FACULTY OF APPLIED SCIENCES

LABORATORY REPORT

FUNDAMENTAL ORGANIC CHEMISTRY

(CHM 457)

Nitration of Methyl Benzoate (Electrophilic Aromatic

Title of Experiment Substitution)

No. Experiment 5
Nur Ain Najwa binti Edi Mohamad
Name of student
2022458464
Student ID

Programme code
AS253
Date of experiment is done
11 May 2023
18 May 2023
Date of lab report is submitted

Lecturer’s name
Pm Dr Mohd Tajudin Mohd Ali
1.0 Objective

- To determined the percentage yield of crude product

- To determine the melting point of methyl m-benzoate

2.0 Introduction

Benzene rings are components of many important natural products and other useful organic
compounds. Therefore, the ability to put substituents on a benzene ring, at spesific positions
relative to each other, is a very important factor in synthesizing many organic compounds.. The
two kain reaction types used for this are both substitutions. Electrophilic Aromatic Substitution
(EAS) and Nucleophilic Aromatic Substitution (NAS). The benzene ring itself is electron-rich,
which makes NAS difficult, unless there are a number of strongly electron withdrawing
substituents on the ring. EAS, on the other hand, is a very useful method for putting many
different susbtituents on a benzene ring, even if there are other substituents already present.
Organic Chemistry text describes the factors involved in the regioselectivity for EAS reactions
using benzene rings which already have substituents on them.

In this experiment, nitro group on a benzene which already has an ester group attached to
methyl benzoate. The actual electrophile in the reaction is the nitronium ion, which generated
in the reaction mixture using concentrated nitric acid and concentrated sulfuric acid.The figure
below shows the mechanism.

Figure 1: Mechanism of Electrophilic Aromatic Substitution

3.0 Procedure

6mL of concentrated sulfuric acid was added into 100mL beaker. The beaker was placed in the
ice bath for 5-10min. Weigh 3.05g of methyl benzoate and placed in the beaker that contain
6mL of concentrated sulfuric acid. Let the mixture rest. 2mL of concentrated sulfuric acid and
concentrated nitric acid was added in the test tube. Placed the test tube in the ice bath. Next, by
using pasteur pippete, drop slowly 𝐻2 𝑆𝑂4 /𝐻𝑁𝑂3 into the methyl bvenzoate mixture. Keep the
mixture in the ice bath to maintain temperature 5-20℃. After that, let the mixture warm in the
room temperature. Next, 25g of ice was crushed and placed in the beaker and pour the entire
mixture into the 25g of crushed iced. Make sure the ice is completely melt before start the
vacuum filtaration. After that start, vacuum filteration. The product was washed with 24mL
cold water and 10mL of cold methanol. After finish the filtaration, dry the product in the oven
and reweigh the product after drying process. Lastly, the melting point of the product was
determined using melting point apparatus.
4.0 Data and Result

The melting point of methy m-nitrobenzoate = 79℃

Mass of methyl benzoate = 3.0529g

Mass of methyl m-nitrobenzoate = 4.9779g

To calculate the theoretical yield of the product:

𝐶6 𝐻5 𝐶𝑂2 𝐶𝐻3 + 𝐻2 𝑁𝑂3 → 𝐶6 𝐻4 𝐶𝑂2 𝐶𝐻3 𝑁𝑂2 + 𝐻2 𝑂

136𝑔
Molar mass of 𝐶6 𝐻5 𝐶𝑂2 𝐶𝐻3 = 𝑚𝑜𝑙

𝑚𝑜𝑙
Mol of 𝐶6 𝐻5 𝐶𝑂2 𝐶𝐻3 = 3.05229𝑔 × 136𝑔 = 0.02244𝑚𝑜𝑙

1 𝑚𝑜𝑙𝐶6 𝐻5 𝐶𝑂2 𝐶𝐻3 → 1 𝑚𝑜𝑙 𝐶6 𝐻4 𝐶𝑂2 𝐶𝐻3 𝑁𝑂2

0.02244 𝑚𝑜𝑙𝐶6 𝐻5 𝐶𝑂2 𝐶𝐻3 → 0.02244 𝑚𝑜𝑙 𝐶6 𝐻4 𝐶𝑂2 𝐶𝐻3 𝑁𝑂2

181𝑔
Molar mass of 𝐶6 𝐻4 𝐶𝑂2 𝐶𝐻3 𝑁𝑂2 = 𝑚𝑜𝑙

181𝑔
Mass of 𝐶6 𝐻4 𝐶𝑂2 𝐶𝐻3 𝑁𝑂2 = 0.02244𝑚𝑜𝑙 × = 4.0616𝑔
𝑚𝑜𝑙

𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑦𝑖𝑒𝑙𝑑 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = × 100
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑

4.9779𝑔
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑦𝑖𝑒𝑙𝑑 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = × 100 = 122%
4.06164𝑔

5.0 Discussion

In the experiment, eletrophilic aromatic substitution has occur where the proton replace on
an aromatic ring with an nucleophile and form a new substitution. Sulphuric acid react as
solvent in the reaction which protonates the methyl benzoate and creating resonance stabilized
arenium ion. The protoanated react with electron deficient and form meta position. The ester
group take place at the meta position because the ortho and para position are not stable. So the
product produce is meta product because nitro groups is powerful electron withdrawing groups.

From the experiment, the actual product produce is 4.9779g and the melting point of the
product is 79℃. The theoretical value of the product is 4.06164g and the percentage value of
the product is 122%.
6.0 Conclusion

In conclusion, the percentage yield of the crude is 122%, the actual yield produce is 4.979g
and the theoretical value is 4.0616g. The melting point of the product is 79℃, so it is in the
range of methyl m-nitrobenzoate.

7.0 Question

1. Why is methyl m-nitrobenzoate formed in this reaction instead of the ortho or para
isomers? What is the melting point of the ortho and para isomers.

The reaction formed in methyl m-benzoate is rather ortho or para isomers because ester is
a electron withdrawing group which cause nitrobenzene became meta position.

2. Draw the structure of the products formed on nitration of each of the following
compunds: benzene, toluene, chlorobenzene, and benzoic acid.
3. Write the full mechanism for the nitration of methyl benzoate.

8.0 Reference
1. https://studylib.net/doc/8106187/nitration-of-methyl-benzoate
2. http://www.chemspider.com/Chemical-Structure.62472.html
3. https://edu.rsc.org/resources/nitration-of-methyl-
benzoate/2323.article#:~:text=Nitration%20is%20the%20substitution%20of,produces%2
0predominantly%20methyl%203%2Dnitrobenzoate.