_________________________________________________________

Experiment # 5: Synthesis and Identification of an Unknown

Acetate Ester.
__________________________________________________________
Pre-Lab Mohrig Readings (Techniques): (1) pp.143-145 (Micro-Scale
Extraction); (2) 88 (Refluxing); (3) 176-188 (Simple Distillation); (4) 163-173
(Drying); (5) 291-307 (Gas Chromatography); (6) 350-405, 408-435 (NMR).

Experimental Objectives
The purpose of this experiment is to provide a practical example of the synthesis of
an unknown acetate ester. The product will be purified by distillation and assessed
by boiling point, gas chromatography (GC) and H-1 / C-13 NMR. Each student
group will be assigned to synthesize, isolate, and identify a specific acetate ester.
To accomplish this, they will be given acetic acid and an unknown alcohol. The
alcohol will be one of the following: ethanol, 1-propanol, 2-propanol, 1-butanol, 2butanol.

Introduction
Esters are derivatives of carboxylic acids, and are mainly prepared by one of four
methods:
1. Direct esterification of a carboxylic acid with an alcohol (Fischer esterification).
2. Alcoholysis of acid chlorides, or nitriles.
3. Reaction of a carboxylic acid salt with an alkyl halide or sulfate.
4. Via the trans-esterification reaction.
For this experiment, we will employ the Fischer esterification method. In this
reaction, esters are prepared by the reversible, acid-catalyzed combination of a
carboxylic acid with an alcohol. Because it is reversible, the reaction must be
shifted to the product side by using excess reagent, or removing one of the
products. This reaction is also limited by any steric hindrance in the carboxylic
acid or the alcohol. To maximize product yield, a large excess of one of the
reactants is often used. The acetic acid used in this experiment has a strong

dehydrating capability and helps soak up the reaction water, thus assisting in
pulling the reaction to the right (ie., Le Chateliers Principle). For this reason, an
excess of acetic acid will be used.

Safety Precautions
Diethyl Ether: highly flammable; avoid inhalation of vapors (anesthetic
effect).
Concentrated Sulfuric Acid: highly corrosive; avoid contact with skin and
other organic materials.
Glacial Acetic Acid: both liquid and vapor are skin and eye irritants and can
cause burns; flammable.
Alcohols: all are toxic if ingested; vapors are harmful to eyes, lings and
skin; highly flammable.
Sodium Bicarbonate: slightly basic but does not pose any specific safety
problems.
Saturated Sodium Chloride: an irritant and hygroscopic.
Sodium Sulfate: an irritant and hygroscopic.

Procedure: Week 1
1. Ester Synthesis.
Set up a reflux apparatus using a 100-mL round-bottom flask. A model of
this set-up is shown in the lab.
Add to the flask the following materials: two boiling stones, 30 mL glacial
acetic acid, and 10 mL of the unknown alcohol (this is provided in a glass
vial having an unknown number on the label; please record this number in
your laboratory notebook). Finally, slowly add 5 drops of concentrated
sulfuric acid. Gently swirl the contents of the flask for ~ 5 seconds to ensure
proper mixing.
Connect the flask to the reflux apparatus and heat the reaction mixture at
reflux for one hour. During this period, collect the materials (glassware and
reagents) needed for the remainder of this experiment.

