Ch. 22 - Condensation ChemistrySee all chapters
All Chapters
Ch. 1 - A Review of General Chemistry
Ch. 2 - Molecular Representations
Ch. 3 - Acids and Bases
Ch. 4 - Alkanes and Cycloalkanes
Ch. 5 - Chirality
Ch. 6 - Thermodynamics and Kinetics
Ch. 7 - Substitution Reactions
Ch. 8 - Elimination Reactions
Ch. 9 - Alkenes and Alkynes
Ch. 10 - Addition Reactions
Ch. 11 - Radical Reactions
Ch. 12 - Alcohols, Ethers, Epoxides and Thiols
Ch. 13 - Alcohols and Carbonyl Compounds
Ch. 14 - Synthetic Techniques
Ch. 15 - Analytical Techniques: IR, NMR, Mass Spect
Ch. 16 - Conjugated Systems
Ch. 17 - Aromaticity
Ch. 18 - Reactions of Aromatics: EAS and Beyond
Ch. 19 - Aldehydes and Ketones: Nucleophilic Addition
Ch. 20 - Carboxylic Acid Derivatives: NAS
Ch. 21 - Enolate Chemistry: Reactions at the Alpha-Carbon
Ch. 22 - Condensation Chemistry
Ch. 23 - Amines
Ch. 24 - Carbohydrates
Ch. 25 - Phenols
Ch. 26 - Amino Acids, Peptides, and Proteins
Johnny Betancourt

Condensation reactions are reactions in which two molecules combine to form a larger molecule, producing a small molecule such as H2O as a byproduct. They typically form a new carbon-carbon bond and result from a nucleophilic enolate and an electrophilic carbonyl. 


P.S. Here is the 2-hour super-comprehensive version if you are not in a time crunch. 

Condensation Overview:

There are a few varieties of condensation reactions, and all require those two pieces. Sometimes metal-complex catalysts are added, but luckily most undergrad Orgo classes focus on base-catalyzed mechanisms! You'll likely see these reactions again later in carbohydrate chemistry or in Biology class.

So, how do we actually form an enolate? We have to deprotonate the alpha-carbon of a carbonyl. Remember that alpha-carbons are much more acidic than standard sp3-hybridized carbons! Let’s quickly go over three condensation reactions here:


Mechanism:

Enolate-formationEnolate formation

A base is used to deprotonate the alpha-hydrogen. The type of condensation reaction the resulting enolate undergoes depends on what kind of electrophile is present. 


Aldol Condensation:

Aldol-condensation

Aldol condensation



The aldol condensation reaction occurs between an enolate and an aldehyde to yield a beta-hydroxy ketone. 


Claisen Condensation: 

Claisen-condensationClaisen condensation

The Claisen condensation reaction involves an ester (or diester) and an enolate. It yields a beta-keto ester or a beta-diketone by displacing the acyl group through nucleophilic acyl subsitutition. The above reaction resulted in a beta-diketone. 

Dieckmann Condensation:

The Dieckmann condensation reaction is an intramolecular reaction of a diester. The enolate forms on the alpha carbon of one carbonyl and then directly attacks the other. This forms a ring with a beta-keto ester. 


Two things to note: 1) the products can undergo dehydration to form an enone (an alpha-beta unsaturated ketone) through an E1cB mechanism and 2) these reactions are reversible through hydrolysis! Let's see what each of our products looks like after dehydration:


Dehydrated-condensation-products

Dehydrated condensation products



Detailed Videos:

There are plenty of different types of condensation reactions:




P.S. Congratulations! You just learned a form of polymerization! Carbonyl compounds can combine to form polymers like nylon through this mechanism!


Johnny Betancourt

Johnny got his start tutoring Organic in 2006 when he was a Teaching Assistant. He graduated in Chemistry from FIU and finished up his UF Doctor of Pharmacy last year. He now enjoys helping thousands of students crush mechanisms, while moonlighting as a clinical pharmacist on weekends.