Synthesis of Methyl butyrate

Patricia Isabel Javison, Alliah Khan, Jose Marie Lazaga, and Marie Patrice Leh
College of Science, University of Santo Tomas, Manila, Philippines

Abstract
Methyl butyrate was synthesized via an acid-catalyzed Fischer esterification reaction
from butyric acid and methanol. The distillate collected at 84.9 °C was a clear colorless liquid
with a percent yield of 46.17%. The product was characterized through Infrared Spectroscopy
which showed significant peaks of the functional groups at 1741 cm-1, 2970 cm-1 and 2879 cm-
1.

Introduction
Methyl butyrate (C5H10O2), or also known as methyl butanoate is the methyl ester of
butyric acid which appears to have a clear colorless liquid at room temperature and has a sweet
and fruity odor that resembles of the apple and pineapple (Lewis, 1997). It is a fatty acid methyl
ester as it contains a fatty acid that is esterified with a methyl group and has a boiling point of
102 Celsius, a melting point of -95 °C and has a density of 0.898 gm/cm3 (Wishart DS, 2018).
Methyl butyrate has low solubility in water that allows it to float to form an oily layer. Although
it is flammable, it has a low vapor pressure, particularly 40 mmHg at 30 °C, this is why special
safety precautions are no longer needed.

Methyl butyrate is mostly used in the manufacturing of flavors, pesticides, adhesives,

pharmaceuticals, plasticizers, solvents of paints, as well as polymerization monomers. It may
also be used as an emulsifier in the food and cosmetic industries. It is present in small amounts
of several plant products, especially pineapple oil. It can be produced through the distillation
of essential oils which is extracted from various plants, but it may also be manufactured on
small scale for the use of perfumes and as food flavoring (Manpreet Kaur, 2019). Methyl
butyrate was suspected to be a potential surrogate for biodiesel. Unfortunately, a variety of
studies shows that methyl butyrate is not suitable as a surrogate for biodiesel (Huynh &
Violi,2007)

Figure 1. Methyl Butyrate Synthesis

Methyl butyrate is synthesized through the use of the esterification of butyric acid with
methanol (Figure 1) (Adhikari, 2019). Fisher esterification method is used to mimic the taste
and scent of methyl butyrate. It is the condensation reaction of an alcohol with a carboxylic
acid and is catalyzed with sulfuric acid, to generate an ester that tastes and smells like the
natural compound. (Massachusetts Institute of Technology, n.d.).

The Fischer esterification is an equilibrium process. Energetically, the products have

nearly identical stability to the starting material and there is no significant driving force for the
reaction. To shift the equilibrium to favor the production of esters, an excess of carboxylic acid
or alcohol. For this experiment, an excess of butyric acid is used because it is easier to remove
than alcohol. Another method is selectively distill away the desired product as it is formed
(West Virginia University,n.d.). Sulfuric acid is used as a catalyst as it can help speed up the
reaction rate and may also act as a dehydrating agent.

Figure 2. Mechanism of the Acid Catalyzed Fischer Esterification

The figure 2 shows the mechanism of the synthesis of methyl butyrate. First, protonation
of carbonyl oxygen lowers the carbonyl π for the addition of methanol. Within the tetrahedral
intermediate, the proton transfer occurs to generate water as the leaving group. Reformation of
the carbonyl π bond by elimination of water generates the protonated ester. Loss of the proton
then regenerates the acid catalyst and provides the product ester in a reaction that is called a
nucleophilic acyl substitution reaction (Boston University,2012).

The experiment used in module five to synthesize the ester compound methyl butyrate
using the Fischer Esterification Method. It also aims to characterize the product using the
Infrared Spectroscopy as an analytical technique.
Results and Discussion
Table 1. Reflux data

Time Temperature
(hot plate)

10:33 am 540 Celsius

10:43 am 55 Celsius

10:45 am 60 Celsius

10:56 am 85 Celsius

10:59 am 100 Celsius

11:01 am 350 Celsius

11:11 am 400 Celsius

11:15 am 425 Celsius

11:29 am 265 Celsius

11:31 am 180 Celsius

11: 33 am 180 Celsius

Table 2. Distillation data

Time Temperature (thermometer)

10:24 am 24 Celsius Start Distillation

10:29 am 24.8 Celsius

10:34 am 27.3 Celsius

10:36 am 43.6 Celsius 1st Drop of Distillate

10:39 am 57.4 Celsius

10:44 am 84.9 Celsius End Distillation

With organic compounds having relatively simple molecular structures and low boiling
points, it is quite volatile and if heat is applied, it would risk evaporating parts of the compound.
Reflux setup was used to administer this experiment, to be able to heat the mixture without
losing significant volume. The reflux had a duration of 60 minutes in total and began with a
temperature of 540 °C using a heating apparatus. Distillation process separates components of
a mixture based on different boiling points. The duration of distillation occurred within a span
of 20 minutes. The first drop of distillate was observed 12 minutes into the process with a
temperature of 43.6°C and ended 8 minutes subsequently with a temperature of 84.9°C. The
distillation process did not reach the boiling point of the product which was 102 °C.

