Lead Author: Lakshmi Subramani

Reviewer: Josh Purvis

Editor: Clara Wan
Fischer Esterification
Introduction:
There are multiple ways to synthesize esters, Fischer Esterification, named after the
German Chemist Emil Fischer, is one of those ways.1 Fischer Esterification is a reaction that
esterifies a carboxylic acid by heating it with an alcohol in the presence of an acid catalyst,
general reaction can be seen in Figure 1. Since the overall reaction is reversible, it is necessary to
continuously remove water, one of the products, or use a large excess of alcohol in the reaction
to drive it to completion.2
Figure 1: Fischer Esterification

Figure 1 shows a general reaction describing a Fischer Esterification

Once the reaction has been completed, the two products, the ester and water, along with
any remaining acid need to be separated and the ester isolated. Usually this can be accomplished
by using a weak base to draw any remaining acid into the aqueous base layer, which is easily

separated, through density, from the organic ester layer. 3 In this experiment, an unknown alcohol
is reacted with Acetic Acid and sulfuric acid is used as the catalyst.
Table 1: Table of Reagents
Name
M.W. (g/mol)
MP(C)
BP(C)
Density (g/mL)
Acetic Acid
60.05
16.0
118.0
1.05
Sulfuric Acid
48.08
337
10.00
1.84
NaHCO3
84.01
50.00
2.20
Na2SO4
142.1
884
1429
2.66
Table 1 shows the reagents used in this experiment and some of the properties associated with
each.
Procedure:
Before the prelab lecture, a 5mL round-bottom flask was obtained and 0.7mL of unknown
alcohol #461, 1.4mL glacial acetic acid, 3 drops of sulfuric acid, and a stir bar were placed
inside. Then a long glass tube was attached to the flask with a rubber joint to set up a reflux
apparatus. A piece of paper towel was soaked in ice water, wrung, and wrapped around the glass
tube to complete the reflux apparatus. A hot sand bath, sand, and one of those controller things
that controls percent of heat used idk the name were obtained and placed on top of a hot
plate/stirrer. The sand bath was heated using the controller and kept at around 30% heat. The
round-bottom flask was placed in the sand bath and held in place by a clamp. The stirrer was set
to setting 7, but the heat setting on the plate was not used. The only heat applied was that of the
sand bath. The solution was allowed to reflux for 90 minutes and the prelab lecture was
conducted.
After 90 minutes, the flask was removed from the stirrer and the heat so that the flask could
cool to room temperature. The condenser was removed and the mixture was transferred to a

conical test tube. Then, 1.0mL of NaHCO3 was added to the test tube and a spatula was used to
stir the solution until no more carbon dioxide bubbles were observed. The organic layer, on top,
was pipetted back into the round bottom flask and the aqueous layer, on bottom, was discarded.
The organic layer was then transferred back to the conical test tube and 1.0mL of NaHCO3 was
again added to the test tube. The new solution was stirred, again, until all of the carbon dioxide
bubbles disappeared. This time, the organic layer, on top, was transferred to a dry vial and
Na2SO4 was added to the vial to dry the solution. The aqueous layer, on bottom, was again
discarded. An NMR tube was prepared and three drops of the dry solution were added to the
tube; an NMR analysis was then conducted.
Experimental:
The following pictures are of the NMR results from the product obtained in the experiment.
Figure 2. Overall NMR Results of Product
Figure 2 shows the overall NMR results of the product, from 0-10ppm.
Figure 3. NMR Results of Product from 0.6-1.7ppm
Figure 3 shows a closer view of the 0.6-1.7ppm NMR results of the product obtained in the
experiment
Figure 4. NMR Results of Product from 1.7-4.2ppm
Figure 4. shows a closer view of the 0-4.2ppm NMR results of the product obtained in the
experiment

Figure 5. Carbon NMR Results of Product

Figure 5 shows the carbon NMR results of the product from 0-200ppm
Table 2. Significant Proton NMR Peaks
Chemical Shift (ppm)

Number of peaks

Integration

0.8-0.9

6.2042

1.4-1.5

1.9937

1.6-1.7 2

1.000

1.9-2.0

5.2202

2.1

7.4516

4.0-4.1 5

1.9985

Table 2 shows significant peaks in the products proton NMR, along with its chemical shift,
integration, and the number of peaks.

