Experiment 13:

Synthesis of Esters via

Nucleophilic Acyl Substitution
Pre-lab and Post-lab Discussion + Experimental Results
Pre-Lab Discussion
Esters
• General formula: RCOOR’
• The names of esters are derived from the names of the alcohol (with
the ending -yl) and the acid (with the ending -ate or -oate). The
portion of the name derived from the alcohol comes first:
tert butyl aclhohol

propanoic acid
Esters
• Synthesis of esters are usually carried out via a reversible nucleophilic
acyl substitution of a carboxylic acid and an alcohol. The reactions is
usually catalyzed by a small amount of concentrated strong acid such
as HCl or H2SO4.
Uses
• Esters are responsible for the aroma or flavor of almost any fruit.
These organic compounds can be either natural or synthetic.
Synthetic esters are usually added to food or beverages to enhance its
flavor.

synthecic
Uses
• Esters are polar, but lacking of essential hydrogen attached to oxygen,
therefore cannot form strong hydrogen bonds to each other.

• Most low-molecular weight esters can be used as solvents with

intermediate polarity.
intermediate polarity lang kasi it lacks a hydrogen unlike sa COOH
nasa boiling flask ang reactants + strong acid secured thru a condenser, open ang nasa top water in closest to the boiling flask; water out kay malapit
dun sa pen thing

lqidui iwll vaporze but will condense back to reaction; usually volatile and reactants basta liquid

Experimental Results
General Experimental Procedure
• Synthesis of each esters are done under REFLUX SET-UP.
• Mix the reactants in a 25-mL round-bottom flask, then add boiling
chips (should not be calcium carbonate).

Flavor Alcohol Volume, mL Acid Volume, mL

Banana 2-Pentanol 9.77 Acetic acid 3.43

Mint Hexanol 11.21 Acetic acid 3.43

Peach Benzyl alcohol 9.36 Acetic acid 3.43

General Experimental Procedure
• Carefully add 3-4 drops of concentrated H2SO4 while gently stirring.
• Heat the mixture under reflux for 45-60 mins, then cool mixture to
room temperature.
• Pour mixture into 30-mL separatory funnel. Rinse the reaction flask
with cold-distilled water then transfer to the separatory funnel.
Repeat until the aqueous layer is twice the volume of organic layer.
Shake and allow to separate.
• Separate layers and discard the aqueous layer. Collect the synthesized
ester into a 50-mL beaker and add NaHCO3 until completely
neutralized.
General Experimental Procedure
• Decant the organic layer into a 25-mL Erlenmeyer flask and add a
spatula-full of anhydrous Na2SO4 until no more clumps are formed
and the organic layer is clear.
• Distill the crude ester product, and determine its boiling point
temperature.
• Weigh the ester and calculate for percent yield.
Result
• Hexyl acetate – colorless, minty, apple-like scent.

• Benzyl acetate – watery-white liquid, sweet and pleasant aroma,

peach scent.

• 2-pentyl acetate – colorless, banana scent.

Post-Lab Discussion
Synthesis of Esters via Nucleophilic Acyl
Substitution
• Carboxylic acids react with alcohols to form esters through a
condensation reaction known as esterification.
• Reversible, Acid-catalyzed.
Synthesis of Esters via Nucleophilic Acyl
Substitution
• Steric factors strongly affect the rate of esterification. Large groups
near the reaction site, whether the alcohol or the acid, slow the
reaction in general.
• For example, tertiary alcohols reacts so slowly in acid catalyzed
esterification that they usually undergo elimination instead.
• Synthesis of these type of esters are usually done with acyl chlorides
or anhydride precursors instead of carboxylic acids to increase ester
yield.
Maximizing Ester Yield
• To maximize the yield, the nucleophile (alcohol) was added in excess, while
the acid component is the limiting reagent. This would ensure the reaction
would proceed forward.

• Esterification is a reversible reaction with water as its by-product.

Introduction of water into the synthesis and purification should be
minimized as much as possible to prevent hydrolysis of the ester product.

• Pure alcohol and concentrated carboxylic is preferred in the synthesis to

prevent addition of water.
Maximizing Ester Yield
• Concentrated acid – to catalyze the reaction, little to no amount of water is
introduced in the reaction.

• Solid NaHCO3 – to neutralize the excess acid. This is preferred over NaOH
since the effervescence would signal if neutralization is complete.

• Anhydrous Na2SO4 – drying agent, to remove excess water.

• Distillation – to separate the ester from the excess alcohol. Purification

process.