Esters; Properties - Chemical

Esters gives nucleophilic substitution reactions similar to the acid halides and anhydrides. The
carbonyl carbon in their molecule is electron-deficient owing to the electron- withdrawing effect
of Oxygen and carries a partial positive charge.

However, esters undergo nucleophilic reactions less readily than do acid halides or anhydrides.
This is attributed to the resonance effect.

Thus the delocalization of unshared electron pair on—ÖR , decreases the electron-deficiency of
carbonyl carbon which becomes less prone to nucleophilic attack.

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 Esters; Chemical Reactions
(1- a) Acid Hydrolysis:
Esters when heated with water in the presence of an acid catalyst (H2SO4 or HCl) are hydrolyzed
to give the parent carboxylic acid and alcohol. The reaction is reversible.

MECHANISM:
Step 1: Attack by H+ on oxygen atom of the carbonyl group.

Step 2: Addition of water to electron-deficient carbon.

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 Esters; Chemical Reactions
Step 3. Hydrogen ion transfer:

Step 4. Elimination of alcohol:

Step 5. Regeneration of the catalyst and formation of carboxylic acid:

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 Esters; Chemical Reactions
(1-b) Base Hydrolysis:
The hydrolysis of an ester can also be achieved by refluxing with aqueous solution of a strong
base such as NaOH.
The alkaline/ basic hydrolysis of an ester to form sodium salt of the parent acid and alcohol is called
Saponification (Latin, Sapon = soap), since this type of reaction is used in preparing soaps from fats.

MECHANISM:
Step 1. Attack by HO– on electron-deficient carbonyl carbon.

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 Esters; Chemical Reactions
Step 2: Elimination of :ŌR'

Step 3: Proton transfer to :ŌR'

Step 4: Carboxylate ion in the presence of Na+ ions (from NaOH) gives sodium carboxylate.

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 Esters; Chemical Reactions
(2) Transesterification:
Ester of an alcohol can react with another lower alcohol in the presence of a mineral acid, to
give the ester of second alcohol. The interchange of alcohol portions of the esters is termed
transesterification.
The lower alcohol being more volatile escapes and the reaction proceeds to completion.

(3) Reaction with Ammonia (Ammonolysis):

Esters react with ammonia, often in a solvent such as ethanol, to give amides.

(4) Reduction to Alcohols:

Esters can be reduced to the primary alcohol corresponding to the acid from which it was
derived by lithium aluminum hydride, LiAlH4, or by sodium and alcohol.

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 Esters; Chemical Reactions
(5) Reaction with Grignard Reagents:
Esters react with Grignard reagents to form ketones which at once react with another molecule
of the Grignard reagent to yield a tertiary alcohol.

(6) Claisen Condensation:

Esters that have hydrogen atoms on the α carbon atom undergo condensation reactions to form
β-keto esters, in the presence of a strong base (C2H5ONa).