Figure 6. Molecular Structure of the Product Ester:

O

1
H3C
A

C
B

3
D

E
4

5
CH3
F

Discussion:
In this experiment, an ester was made from an unknown alcohol and acetic acid (the
aldehyde). Through, carbon and proton NMR analysis of the ester product, this unknown alcohol
needed to be determined from four choices: 1-propanol (which with acetic acid will yield propyl
acetate), 1-butanol (which with acetic acid will yield butyl acetate), isobutyl alcohol (which with
acetic acid will yield isobutyl acetate), 1-pentanol (which with acetic acid will yield n-amyl
acetate). The first step in doing so, was to analyze the carbon NMR. There are 6 distinct peaks
meaning there are 6 different carbon types in the ester molecule. This rules out 1-propanol,
which yields a 5 carbon ester, and 1-pentanol which yields a 7 carbon ester. This left the
unknown alcohol between two choices: 1-butanol and isobutyl alcohol.

Next, proton NMR had to be analyzed to distinguish between 1-butanol and isobutyl
alcohol. The NMR results had 6 distinct peaks- meaning 6 different type of hydrogens. However,
neither 1-butanol or isobutyl alcohol have 6 different hydrogens: 1-butanol has five hydrogen
types and isobutyl has four hydrogen types. So, further analysis was required. The easiest to pick
out, was Hydrogen Type 2 (shown on the molecule above). Its proximity to the oxygen
molecules give it a chemical shift around 4.0ppm. This peak on the NMR results had a splitting
pattern of 2 and an integration value of 2. This was proven true because Hydrogen Type 2 does
have 1 type of hydrogens (Hydrogen Type 3) next to it. Hydrogen Type 1 was also distinctive
because of its proximity to the carbonyl group. This hydrogen peak had a chemical shift of about
2.1 ppm, with a splitting pattern of 1 and integration of 7.4516. This holds true because
Hydrogen Type 1 does not have any hydrogen types next to it, causing a splitting pattern of one.
While there are not 7 hydrogens in the hydrogen type 1, it is false to interpret the integration
value this way because the integration value does not give the number of hydrogens but rather in
a ratio. So, this still holds true.
However, Hydrogen Types 1 and 2 would have been similar in both butyl acetate and
isobutyl acetate, so it is the remainder of the hydrogen splittings that need to be analyzed to
distinguish between the two esters and alcohols. Hydrogen Types 3 and 4, with their splitting
patterns, especially proved this. For example, Hydrogen Type 3 had a splitting pattern of 6 (since
there are 5 surrounding hydrogens) and an integration of 2 which closely resembles the peak at
1.6ppm. Hydrogen Type 4 had a splitting pattern of 5 (since there are 4 surrounding hydrogens)
and an integration of 2 which closely resembles the peak at 1.4. These two peaks indicate that the
ester was indeed, butyl acetate, meaning the unknown alcohol was 1-butanol.

There was some error to this experiment. The main example of this, was that there was an
extra peak in the NMR results. This could result from not having a pure product- having some
alcohol or acetic acid remaining in the product solution could have caused this extra peak to form
in the results. The best way to fix this, is to allow the solution to reflux for a longer time to
ensure that all the solution is reacted.

Conclusion:
Using carbon and proton NMR, the structure of the unknown alcohol was determined to
be 1-butanol. There were some extra peaks in the NMR results, which can be remedied next time
by allowing the reaction to reflux for a longer time.
Questions:
1. Write a detailed mechanism for Fischer Esterification
H

H+
H3C

OH

H3 C

OH

OH

+
H3 C

OH

HO

CH3

H3 C
H

OH
O

CH3

OH

H3C

H+
O

OH

CH3

OH2

O
OH

H3C

O
OH

CH3

H3 C

H2 O

H3 C

CH3

OH2

H3 C

OH
O

CH3

CH3

H3 C

CH3

H3 O

2. What is the IUPAC name of isoamyl alcohol? Of isoamyl acetate?

Isoamyl alcohol = 3-Methyl-1-butanol
Isoamyl acetate = 3-methylbutyl acetate
3. Write an equation for the Fischer preparation of
a. Benzyl isobutyrate
OH

OH
H3C

H+

CH3
O

b. Isobutyl benzoate
O

OH

H+

H3C

OH
CH3

CH3

O
CH3

Resources:
1. Brown, William; Iverson, Brent; Anslyn, Eric; Foote, Christopher. Organic Chemistry. 7th
Edition; Cengage Learning, 2011.
2. Farmer, Steven. Fischer Esterification. UCDavis ChemWiki.
http://chemwiki.ucdavis.edu/Core/Organic_Chemistry/Carboxylic_Acids/Reactivity_of_
Carboxylic_Acids/Fischer_esterification
3. Barbaro, John; Hill, Richard. Experiments in Organic Chemistry, 3rd Edition;
Contemporary Publishing Co. of Raleigh, Inc., 2005.