Table 3. Methanol Data

Volume 30.0 mL

Mass 23.73 g

Density 0.791 g/mL

Molar Mass 32.042 g/mol

Table 4. Butyric acid Data

Volume 40.0 mL

Mass 38.56 g

Density 0.964 g/mL

Molar Mass 88.11 g/mol

Table 5. Experimental Data

Amount of 4.0332 g
Na2SO4

Erlenmeyer 40.2265 g
Flask (50 mL)

Erlenmeyer with 60.8622 g

product

Mass of product 20.6357 g

(Methyl
butyrate)

Density of 0.898 g/mL

Methyl butyrate

Molar Mass of 102.13 g/mol

Methyl butyrate

In the experiment, 40 mL of 5% Sodium bicarbonate was first added twice in the

separated organic layer to remove the remaining acid from the catalyst. After the two
extraction, the litmus paper testing showed that the reaction mixture was still acidic. Another
two 40 mL of 5% Sodium bicarbonate was added and the litmus paper testing resulted to a
basic product. A litmus paper was used to determine whether it was basic or acidic. The organic
layer was also exposed to a drying agent which was Na2SO4. This drying agent removed the
possible excess water in the organic layer.

In this experiment, the 40 mL butyric acid is the limiting reagent with 0.4376 moles as
compared to 30 mL methanol with 0.7406 moles. The limiting reagent would be the basis in
calculating the percent yield of the experiment. After the distillation process, 20.6357 g of
methyl butyrate product was collected. With the actual and theoretical yield, the calculated
percent yield was 46.17%. The percent yield of the product could have been affected by
numerous factors such as inaccurate measurement of the reactants and improper separation of
organic layer.
Figure 3. IR Spectra of Methyl butyrate
Figure 4. IR Spectra of Product

The figure 3 shows the IR spectra of Methyl butyrate. This IR spectra contains the peaks
that correspond to functional groups or different stretches present in the compound. The figure
4 is an IR spectra of the formed Methyl butyrate product from the experiment. The two IR
spectra shows evident similarities of important peaks that is essential in the determination of
the product. One of the important peaks is the carbonyl stretching which should be evident at
1742 cm-1. The product showed this significant stretch at 1741 cm-1 which can be seen in figure
4. The C-H stretches could be present at around 2987 cm-1 to 2846 cm-1. The product showed
a C-H stretch at 2970 cm-1 and 2879 cm-1.

In conclusion, the experiment was a success and the correct product was produced
which was confirmed by the IR spectra. However, there are certain areas or procedures where
the results could have been affected. The possible errors of the experiment are the inaccurate
measurements of the reactants, the loss of the organic layers during separation and the
contamination of the product which led to the percent yield of 46.17%.

Experimental
The reflux set-up used a 250 mL round bottom flask, condenser, and electric heating
mantle. In a 250 mL round bottom flask, a funnel was used to add 40 mL Butyric acid followed
by 30 mL Methanol. The flask was gently swirled to mix the added carboxylic acid and alcohol.
Using a dropper, 3 mL of concentrated sulfuric acid was added while gently swirling the flask.
A magnetic stir bar was placed in the flask, then it was attached to the lightly greased reflux
condenser. The heating mantel will boil and reflux the solution for 1 hour. The reaction solution
was then transferred to a 250 mL separatory funnel then 60 mL of cold distilled water was
added. Another 20 mL of water was added to rinse the reaction from the flask and was then
added to the separatory funnel. The solution was swirled to separate the layers and remove the
aqueous layer after that the organic layer was poured into a 500 mL beaker. About 40 mL of
5% sodium bicarbonate was slowly added while stirring the reaction mixture. Once the fizzing
reaction subsides, the reaction mixture was transferred back to the separatory funnel. With the
second extraction of 40 mL 5% sodium bicarbonate, the extraction was tested using litmus
paper. The result should indicate that it is basic. The top organic layer was poured into a 125
mL Erlenmeyer flask. 4 grams of Na2SO4 was added and was gently swirled into a flask. After
this, the liquid was clear. The organic layer was decanted into a scintillation vial.

The ester was poured into a 250 mL distilling flask and a magnetic stir bar was then
added. The distillate was collected into a test tube that is immersed in a beaker filled with ice.
It was then placed into a heating apparatus and the temperature was monitored. After 10-15
drops of distillate on the first test tube, the second part of the distillate was collected onto a
separate test tube. Once the distillation was completed, the apparatus was cooled down.

The product will be analysed using Infrared Spectroscopy through determining the
functional groups and peaks present in the Infrared Spectra. The IR spectra of the product from
the experiment would be compared to the theoretical IR spectra of the desired product which
is Methyl butyrate.

References
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