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* Rainer Ludwig Claisen (1851-1930) Developed the “Claisen Condensation” in 1887 What are the building blocks? sp2 orbitals p orbitalsπ bond sp3 orbitals α hydrogens α hydrogens Sites for nucleophilic attacks High Electronegativity of Oxygen Resonance Energy“Stabilization energy” Ethyl propanoate Formation of the enolate Condensationwith ethyl benzoate to form β-keto ester Et -O - C - CH2 – CH3 O|| Loss of 2nd alpha hydrogen on β-keto ester Et -O - C - CH – CH3 O|| - Ethyl Propanoate 0.04 pKa of alpha hydrogens ≈ 24 or Ka ≈ 10-24 Bond Angles 120o sp2 orbitals 109.5o sp3 orbitals 180o sp orbitals 90o p orbitals Overview of the Claisen Condensation Reaction Ethyl Propanoate Ethoxide ion Ethyl Benzoate 1. Ethoxide ion acting as a strong base deprotonates ethyl propanoate. 2. The enolate of ethyl propanoate is formed. 3. The enolate of ethyl propanoate is a strong nucleophile that attacks the partially positive carbon of the carbonyl group on ethyl benzoate. 4. The alpha substitution makes this a carbonyl condensation reaction. 5. A β-keto ester is formed. ?+ 6. The driving force for this reaction is the transfer of the second alpha hydrogen to the ethoxide ion. This is exothermic. Deprotonation of Ethyl Propanoate Resonance The enolate ion is a strong nucleophile and will attack the partially positive carbon of a carbonyl group. ?+ Ethyl Propanoate Ethyl Benzoate Enolate of Self condensation of ethyl propanoate *