Esterification

Pre Lab Assignment: Complete the pre-lab cover page and develop a procedure. Draw the
mechanism of the reaction you will complete in lab. Use the proper arrow drawing convention
to show all bond making and bond breaking steps in the reaction. Include all intermediates,
including resonance structures.
Learning Goals:
Understand the mechanism of esterification and how it relates to ester hydrolysis.
Understand how column chromatography can be used to separate compounds of
different polarity.
Relate column chromatography to TLC separation
Introduction:
An ester is a functional group where a carbonyl carbon is bonded to an alkoxyl group. These
compounds are commonly found in nature.
O

OCR 1R 2R 3

Generic Ester

methyl butyrate

ethyl 2-methylpropionate

The portion of the molecule in red is the ester f unctionality

Many esters have strong and pleasant odors. The fragrances and odors of flowers and fruits are
usually due to a complex mixture of several different chemicals, including esters, where one
ester typically predominates over the rest. The dominant ester in pineapples is ethyl butyrate,
while methyl butyrate is the predominating ester in apples. Esters are commonly used as
artificial flavors in the food and beverage industry.
Despite pleasant flavors and smells, esters are rarely used in perfumes or other scents designed to
be applied to skin due to their tendency to hydrolyze to the alcohol and acid. Ester hydrolysis,
resulting from the water in perspiration, gives medium chain length fatty acids that smell terrible
(think rancid butter or milk!), defeating the purpose of a perfume.
In this lab you will synthesize isopentyl acetate using isopentyl alcohol and acetyl chloride to
make isopentyl acetate.
OH

Cl

For humans, isopentyl acetate has a characteristic smell that is associated with bananas (hence
the banana oil nickname for isopentyl acetate). Isopentyl acetate is also one of the components
of the honeybee alarm pheromone. Pheromones are compounds secreted by organisms that

affect the behavior of members of the same species. The honeybee alarm pheromone is released,
along with venom, when a honeybee stings an intruder, and signals to other bees to attack the
intruder.
Procedure:
Obtain a hotplate from the stockroom. Prepare your drying tube (see the picture below) by
inserting a piece of cotton up to the bend in the tube using a spatula. Next fill the remaining tube
volume with calcium chloride to 1cm from the end. What is the function of the calcium chloride
in this set up? Place another piece of cotton into the end to keep the calcium chloride from
falling out.

Cotton

CaCl2

Cotton

Combine 200 L of isopentyl alcohol and

800uL of acetyl chloride in your 5mL
conical vial equipped with a conical spin
vane. Assemble the conical vial, a water
condenser and the drying tube and clamp
securely to your hood support bar (As
shown in the picture below).

Stir your reaction mixture for 15 minutes.

Disassemble your condenser and drying tube, being
careful not to spill your reaction. Using forceps,
remove the spin vane from the vial. Add
approximately 1mL of 5% sodium bicarbonate
solution with a Pasteur pipette (caution: bubbling!
What are the bubbles?). Cap the vial and gently mix
without inversion. Re-clamp the vial and wait for the
aqueous and organic phases to separate. Carefully
remove the bottom layer (what is it?) using a Pasteur
pipette and discard. Repeat this procedure three
additional times using 1mL of 5 % sodium bicarbonate
for each wash.
Next, prepare a small silica column by packing a small
piece of cotton into a 5 Pasteur pipette using the tip
of a 9 Pasteur pipette. Once the cotton plug is in
place, add silica gel to a level of 2 cm from the
plugged end of the pipette. Tap the pipette gently on

the bench to pack the silica. Next, add the same amount of anhydrous sodium sulfate (Na2SO4)
(what does this do?) to the top of the silica bed and clamp the pipette to the bench support. Add
one boiling stone to a product vial and weigh (including the cap) the container.
Place this vial under the pipette so the end of the pipette is just below the rim of the vial. Wet
(wet: to add pure solvent to a solid prior to addition of a solution of a compound) the column
with approximately 1 mL of methylene chloride. Next, transfer the crude product solution from
the reaction vial into the column using a pipette. When all the solution has been transferred to
the column, rinse the reaction vial with 500 L of methylene chloride and add this to the column.
When the solvent level in the column has reached the level of the Na2SO4 add another 1 mL of
methylene chloride to the column to make sure all of the product is eluted from the column.
How is this column aiding in the purification process?
Evaporate the solvent from the product vial by heating at 75C until the vial comes to a constant
weight. Youll know if your reaction was successful based on the smell. Transfer to and label a
product vial and place in the glassware container above your fume hood.
Post Lab:
Include what is required in the Lab Expectations handout.
Calculate percent yield for your reaction (this will require you to determine which
reactant is limiting).
Answer the following questions separate from your conclusions.
1. Draw the mechanism of an esterification using an acid chloride and alcohol.
2. Could acetic acid be used in the esterification, instead of acetyl chloride? Why or why
not?
3. Could acetic anhydride be used?
4. Instead of getting your desired product, what would happen if your glassware was wet
before you started the reaction?
5. What is the relationship between TLC and Column Chromatography?
6. What is the limiting reagent in the reaction that you ran? Prove your answer with
limiting reagent calculations in the calculation section of the post-lab.