Química Orgánica 2 · Condensación de Claisen y adición conjugada
3-Phenylpropanoic acid by malonic ester synthesis
Condiciones: NaOEt, EtOH; then H3O⁺, Δ
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Arrastra desde los electrones que se mueven hasta donde van, o toca uno y luego el otro. Cada flecha se revisa; Pista te ayuda cuando te atascas. No necesitas cuenta.
El mecanismo, paso a paso
Siguiente reproduce las flechas curvas de cada paso y las explica. Los pasos escritos están abajo.
Leer los 19 pasos escritos
Form the malonate enolate
Ethoxide removes one of the doubly activated hydrogens of diethyl malonate (pKa ≈ 13).
Las flechas curvas
- Ethoxide's lone pair takes the acidic hydrogen.
- The C–H pair stays on carbon, delocalized onto both esters.
SN2 alkylation with benzyl bromide
The enolate carbon attacks the benzylic CH2 of benzyl bromide from the back side, displacing bromide.
Las flechas curvas
- The enolate carbon forms the new C–C bond.
- The C–Br bond breaks and bromide leaves.
What will leave as CO2?
Planning the malonic ester synthesis.
Protonate the carbonyl of the first ester
Hydronium protonates the carbonyl oxygen of the first ester, making its carbon much more electrophilic toward weakly nucleophilic water.
Las flechas curvas
- A carbonyl oxygen lone pair takes a proton from hydronium.
- The O–H pair returns to oxygen, releasing water.
Water adds to the carbonyl carbon
Water attacks the activated carbonyl carbon, giving a tetrahedral intermediate with a positively charged oxygen.
Las flechas curvas
- A water lone pair forms the new C–O bond.
- The C=O π pair moves onto the protonated oxygen, neutralizing it.
Deprotonate the added water
Water removes a proton from the oxonium oxygen, giving a neutral tetrahedral intermediate.
Las flechas curvas
- Water's lone pair takes the oxonium proton.
- The O–H pair stays on oxygen.
Protonate the ethoxy oxygen
Hydronium protonates the ethoxy oxygen, turning it into a good leaving group (neutral ethanol).
Las flechas curvas
- The ethoxy oxygen lone pair takes a proton from hydronium.
- The O–H pair returns to oxygen as water.
Expel ethanol
An OH lone pair re-forms the C=O bond and pushes out ethanol.
Las flechas curvas
- An oxygen lone pair forms the C=O π bond.
- The C–O bond breaks and ethanol leaves.
Deprotonate to the carboxylic acid
Water removes the proton from the protonated carbonyl, giving the neutral carboxylic acid and regenerating hydronium.
Las flechas curvas
- Water's lone pair takes the proton.
- The O–H pair stays on oxygen, giving C=O.
Protonate the carbonyl of the second ester
Hydronium protonates the carbonyl oxygen of the second ester, making its carbon much more electrophilic toward weakly nucleophilic water.
Las flechas curvas
- A carbonyl oxygen lone pair takes a proton from hydronium.
- The O–H pair returns to oxygen, releasing water.
Water adds to the carbonyl carbon
Water attacks the activated carbonyl carbon, giving a tetrahedral intermediate with a positively charged oxygen.
Las flechas curvas
- A water lone pair forms the new C–O bond.
- The C=O π pair moves onto the protonated oxygen, neutralizing it.
Deprotonate the added water
Water removes a proton from the oxonium oxygen, giving a neutral tetrahedral intermediate.
Las flechas curvas
- Water's lone pair takes the oxonium proton.
- The O–H pair stays on oxygen.
Protonate the ethoxy oxygen
Hydronium protonates the ethoxy oxygen, turning it into a good leaving group (neutral ethanol).
Las flechas curvas
- The ethoxy oxygen lone pair takes a proton from hydronium.
- The O–H pair returns to oxygen as water.
Expel ethanol
An OH lone pair re-forms the C=O bond and pushes out ethanol.
Las flechas curvas
- An oxygen lone pair forms the C=O π bond.
- The C–O bond breaks and ethanol leaves.
Deprotonate to the carboxylic acid
Water removes the proton from the protonated carbonyl, giving the neutral carboxylic acid and regenerating hydronium.
Las flechas curvas
- Water's lone pair takes the proton.
- The O–H pair stays on oxygen, giving C=O.
Decarboxylate through a cyclic transition state
On heating, the β-carbonyl oxygen takes the carboxyl proton while CO2 leaves, all in one six-membered cyclic step. This gives carbon dioxide and an enol.
Las flechas curvas
- The C=O π pair of the β-carbonyl bonds to the carboxyl hydrogen.
- The O–H pair becomes the second C=O of carbon dioxide.
- The C–C bond pair becomes the C=C π bond of the enol.
Protonate the enol on carbon
Hydronium protonates the enol at its α-carbon, giving a protonated carbonyl.
Las flechas curvas
- The enol oxygen lone pair forms a C=O π bond as the C=C π pair leaves.
- The enol C=C π pair bonds to a proton from hydronium.
- The O–H pair returns to oxygen as water.
Deprotonate oxygen
Water removes the O–H proton, completing the tautomerization to the carboxylic acid.
Las flechas curvas
- Water's lone pair takes the O–H proton.
- The O–H pair stays on oxygen, forming the C=O bond.
3-Phenylpropanoic acid
The product is 3-phenylpropanoic acid: the malonate supplied the CH2–COOH unit and benzyl bromide the benzyl group; one carboxyl carbon left as CO2.
Qué vas a practicar
Draw the malonic ester synthesis of 3-phenylpropanoic acid: benzylation of the malonate enolate, hydrolysis of both esters, decarboxylation and tautomerization.
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