University of Bahrain

College of science
Department of Chemistry

Experiment 03
Synthesis of Methyl Benzoate by
Fischer Esterification

Done by:
Fatima Ali Ebrahim – 20185895
Jenan Jaffer Safwan – 202002581
Noor Zubair Janahi – 202002768
Mahmood Mohamed Ahmed – 202004044
Instructor: Dr. Tariq Mahmood
Aim:
• To synthesize Methyl Benzoate by using Fischer esterification reaction.

• To calculate the percentage yield of methyl benzoate.

• To recognize the different fragrances that ester compounds produce from ester formation
reactions.

Introduction:
Esters, along with acid chlorides, acid anhydrides, and amides, belong to a class of compounds
frequently referred to as carboxylic acid derivatives. As a group, these compounds are important.
Acid chlorides and anhydrides, the most reactive of the group, are not found in nature but are
important tools in the synthesis of other compounds. Esters and amides, less reactive than the
other two, are the basis for many biologically important molecules. Many lipids are esters, while
polypeptides, or polyamides, provide the structural backbone for all proteins.
Esters are also important industrially as solvents, and, because they often have pleasant odors,
are important as synthetic flavoring agents and fragrances. “We will observe the pleasant smell
of the ester that we will prepare in today’s experiment”. Amides are also important commercially
in the pharmaceutical industry, while polyamides are important synthetic fibers.

The reactions that all acid derivatives undergo are nucleophilic acyl substitution reactions. For
acid chlorides and anhydrides, these substitution reactions are very rapid. For esters, the
reactions are slower, and for amides slowest of all. Carboxylic acids themselves also undergo
these substitution reactions, and the synthesis you will be doing in this experiment is the acid
catalyzed nucleophilic acyl substitution reaction of benzoic acid with methanol to produce the
ester, methyl benzoate.

C6H5COOH + CH3OH ⮀ C6H5COOCH3 + H2O

In this experiment, methyl benzoate was produced by Fisher esterification, which is the simplest and most
widely used industrial method. This method consists of adding concentrated sulfuric acid as a
homogeneous catalyst to a mixture of benzoic acid and methanol in excess quantities .

In the acid catalyzed nucleophilic acyl substitution mechanism. In it, the acid’s carbonyl group is
protonated to ease the addition of the weak nucleophile, methanol. Once the methanol has been
added to the carbonyl, proton transfer leads to an intermediate with a protonated hydroxyl group
which leaves to form a carbocation and water. Deprotonation of this carbocation yields the
methyl benzoate product. The two carbocations formed throughout this mechanism each have
extensive resonance stabilization.

Figure – 1 : benzoic acid and methanol reaction

Procedure:
1- 10 .0 g benzoic acid + 25 ml methanol and Cool the mixture in ice ( in one neck round bottom )
2- Add pour 3 ml of concentrated sulfuric acid
3- Reflux gently for 1hr
4- Transfer to separatory funnel containing 50 ml H2O
5- Add with 35 ml ether (Shake)
6- Drain off the water layer (contain sulfuric acid and methanol )
7- Shake with 25 ml of water and drain the lower aqueous layer
8- Add 25 ml of 0.5 M NaHCO3(to remove unreacted benzoic acid)
9- Test the aqueous lower layer acidity with red litmus
10- Add 25 ml of saturated NaCl and shake
11- Transfer the organic layer to a conical flask
12- Add CaCl2 to dry then removed by filtration
13- Wash drying agent with 5 ml of ether
14- Let the mixture air-dry
15- Perform TLC , IR and calculate % yield
16- Mix the following alcohols and carboxylic acid then observe the odor of ester products
a) Isopentyl alcohol + Acetic acid b) 1-propanol + Acetic acid
c) 1-octanol + Acetic Acid d) 1-propanol + Formic Acid

Results:

Figure – 2: TLC
sheet for standard
and extracted
methyl benzoate

Distance traveled by solvent: 4.6 cm.

Distance traveled by standard Methyl Benzoate : 4 cm
Distance traveled by extracted Methyl Benzoate : 4 cm
𝑅f = 𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑡𝑟𝑎𝑣𝑒𝑙𝑒𝑑 𝑏𝑦 𝑠𝑙𝑢𝑡𝑒/ 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑡𝑟𝑎𝑣𝑒𝑙𝑒𝑑 𝑏𝑦 𝑠𝑜𝑙𝑣𝑒𝑛
𝑅f 𝑜𝑓 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 Methyl Benzoate : 4 / 4.6 = 0.8695
𝑅f 𝑜𝑓 extracted Methyl Benzoate : 4 / 4.6 = 0.8695
 C6H5COOH + CH3OH ⮀ C6H5COOCH3 + H2O

