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.

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:

Esters are common in nature,

they are formed from a
condensation reaction between an
alcohol and a carboxylic acid
derivative. They consist of a
carbonyl carbon bound to an alkoxy
group. Esters give flowers their
pleasant aromas and fruits their
tastes. Most flavors and aromas
consist of a mixture of many
different esters however; one ester
that predominates. The difference
of the smells and tastes are derived
from how they fit in your taste and
olfactory receptors. Slight changes
in the chemical structure of an ester
can result in dramatically differing
tastes, because of this esters are
used as flavorings in food and
beverages. Examples of this can be
found in pineapples and apples,
pineapples gain their taste and
smell from ethyl butyrate whereas
apples gain their smell and taste
from methyl butyrate (see Figure
1).
Despite the pleasant nature of
esters, they are seldom used in
products applied to skin. The low
pH of skin combined with body
heat facilitate hydrolysis of esters in to carboxylic acids with small carbon chains and alcohols
that smell vinegar and rancid milk, thus defeating the purpose of application.
In this lab you will synthesize isopentyl acetate using isopentyl alcohol and acetyl chloride
to make isopentyl acetate.

For humans, isopentyl acetate has a characteristic smell that is associated with bananas
(thus isopentyl acetate is nicknamed banana oil).

Lab setup:
Isopentyl acetate is a component of honeybee alarm pheromones. Pheromones are compounds
that when released affect the behavior of members of the same species. If this compound is spilled
on an item, it can cause bees to attack the item. If you spill it on you wash your hands and flush
with water for ten minutes.
Procedure:
1.) Obtain a hot plate and an aluminum block
from the stock room. CaCl2
2.) Prepare a drying tube by inserting a piece of
cotton up to the bend of the tube using a
spatula. Next fill the tube with ~1 cm of
calcium chloride (CaCl2) and plug with
cotton as shown in Figure 2.
3.) Obtain a 5 ml conical vial with a spin vane.
4.) Add to the vial 200 l of isopentyl alcohol Cotton Plug
and 800 l of acetyl chloride.
5.) Place the vial in the largest hole in the
aluminum block and clamp to a ring stand in
your hood with a three-fingered clamp.
Figure 2: proper setup of a drying tube.
6.) Attach to the top of the vial a reflux
condenser with a drying tube and secure to
the ring stand in your hood.
7.) Stir reaction mixture for 15 minutes at room temperature with water flowing through the
condenser.
8.) Carefully disassemble you condenser and use a forceps to remove the spin vane from your
reaction mixture.
9.) Slowly add ~1 ml of a 5% sodium bicarbonate solution via Pasteur pipette.
10.) Cap the vial and gently mix the vial and let the layers separate.
11.) Using a Pasteur pipette carefully remove the bottom layer with a Pasteur pipette and discard
in the waste container.
12.) Repeat steps 9 11 three additional times.
13.) Prepare a silica gel column by packing a small piece of
cotton down a 5 Pasteur pipette using the tip of a 9
Pasteur pipette (see Figure 3.).
14.) Once the cotton plug is in place add ~3 cm of silica gel
to the Pasteur pipette make sure to tap the pipette gently
against the bench top to pack it down uniformly.
a. Caution silica gel can aerosolize and irritate your
lungs if you breathe it in.
15.) After packing down the silica gel bed, carefully overlay
~2 cm of sodium sulfate (Na2SO4) to the pipette.
16.) Clamp your pipette to the ring stand in your hood.
17.) Prepare a vial with a boiling stone in it
18.) Determine the mass of the vial and boiling stone and
record in the data section of your lab report.
19.) Place the reweighed vial from step 18 underneath the
tip of the Pasteur pipette.
20.) Before adding your reaction mixture from step 12, add
~2-3 mL of methylene chloride to your pipette to wet
the silica gel completely.
a. This is step is crucial in separation.
21.) Once the column is wet add your reaction mixture to the pipette.
22.) Rinse the crude reaction vial with ~0.5mL of methylene chloride and add to the Pasteur
pipette.
23.) Let the solvent drain through the pipette until it reaches the top of the sodium sulfate bed,
then add ~1mL of methylene chloride to the pipette and let drain down to the sodium sulfate
layer.
24.) Next carefully boil off the solvent from the pre-weighed vial by heating to 75 oC.
25.) Once the vial has reached a constant mass, i.e. all the solvent is gone, calculate your percent
yield and record in the data section of your lab report.
26.) Allow your hot plate to cool to room temperature and return it to the stockroom.
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 as the last part of your lab report.

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.