Baseninduzierte Esterhydrolyse unumkehrbar?

Auf Wikipedia steht, dass die Baseninduzierte Esterhydrolyse NAHEZU unumkehrbar ist?!
Was heißt nahezu?
Wie oder unter welchen Umständen ist sie denn reversibel?

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pchem
11 months ago

The acid ester hydrolysis is reversible. Both the back and back reaction first require protonation. Subsequently, the deprotonation occurs again. Since protons are always available under acidic conditions in order to initiate either the back- or back-reaction, a chemical equilibrium is present here. The acid used for this reaction is in fact a catalyst here, since the protons are re-formed at the end of each reaction:

The basic ester hydrolysis ( hydrolysis) proceeds via another mechanism. Hydroxide ions enter into the reactions, but they are not re-formed, but instead alkholate ions. This is why it makes sense to speak of base-induced and not of base-catalyzed. This is also an equilibrium reaction:

Alcoholates are generally more powerful bases than carboxylates. For comparison: Hydroxide has a pKb value of -1.74, acetate of 9.25 and ethanolate of -1.9. The carboxylic acid formed thus does not retain its proton, but is deprotonated by the alcoholate and this step is irreversible. However, since the reaction requires a carboxylic acid, it cannot take place. In theory, the pure formation of the carboxylic acid is reversible. However, since this reaction is inevitably followed by an irreversible step, this leads to the entire hydrolysis becoming irreversible.

pchem
11 months ago
Reply to  Jeremy Edberg

The “nearly” means that the esterification can take place in principle. In the sense that there is no large thermodynamic barrier here that makes this step impossible under normal conditions. A carboxylic acid (not the carboxylate) is formed with alcoholate in small amounts. This, however, again immediately hydrolyses, driven by the fact that, at the same time, carboxylic acid is continuously removed from the equilibrium by deprotonation. Efficient esterification is thus nevertheless not possible.