the enol
form to the keto form or vice versa, depending on
the reaction conditions.
The overall reaction can be summarized as follows:
 For aldehydes: RCHO + R'CHOH → RCH(OH)CHRR'
(aldol) + Base (B)
 For ketones: R2C=O + R'CHOH → R2C(OH)CHRR'
(aldol) + Base (B)
 It's important to note that the reaction conditions,
such as the choice of base and solvent, as well as
the steric and electronic effects of the reactants,
can influence the reaction mechanism and the
selectivity of the Aldol condensation. Additionally,
under acidic conditions, the enol mechanism might
be favored instead of the enolate mechanism.
Reactions associated to aldol reaction
Aldox Process:-
 In industry the Aldox process developed by Royal
Dutch Shell and Exxon, converts propylene and
syngas directly to 2-Ethylhexanol via
hydroformylation to butyraldehyde, aldol
condensation to 2 ethylhexenal and finally
hydrogenation.In one study crotonaldehyde is
directly converted to 2-ethylhexanal in a palladium /
Amberlyst / supercritical carbon dioxide system
Perkin Reaction
 The Perkin reaction is an organic reaction developed
by William Henry Perkin that can be used to make
cinnamic acids by the aldol condensation of aromatic
aldehydes and acid anhydrides in the presence of an
alkali salt of the acid
Meerwein-Ponndorf-Verley Reaction

 The Meerwein-Ponndorf-Verley Reduction in organic

chemistry is the reduction of ketones to secondary
alcohols with aluminumisopropylate catalysis in
isopropanol solution
 Reduction of a ketone 1 to the alcohol 3 in the
presence of aluminumisopropylate 2.

Mechanism

 First the carbonyl-oxygen coordinates to the

aluminumisopropylate 2. This makes the carbonyl-
carbon even more positive. In the next step the
hydride attacks the carbonyl-carbon and a 6-membered
cyclic transition state is formed. After the hydride shift
the alcoholate of the desired alcohol 5 and acetone 6
remain. The alcoholate reacts with another isopropanol
molecule to form the alcohol 3 and recover the
Aluminumisopropylate
 All of these reactions are reversible, and complete
conversion can be achieved by employing excess
alcohol as the reaction solvent or by removal of
acetone from the reaction mixture by distillation.
 The same process in the opposite direction is called
Oppenauer oxidation
 Aldol condensation
Advantage
 The discovery of Aldol condensation was driven
by the need to develop new and efficient
methods for the synthesis of complex organic
molecules. Organic chemists have always been
interested in finding ways to build more
complex compounds from simpler starting
materials. Aldol condensation provided a
powerful tool for creating carbon-carbon bonds
and introducing functional groups in a single
step, which greatly expanded the possibilities
for organic synthesis.
 The Aldol condensation reaction has several
important advantages that make it valuable for
organic chemists:
 Carbon-carbon bond formation: The reaction
allows for the formation of a new carbon-
carbon bond, which is a key step in building
more complex organic molecules. This bond
formation is important for the synthesis of a
wide range of compounds, from
pharmaceuticals to natural products and
various other organic materials.
 Efficiency: Aldol condensation allows for the creation
of two functional groups (aldehyde and alcohol) in a
single step, reducing the number of synthetic steps
required and making the overall synthesis more
efficient.
 Stereoselectivity: Depending on the reactants and
reaction conditions, Aldol condensation can exhibit
stereoselectivity, leading to the formation of specific
stereoisomers. This stereoselectivity is valuable for
controlling the stereochemistry of the final product.
 Natural product synthesis: Aldol condensation has
been particularly useful in the synthesis of many
natural products, which often have complex structures
and functional groups that can be efficiently
assembled using this reaction.
 Overall, the discovery of Aldol condensation provided
chemists with a powerful tool to construct complex
molecules more efficiently, enabling the synthesis of a
wide range of compounds that have significant
practical applications in medicine, agriculture,
materials science, and many other fields.
Use in practical world