MM of benzoic acid = 122.123 g/mol

Mass of benzoic acid = 10.0 g
MM of methyl benzoate = 136.150 g/mol.
Mass of beaker = 55.098 g
Mass of beaker with sample = 64.058 g
Experimental yield of Methyl Benzoate = 64.058 g - 55.098 g = 8.96 g
Moles of benzoic acid = Mass / MM = 10 / 122.123 =0.08188 mol
1 mol of benzoic acid → 1 mol of methyl benzoate
0.08188 mol of benzoic acid = 0.08188 mol of Methyl benzoate
Theoretical yield of methyl benzoate = 0.08188 mol × 136.150 g/mol = 11.14 g
% yield of methyl benzoate = experimental / theoretical x 100 = 8.96 / 11.14 = 80.43 %

Discussion :
Methyl benzoate is an organic ester with the chemical formula C6H5CO2CH3 . Methyl benzoate can be
synthesized in many ways, but Fischer's esterification is the simplest and most widely used industrial
method. This method consists of adding concentrated sulfuric acid as a homogeneous catalyst to a
mixture of benzoic acid and methanol in excess.
Here are some additional details about Methyl Benzoate :
• Methyl Benzoate is a colorless liquid and has a pleasant smell
•Methyl benzoate It is a very weak base, and an extremely weak acid.

Figure – 3 : structure methyl benzoate

:
The first step We prepared a mixture of benzoic acid and methanol, then cooled the mixture in ice
before adding concentrated sulfuric acid, then added the boiling chips. These tiny boiling chips are
highly porous rocks that release bubbles of air trapped in the solution being heated. These bubbles
provide a path through which the boiling foil vapor can be smoothly directed to the surface and
released. After placing the boiled chips, we perform the reflux involves heating the chemical reaction
for a specific amount of time, while continually cooling the vapor produced back into liquid form,
using a condenser.

Figure – 4 :
how to reflux
the mixture

The vapors produced above the reaction continually undergo condensation, returning to the flask as a
condensate and returned to the flask. Then we transfer it to the separating funnel, then add the ether,
shake it repeatedly, and release the pressure Then we Drain off the water layer containing sulfuric
acid and methanol. Then we put 25 ml of water, shake it, then drain the bottom layer of water. It is
important to use aqueous NaHCO3 because NaHCO3 will form a salt for the reaction, which is very
important.

We tested the bottom water layer by placing red litmus paper. Red litmus paper turns blue due to basic
or alkaline conditions. Then we add NaCl, helps to Shift the equilibrium towards ester Product.
position of equilibrium can be shifted by increasing the concentration of product, so removing water
by adding salts could help in shifting equilibrium toward forward direction and helps to salt out ester
making it more soluble in organic layer. .We used a drying agent to remove water and increase the
concentration, which disturbed the balance and increased production. We used calcium chloride in its
anhydrous form, which is an economical drying agent that is very important for laboratory drying
processes. For example: drying of neutral liquids and gases. It is also a very good drying agent for a
wide range of solvents. Drying agents are characterized by power, efficiency and speed. Capacity
refers to the maximum number of water molecules that drying agents can bind. It is highly soluble in
water and it is deliquescent. It is a salt that is solid at room temperature, and it behaves as a typical
ionic halide.
Next, we conducted four reactions to obtain the banana, pear, orange and raspberry smell
The first time we mixed isopentyl alcohol and acetic acid and got a banana smell
The second time we mixed 1-propanol and acetic acid and got a pear smell
The third time we mixed 1-octanol and acetic acid and got an orange smell
The fourth time we mixed 1-propanol and formic acid and got a raspberry smell
In Figure – 4 we will see mechanism for Methyl Benzoate

Figure – 5 :
mechanism
for Methyl
Benzoate

At this point the purity of the product wasn’t confirmed, so we did perform some tests as following:
Thin-layer chromatography (TLC):
an analytical technique often used to separate and identify compounds present in a given mixture .
TLC can be used to help determine the number of components in a mixture . By observing the
appearance of a product or the disappearance of a reactant, it can also be used to monitor the progress
of a reaction.
Compounds with the same Rf value will move up the TLC plate at the same speed, making it possible
to identify them in mixtures using their Rf values . One of the most significant mistakes we made
during TLC was adding extracted methyl benzoate at a very high concentration, which caused some
kind of tailing to the standard Methyl Benzoate spot. However, they all travelled to the same level,
and that is how the purity was confirmed .
 IR spectroscopy :
An IR spectrum is essentially a graph plotted with the infrared light absorbed on the Y-axis against.
frequency or wavenumber on the X-axis.
IR Spectroscopy detects frequencies of infrared light that are absorbed by a molecule. Molecules tend
to absorb these specific frequencies of light since they correspond to the frequency of the vibration of
bonds in the molecule.
By comparing to the IR spectrum of a pure sample of the desired compound, if the two spectra are
identical, then the sample is likely to be pure, however, if the two spectra are different, then the
sample is likely to be impure.
In this experiment, we did not measure infrared radiation, but if we measured it, this diagram would
appear to us as following :

Figure – 6: IR for methyl benzoate

the most important peaks that should be noticed are :