2. Ester Isolation and Purification.

Remove the heating mantle and cool the reaction mixture to room
temperature. Notes: (1) You may speed the cooling up by placing the
stoppered flask into a cold tapwater bath for 5-7 minutes; (2) For the
following two steps, chill ~25 mL each of distilled water and saturated
NaCl.
Pour the cooled mixture into a separatory funnel containing 15 mL of cold
saturated NaCl. Rinse the flask with a further 5 mL of cold saturated NaCl
and also add this to the separatory funnel. Stopper the funnel and invert it
several times to provide proper mixing. This will ensure quantitative transfer
of the crude ester into the ether during the next step.
Add 25 mL of diethyl ether to the mixture and extract it using the method
demonstrated by the instructor. Allow the layers to separate. Drain the lower
aqueous layer into a 250-mL beaker. Keep the upper ether layer in the funnel
for the next extraction step.
Extract the ether with 20 mL of cold distilled water. The purpose of this step
is to remove the water-soluble neutral impurities. Drain the lower aqueous
layer into the same beaker holding the previous aqueous layer. Transfer the
ether layer to a clean 250-mL beaker. This is done to avoid the hazardous
excessive pressure build-up inside the separatory funnel during the following
step.
Add 20 mL of 5% sodium carbonate to the ether. Mix for 30 seconds or until
gas bubbles no longer evolve. Transfer the mixture back into the separatory
funnel and allow the layers to completely separate. Drain the lower aqueous
layer into the same beaker holding the previous aqueous layers.
Extract the ether layer with 20 mL of cold saturated sodium chloride. Drain
the lower aqueous layer into the beaker. At this time, check the pH of the
aqueous solution. It should be close to 7.0. If so, estimate and record the
volume on a waste slip and discard the solution down the sink.
Pour the ether layer from the separatory funnel into a 50-mL Erlenmeyer
flask containing enough anhydrous sodium sulfate to just cover the bottom.
Stopper and swirl the flask periodically for ~ 3 minutes. If the solid clumps
(becomes cakey), add more of the drying agent so that some of it is still
freely moving in the liquid (snowflake effect).
When the ether layer is dry, it should be clear and transparent; cloudiness at
this point indicates that water is still present. Carefully decant the liquid into
a clean 50-mL round bottom flask containing two boiling stones. Set-up a
simple distillation apparatus (a model of this is shown in the lab). Distill the

crude ester, collecting first any fraction that distills before 600C (this should
be the ether) in a 30-mLbeaker.The actual ester is then collected in a premassed vial. Note: Depending on the volume (yield) of the ester, you may
need more than one vial for collection. Note and record the temperature
range at which the ester is collected, noting that the final distillation
temperature reading is closest to the actual boiling point of the ester. Apply
the boiling point correction to this temperature as noted below. Seal the vial
with a plastic cap and place in storage for next week (Week 2).
Waste Disposal:
The volume of the final aqueous extracts must be estimated and recorded on
the waste slip before disposal down the sink.
The glass vial containing the unknown alcohol must be rinsed with acetone.
This volume is measured and recorded on the waste slip. The acetone is
poured into the hazardous waste container. The glass vial is placed in the
glass waste receptacle.
Both round-bottom flasks (reflux / distillation) must be rinsed with acetone
to remove traces of organic residue. Measure and record the acetone volume
on the waste slip. Place the acetone in the hazardous waste container.
Procedure: Week 2
1. GC Assay.
The isolated ester will be qualitatively analyzed by GC. As done for Lab 2, a
1-ul sample of the pure liquid (along with 1 uL of air) is injected on the GC
column.
Upon completion of the GC run, determine the retention time of the ester
peak and match this value with the retention times posted near the
instrument that you used. Note: there will likely be a small peak
corresponding to an ether residue that may have stayed in the liquid after the
distillation. This peak should likely appear around 1.5-1.8 minutes. There
also may be another peak corresponding to the presence of unreacted
alcohol. Retention times for any alcohol will be posted near the GC.
Upon completion of the GC assay, show the product to your instructor and
prepare it for proper disposal. Save the GC print-out (obtain one for each
member of the group) for labeling and submission with your report.

 At this point, you have a tentative identification of your unknown ester (and
the corresponding alcohol). You can now proceed to calculate the following
data in your laboratory notebook for submission in your report: theoretical
yield of ester, % yield of ester.
2. NMR Assay.
Once you have completed the GC assay of your unknown and have
tentatively identified it with your instructor, you will be provided a copy of
the H-1 and the C-13 NMR spectra of the ester.
Complete the required spectral information on the report sheet and include
the labeled structures (see the examples for H-1 and C-13 labeling shown in
Lab 6) on each spectra sheet.
3. IR Assay. Obtain an IR of your unknown ester. Label the characteristic peaks
and submit the spectrum with your report.
Waste Disposal
Record the mass of ester on the waste slip and dispose it in the hazardous
waste container.
Rinse the glass vial with acetone, measure and record the volume, and
dispose in the above waste container. The glass vial is disposed in the waste
glass receptacle.
Report
Complete and submit the report sheet. Attach the following to the sheet: labeled
GC print-out; labeled IR; H-1 and C-13 NMR spectra sheets.