. Industries that might utilize Aldol

condensation in their research and
development or manufacturing processes
include:
 Pharmaceutical industry: Aldol condensation
is a valuable tool in the synthesis of
pharmaceutical compounds. It can be used to
construct complex molecules that are
important for drug development.
 Finechemicals and specialty chemicals:
Companies involved in the production of
specialty chemicals or high-value-added
compounds may use Aldol condensation in
their synthesis routes.
 Agrochemicalsindustry: Aldol condensation
can be employed in the synthesis of certain
agrochemical compounds used in agriculture.
 Fragrance and flavor industry: Some aroma
compounds and flavoring agents may be
synthesized using Aldol condensation.
 Polymer industry: Although Aldol
condensation is not a primary method for
polymer synthesis, it can be used in the
preparation of certain monomers or precursor
compounds.
 Academic and research institutions: Aldol
condensation is a fundamental reaction
widely used in laboratories for the
preparation of various organic compounds and
in the study of organic chemistry.
 It's
important to note that while Aldol
condensation is a well-known reaction, its
application may vary depending on the
specific needs of a company or research
project. Various other chemical reactions and
processes are also used in these industries,
depending on the desired end products.
Experiment:-

Experiment Aim: Synthesizing a Perfume

Compound via Aldol Condensation
Materials:
 Benzaldehyde
 Acetone
 Sodium hydroxide (NaOH) solution (10%
w/v)
 Ice bath
 Distillation setup
 Separatory funnel
 Drying agents (e.g., anhydrous
magnesium sulfate)
 Perfume bottles or vials
Procedure:
 Preparation: Set up the required apparatus for
distillation and a separatory funnel. Ensure all
glassware is clean and dry.
 Preparation of Reagents: Prepare a 10% w/v
sodium hydroxide solution by dissolving 10
grams of sodium hydroxide in 100 mL of water.
Measure out the required amounts of
benzaldehyde and acetone.
 Aldol Condensation:
 In a small round-bottom flask, mix
benzaldehyde (0.5 mol) and acetone (0.5
mol).
 Place the flask in an ice bath to control the
reaction temperature.
 Adding NaOH Solution:
 Gradually add the 10% sodium hydroxide
solution dropwise to the flask while stirring
vigorously. This will catalyze the aldol
condensation reaction.
 Heating and Reflux:
 Carefully set up the apparatus for
distillation. Attach a condenser and a
receiving flask.
 Gently heat the reaction mixture to initiate
the aldol condensation. As the reaction
progresses, the mixture may start to reflux.
  Continue refluxing for a specific period (e.g.,
1-2 hours) while monitoring the progress of
the reaction. The solution may become
darker as the new perfume compound forms.
 Workup:
 After the desired reaction time, remove the
heat source and allow the reaction mixture
to cool.
 Carefully transfer the reaction mixture to a
separatory funnel and add water to extract
the perfume compound.
 Separation and Drying:
 Shake the separatory funnel gently to mix
the layers, then allow the layers to separate.
The perfume compound should be present in
the organic layer.
 Transfer the organic layer to a dry container
and add a small amount of drying agent
(e.g., anhydrous magnesium sulfate) to
remove any remaining water content. Stir
and let it stand for a short period.
 Isolation:
 Filter the mixture to remove the drying
agent.
 Distillation:
 Set up a distillation apparatus to purify the
synthesized perfume compound. Collect the
fraction that boils at the appropriate
temperature.
 Bottling:
 Once the purified perfume compound is
obtained, carefully transfer it to perfume
bottles or vials. Seal the bottles to prevent
evaporation.
Observation:
 Perfume fragrance obtained

Note:
 Remember that this is a simplified outline and
the actual process can be more complex,
involving optimizations and variations depending
on the specific compounds being synthesized and
the desired fragrance profile. Additionally, safety
precautions, such as proper ventilation,
protective equipment, and adherence to local
regulations, should always be observed when
working with chemicals. It's also important to
consult reliable sources and literature for
detailed protocols tailored to your specific goals.
Bibliography

Here is a bibliography for Aldol condensation, a

fundamental reaction in organic chemistry:
 Aldol Reaction - Comprehensive Organic Name
Reactions and Reagents:
https://doi.org/10.1002/9780470638859.conrr003 This
is a comprehensive reference for the Aldol reaction and
its various aspects.
 Aldol Condensation - Organic Chemistry Portal:
https://www.organic-chemistry.org/namedreactions/al
dol-condensation.shtm
The Organic Chemistry Portal provides a useful
overview and references for the Aldol condensation
reaction.
 Carey, F. A., & Sundberg, R. J. (2007). Advanced
Organic Chemistry, Part B: Reaction and Synthesis (5th
ed.). Springer. This textbook contains detailed
information on the Aldol condensation reaction, its
mechanisms, and applications.