1- Aromatic C-H stretch : 3100-3000 cm-1 (weak)
2- Methyl C-H stretch : 2960 and 2870 cm-1 (medium)
3- Conjugated ester C=O stretch : 1730-1715 cm-1 (strong)
4- Aromatic C-C stretch : 600-1585 cm-1 (medium) and 1500-1400 cm-1 (medium)
5- Methyl C-H bend : 1380 cm-1 (weak) and 1260 cm-1 (medium)
6- C-O stretch : 1300-1000 cm-1 (strong)
7- Aromatic C-H 'out-of-plane' bend : 750-700 cm-1 (strong) and 710-690 cm-1 (medium)
Error sources:
The problem that occurs during reflux is a reflux temperature error that can quickly build up
pressure, leading to spillage and some sources of error that can occur are:
• leakage (loos chips)
• improper drying of product
• high concentrations of samples in TLC
Conclusion:
In this experiment, we synthesized methyl benzoate using Fisher esterification. A yield of 80.48% was
obtained, the resulting water was removed and the equilibrium shifted forward. The yield of benzoic acid
was 8.96 g. The return rate is high, which means the experiment was successful.

References :
1- Benzoic acid, methyl ester. Nist.gov. Published 2018. Accessed October 18, 2023.
https://webbook.nist.gov/cgi/cbook.cgi?ID=C93583&Type=IR-SPEC&Index=1

2- Swamy Arêa Maruyama; Lisboa, S.; Luiz Pereira Ramos; Wypych, F. Alkaline Earth
Layered Benzoates as Reusable Heterogeneous Catalysts for the Methyl Esterification of
Benzoic Acid. Química Nova 2012, 35 (8), 1510–1516. https://doi.org/10.1590/s0100-
40422012000800004.

3- “Chemistry Online @ UTSC,” Utoronto.ca, 2023.

https://www.utsc.utoronto.ca/webapps/chemistryonline/production/reflux.php#:~:text=Re
flux%20involves%20heating%20the%20chemical,the%20flask%20as%20a%20condensa
te (accessed Oct. 18, 2023).

4- University of Massachusetts Amherst, “Thin Layer Chromatography,” 2022. Available:

https://people.chem.umass.edu/samal/269/tlc.pdf

5- BYJU'S. What are drying agents- desiccating agents- and dehydrating agents- Explain
how they work- their nature- uses- and give examples for the same-. Byjus.com.
https://byjus.com/question-answer/what-are-drying-agents-desiccating-agents-and-
dehydrating-agents-explain-how-they-work-their-nature/ (accessed 2023-10-18).

6- Untitled Document [Internet]. Chem.ubc.ca. 2023 [cited 2023 Oct 18]. Available from:
https://groups.chem.ubc.ca/chem235/danalabsess/boiling_chip.html#:~:text=Many%20ex
periments%20will%20ask%20you,to%20the%20surface%20and%20released.

7- Experiment 6 Extraction: Separation of Benzoic Acid and Phenanthrene Study Questions

[Internet]. Available from: https://www.orgchemboulder.com/Labs/SQ/SQ-
Extraction.pdf
Question and answers
Ethyl salicylate has mint smell, ethyl butanoate has pineapple smell Write the equations for the
formation of these esters

1. +

salicylic acid + Ethanol ethyl salicylate

2. +

butanoic acid + Ethanol ethyl butanoate

Write few other reactions for the preparation of esters ?

1. +

benzyl alcohol + acetic acid benzyl acetate

2. +

heptanoic acid + Ethanol ethyl heptanoate

In this reaction, it is important to reduce the amount of water produced? Explain why? How
would you remove water from this reaction?
We used a drying agent to remove water and increase the concentration that make upset equilibrium
and higher yield. We used calcium chloride in its anhydrous form, an economical drying agent that is
very important for drying processes in laboratories. For example: drying liquids and neutral gases. It
is also a very good drying agent for a wide range of solvents.

What is refluxing?
Reflux involves heating the chemical reaction for a specific amount of time,
while continually cooling the vapor produced back into liquid form, using
a condenser. The vapors produced above the reaction continually undergo
condensation, returning to the flask as a condensate.

Write a detailed mechanism for this reaction?

Calculate the % yield of methyl benzoate. Show all steps

MM of benzoic acid = 122.123 g/mol

Mass of benzoic acid = 10.0 g
MM of methyl benzoate = 136.150 g/mol.
Mass of beaker = 55.098 g
Mass of beaker with sample = 64.058 g
Experimental yield of Methyl Benzoate = 64.058 g - 55.098 g = 8.96 g
Moles of benzoic acid = Mass / MM = 10 / 122.123 =0.08188 mol
1 mol of benzoic acid → 1 mol of methyl benzoate
0.08188 mol of benzoic acid = 0.08188 mol of Methyl benzoate
Theoretical yield of methyl benzoate = 0.08188 mol × 136.150 g/mol = 11.14 g
% yield of methyl benzoate = experimental / theoretical x 100 = 8.96 / 11.14 = 80.43 %