Mechanism of the Claisen Condensation
Reaction type : Nucleophilic Acyl Substitution
Summary
- The Claisen condensation is the ester analogue of the Aldol condensation.
- Reagents : most commonly the base would be the alkoxide, R'O-
- The reaction involves an ester enolate reacting with another molecule of the ester.
- Remember enolates are good nucleophiles and the ester carbonyl C are electrophilic.
- The products of these reactions are b-ketoesters which are important, useful synthetic intermediates.
- Note that the product is the original ester with an acyl group added i.e. an acylation reaction has occurred.
- A simple example of a Claisen condensation is the reaction of ethyl ethanoate which is shown below in two representations:
Step 1:
First, an acid-base reaction. The alkoxide functions as a base and removes the acidic a-hydrogen giving the reactive ester enolate
First, an acid-base reaction. The alkoxide functions as a base and removes the acidic a-hydrogen giving the reactive ester enolate
Step 2:
The nucleophilic ester enolate attacks the carbonyl C of another ester in a nucleophilic substitution process giving the tetrahedral intermediate.
The nucleophilic ester enolate attacks the carbonyl C of another ester in a nucleophilic substitution process giving the tetrahedral intermediate.
Step 3:
The intermediate collapses, reforming the C=O, resulting in loss of the leaving group, the alkoxide, leading to the b-ketoester product.
The intermediate collapses, reforming the C=O, resulting in loss of the leaving group, the alkoxide, leading to the b-ketoester product.
(nguồn: http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch21/ch21-3-1.html
http://www.mhhe.com/physsci/chemistry/carey/student/olc/graphics/carey04oc/ref/ch21enolatereactions.html)
http://www.mhhe.com/physsci/chemistry/carey/student/olc/graphics/carey04oc/ref/ch21enolatereactions.html)
More than:
The general form of a Claisen condensation is as follows:
![Mechanism of the Claisen Condensation Mechanism of the Claisen Condensation](http://www.chemhelper.com/images/pictures/claisen1.gif)
The first step involves adding a strong base to an ester to generate an enolate at the a carbon (note that the enolate has an additional resonance structure).
![Mechanism of the Claisen Condensation Mechanism of the Claisen Condensation](http://www.chemhelper.com/images/pictures/claisen2.gif)
The enolate can then add to another ester molecule by attacking the carbonyl to make the tetrahedral intermediate. The carbonyl reforms with loss of the alcoxy group to make the b-keto ester.
Example of a Claisen condensation:
![Mechanism of the Claisen Condensation Mechanism of the Claisen Condensation](http://www.chemhelper.com/images/pictures/dieckmann.gif)
This is an example of an intramolecular Claisen reaction, called a Dieckmann condensation.
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